JP6065596B2 - Radiation-sensitive coloring composition, colored cured film, and display element - Google Patents

Description

  The present invention relates to a radiation-sensitive colored composition, a colored cured film, and a display element. More specifically, the present invention is used for a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, and the like. The present invention relates to a radiation-sensitive colored composition used for forming a colored cured film, a colored cured film formed using the colored composition, and a display device including the colored cured film.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. A method of obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development is known (for example, see Patent Documents 1 and 2). In addition, a method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (for example, see Patent Document 4).

In recent years, display devices have been required to have a larger screen, higher brightness, thinner thickness, and the like. For this reason, even for colored resin compositions used to form pixels, black matrixes, etc. that make up display elements, high sensitivity and high brightness are also taken into account in terms of reduction in process time and cost reduction. Higher resolution is required.
Further, in the production of a color filter, since a high temperature process generally exceeding 200 ° C. is performed, the color filter is required to have high heat resistance. Thus, the colored resin composition is required to satisfy a plurality of characteristics at a high level.

Under such circumstances, the use of an oxime ester photopolymerization initiator has been studied as a measure for increasing the sensitivity of the radiation-sensitive resin composition (see, for example, Patent Documents 5 to 7). However, even with such a photopolymerization initiator, it has been difficult to achieve a plurality of characteristics such as sensitivity, luminance, resolution, heat resistance and the like at a high level. Further, when a cured film is formed using such a conventional photopolymerization initiator, the cured film may be slightly yellowed, so that it may be difficult to apply depending on the display element.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A Japanese Patent Laid-Open No. 2005-62494 JP 2005-215378 A JP 2006-36750 A

  Therefore, the subject of this invention is providing the coloring composition suitable for formation of the colored cured film which can make compatible several characteristics, such as a sensitivity, a brightness | luminance, a resolution, and heat resistance, on a high level. Furthermore, the subject of this invention is providing the display element which comprises the colored cured film formed using the said coloring composition.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by using a photopolymerization initiator having a specific structure.

  That is, the present invention is a radiation-sensitive colored composition containing (A) a colorant, (B) a binder resin, (C) a polymerizable compound, and (D) a photopolymerization initiator, The polymerization initiator contains at least one selected from the compound represented by the following formula (1) and the compound represented by the formula (2) (hereinafter also referred to as “specific compound”). The present invention provides a radiation coloring composition (hereinafter also simply referred to as “coloring composition”).

[In Formula (1),
R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. An alkyl group, or R ¹ and R ² are bonded to each other to represent a fluorene group;
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 4 to 20 carbon atoms. A heterocyclic group,
X represents a direct bond or a carbonyl group. ]

[In Formula (2),
R ^{1, R} 2, ^{R 3} and ^{R 4} have the same meanings as ^{R 1,} R 2, ^{R 3} and ^{R 4} in Formula (1),
R ⁵ is —R ⁶ , —OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , —OCSR ⁶ , —COSR ⁶ , -CSOR ⁶ , -CN, halogen, hydroxyl group,
R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms,
X represents a direct bond or a carbonyl group,
a represents an integer of 0 to 4. ]

  Moreover, this invention provides the display element which comprises the colored cured film formed using the said coloring composition, and this colored cured film. Here, the “colored cured film” means each color pixel, black matrix, black spacer, and the like used for a display element and a solid-state imaging element.

If the colored composition of this invention is used, the colored cured film which makes compatible several characteristics, such as a sensitivity, a brightness | luminance, resolution | decomposability, heat resistance, at a high level can be formed.
Therefore, the colored composition of the present invention can be used very suitably for the production of solid-state imaging devices such as color liquid crystal display devices, organic EL display devices, display devices such as electronic paper, and CMOS image sensors.

The spectrum distribution map of the light source of Type 1. The spectrum distribution map of the light source of Type 2. The spectrum distribution map of the light source of Type 3. The spectrum distribution map of the light source of Type 4.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described in detail components of the colored composition of the present invention.

-(A) Colorant-
The (A) colorant in the present invention can be used without any particular limitation, and the color and material can be appropriately selected according to the use such as a color filter. Specific examples of the colorant include pigments, dyes, and natural pigments, and these can be used alone or in combination of two or more. When the colored composition of the present invention is used for forming each color pixel constituting the color filter, the colorant is at least selected from the group consisting of a pigment and a dye from the viewpoint of obtaining a pixel having high luminance, contrast and color purity. 1 type is preferable and especially at least 1 sort (s) chosen from the group which consists of an organic pigment, an inorganic pigment, and organic dye is preferable.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) numbers. Can be mentioned.

C. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 254, C.I. I. Red pigments such as CI Pigment Red 264;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Green pigments such as CI Pigment Green 58;
C. I. Pigment blue 15: 6, C.I. I. Pigment blue 16, C.I. I. Blue pigments such as CI Pigment Blue 80;
C. I. Pigment yellow 83, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 179, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 211, C.I. I. Yellow pigments such as CI Pigment Yellow 215;
C. I. Orange pigments such as CI Pigment Orange 38;
C. I. Purple pigment such as CI Pigment Violet 23.

  In the present invention, a “rake pigment” in which a soluble dye is used as an insoluble pigment by a precipitant can also be preferably used as an organic pigment. Examples of the precipitating agent for rake formation include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, katanol, tamol, isopolyacid, heteropolyacid, and the like. Examples of the isopolyacid include isopolytungstic acid, isopolyvanadic acid, and isopolymolybdic acid. Examples of the heteropolyacid include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, and the like. , Silicotungstic molybdic acid, silicotungstic acid, silicomolybdic acid, and the like. Of these, lake pigments that have been laked using isopolyacid or heteropolyacid as a precipitating agent are preferred, and lake pigments that have been laked using heteropolyacid as a precipitating agent are particularly preferred. The lake pigments that have been raked using isopolyacid or heteropolyacid as a precipitating agent can be produced, for example, by the method described in JP-A-2011-186043.

  In the present invention, the lake pigment is not particularly limited. For example, in addition to xanthene lake pigment, triarylmethane lake pigment, azo lake pigment, phthalocyanine lake pigment, JP-A-2001-081348. JP 2010-026334 A, JP 2010-191304 A, JP 2010-237384 A, JP 2010-237369 A, JP 2011-006602 A, JP 2011-145346 A, etc. Mention may be made of the described lake pigments. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination.

  As the organic dye, any of acidic dyes, basic dyes and nonionic dyes can be suitably used. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination. Here, in this specification, an acidic dye means an ionic dye having an anion portion as a chromophore, and an ionic dye forming an inner salt is also included in the acidic dye. In this specification, the basic dye refers to an ionic dye having a cation moiety as a chromophore. The “nonionic dye” is a dye that does not correspond to any of the aforementioned acidic dye and basic dye.

  Examples of the acid dye include azo acid dyes, triarylmethane acid dyes, anthraquinone acid dyes, xanthene acid dyes, quinoline acid dyes, nitro acid dyes, and cyanine acid dyes. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination.

As such an acid dye, for example,
C. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Moldant Black 7, C.I. I. Azo acid dyes such as Direct Green 28;
C. I. Triarylmethane acid dyes such as Acid Blue 9;
C. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Anthraquinone acid dyes such as Reactive Blue 49;
C. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. In addition to Acid Red 388, Xanthene acid dyes disclosed in Synthesis Examples 1 to 3 of JP 2010-32999 A and JP 2011-138094 A;
C. I. Quinoline acid dyes such as Acid Yellow 3;
C. I. Acid Yellow 1, C.I. I. Nitro acid dyes such as Acid Orange 3;
C. I. Examples include cyanine acid dyes such as Reactive Yellow 1.

  Examples of the basic dye include azo-based basic dyes, triarylmethane-based basic dyes, xanthene-based basic dyes, quinoneimine-based basic dyes, and cyanine-based basic dyes. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination.

Examples of such basic dyes include:
C. I. Basic Blue 41, C.I. I. In addition to the basic red 18, an azo basic dye described in JP2011-145540A;
C. I. In addition to Basic Blue 7, triarylmethane basic dyes described in International Publication No. 10/123071, pamphlet, JP-A 2011-116803, JP-A 2011-117995, and JP-A 2011-133844;
C. I. Xanthene-based basic dyes such as Basic Violet 11;
C. I. Basic Blue 3, C.I. I. Quinone imine basic dyes such as Basic Blue 9;
C. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Basic Red 14, C.I. I. Basic Violet 7, C.I. I. Basic Violet 16, C.I. I. Basic Yellow 1, C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 13, C.I. I. Basic Yellow 21, C.I. I. Basic Yellow 28, C.I. I. Cyanine basic dyes such as Basic Yellow 51;
In addition, various basic dyes described in JP-T-2007-503477 can be exemplified.

  Examples of nonionic dyes include azo nonionic dyes, anthraquinone nonionic dyes, phthalocyanine nonionic dyes, quinoline nonionic dyes, nitro nonionic dyes, and methine nonionic dyes. Etc. These can be used alone or in combination of two or more, and can be arbitrarily combined when two or more are used in combination.

  In the present invention, these dyes can be appropriately selected and used, among which acidic dyes and basic dyes are preferable. In view of the structure of the chromophore, triarylmethane dyes, xanthene dyes, azo dyes, methine dyes, and cyanine dyes are preferable. Among these, xanthene acid dyes, triarylmethane acid dyes, triarylmethane basic dyes, and cyanine basic dyes are particularly preferable.

When the coloring composition of the present invention is a radiation-sensitive black composition used for forming a black matrix, a black spacer, etc., the coloring agent includes a coloring agent containing a black coloring agent, and a coloring agent containing a red pigment and a blue pigment. Is preferred.
Examples of black colorants include C.I. I. Pigment black 1, C.I. I. Pigment black 7, carbon black, titanium black, perylene-based black pigment, and the like can be mentioned, and these can be used alone or in combination of two or more. Of these, carbon black and perylene-based black pigment are preferable because they can form a cured film having high light-shielding properties and heat resistance, and carbon black is particularly preferable.
Moreover, among the colorants containing a red pigment and a blue pigment, a colorant containing a red pigment, a blue pigment and a yellow pigment, and a colorant containing a red pigment, a blue pigment and a green pigment are more preferable.

The primary particle size of the carbon black is preferably 20 to 60 nm, and more preferably 30 to 45 nm. By setting it as such an aspect, the highly sensitive and dispersible radiation sensitive coloring composition can be obtained, and the cured film which shows a uniform OD value (optical density) can be formed. The OD value in the present invention is defined by the method described later.

  The dispersed particle diameter of carbon black is preferably 100 to 250 nm, more preferably 150 to 200 nm, and still more preferably 170 nm to 200 nm. By setting it as such an aspect, the highly sensitive and dispersible radiation sensitive coloring composition can be obtained, and the cured film which shows a uniform OD value can be formed.

  In the present invention, when a pigment is used as a colorant, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface 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. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after the primary particles are refined by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  In the present invention, when a pigment is used as a colorant, a known dispersant and dispersion aid can be further added. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. A dispersant, a polyester-based dispersant, an acrylic-based dispersant and the like, and examples of the dispersion aid include a pigment derivative and the like.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) ), And as a urethane-based dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (manufactured by BYK Corporation (BYK) 76) Lubrizol Co., Ltd.), polyethyleneimine dispersant, Solsperse 24000 (Lubrisol Co., Ltd.), polyester dispersant And, Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like.

  In addition, JP2009-294665, JP2009-222761, JP2009-222762, JP2006-058601, JP2008-298967, JP2003-315998, The dispersants described in JP-A-2006-259351, JP-A-2008-039952, JP-A-2009-237466, JP-A-10-300919, JP-A-10-213898 and the like can also be used. .

  Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.

  (A) The content ratio of the colorant is usually 5 in the solid content of the colored composition from the viewpoint of forming a pixel having high heat resistance and high brightness and excellent color purity, or a black matrix and black spacer excellent in light shielding properties. It is -70 mass%, Preferably it is 5-60 mass%. The coloring composition of the present invention is excellent in developability even when the colorant concentration is high, and has an effect that a colored cured film can be formed with a high product yield. The solid content can be 30% by mass or more, further 35% by mass or more, and particularly 40% by mass or more. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
Although it does not specifically limit as binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itacone Acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or anhydrides thereof; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as acryloyloxyethyl]; having carboxy groups and hydroxyl groups at both ends such as ω-carboxypolycaprolactone mono (meth) acrylate Polymer mono (meth) acrylate; p-vinylbenzoic acid and the like can be mentioned.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as an unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 -10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
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 (b2) can be used alone or in admixture of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.
The copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) can be produced by a known method. For example, JP 2003-222717 A, JP 2006-259680 A The structure, Mw, and Mw / Mn can also be controlled by the method disclosed in the gazette, International Publication No. 07/029871 pamphlet and the like.

  In the present invention, a resin having a polymerizable unsaturated bond such as a (meth) acryloyl group and a carboxy group in the side chain can also be used as a binder resin. Such an embodiment is preferable in that a highly sensitive coloring composition can be obtained and the curability of the coating film can be increased.

As a binder resin having a polymerizable unsaturated bond and a carboxy group in such a side chain, for example,
(B3) A copolymer of a monomer containing a polymerizable unsaturated compound having a hydroxyl group and (b5) an unsaturated carboxylic acid (hereinafter sometimes referred to as “precursor copolymer (1)”). (B4) A resin obtained by reacting an unsaturated isocyanate compound (hereinafter also referred to as “resin (B1)”),
(B5) A monomeric unsaturated carboxylic acid copolymer (hereinafter sometimes referred to as “precursor copolymer (2)”) and (b6) polymerizable unsaturated group having an oxiranyl group A resin obtained by reacting a compound (hereinafter, also referred to as “resin (B2)”),
(B6) A monomer copolymer containing a polymerizable unsaturated compound having an oxiranyl group (hereinafter sometimes referred to as “precursor copolymer (3)”) is added to (b5) unsaturated carboxylic acid. Resin obtained by reacting a polybasic acid anhydride (hereinafter, referred to as “precursor copolymer (4)”) obtained by reacting an acid (hereinafter referred to as “precursor copolymer (4)”) And (b8) a compound obtained by reacting an unsaturated carboxylic acid with (b8) a compound having two or more oxiranyl groups, and (b9) a polybasic acid anhydride. Resin obtained by reacting a product (hereinafter also referred to as “resin (B4)”)
At least one selected from the group consisting of can be used.

Hereinafter, (b3) a polymerizable unsaturated compound having a hydroxyl group, (b4) an unsaturated isocyanate compound, (b5) an unsaturated carboxylic acid and (b6) a polymerizable unsaturated compound having an oxiranyl group are referred to as “compound (b3)”. ”,“ Compound (b4) ”,“ compound (b5) ”, and“ compound (b6) ”. In addition, polymerizable unsaturated compounds other than the above compounds (b3) to (b6) may be hereinafter referred to as “compound (b7)”.
In addition, (b8) a compound having two or more oxiranyl groups and (b9) polybasic acid anhydride may be referred to as “compound (b8)” and “compound (b9)”, respectively.

As the compound (b3), any polymerizable unsaturated compound having a hydroxyl group can be used without particular limitation. For example, JP-A-2000-105456, JP-A-2004-341278, JP-A-2007-204657 And those described in JP-A-2011-033952 and the like. Among them, from the viewpoint of copolymerization reactivity and reactivity with the compound (b4), (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl (Meth) acrylic acid hydroxyalkyl esters such as esters; (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl esters such as 2- (6-hydroxyhexanoyloxy) ethyl ester; (meth) (Meth) acrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -alkyl esters such as acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester; ) 4-Hydroxymethyl-cyclohexylmethyacrylate Esters, (meth) acrylic acid hydroxyalkyl esters having an alicyclic structure such as (meth) acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester; (meth) acrylic acid 2,3-dihydroxypropyl ester, etc. (Meth) acrylic acid polyhydroxyalkyl ester is preferred.
A compound (b3) can be used individually or in mixture of 2 or more types.

The compound (b4) is a compound having an ethylenically unsaturated bond and an isocyanato group. From the viewpoint of reactivity with the compound (b3), 2- (meth) acryloyloxyethyl isocyanate, 4- (meth) acryloyl Oxybutyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) methacrylate, and 1,1- [bis (meth) acryloyloxymethyl] ethyl isocyanate are preferred.
The commercial name of 2-acryloyloxyethyl isocyanate is Karenz AOI (manufactured by Showa Denko KK) under the trade name, and the commercial name of 2-methacryloyloxyethyl isocyanate is Karenz MOI (manufactured by Showa Denko KK). ), Commercially available 2- (2-isocyanatoethoxy) ethyl methacrylate as commercial products of Karenz MOI-EG (manufactured by Showa Denko KK) and 1,1- (bisacryloyloxymethyl) ethyl isocyanate under the trade names May include Karenz BEI (manufactured by Showa Denko KK) under the trade name.
A compound (b4) can be used individually or in mixture of 2 or more types.

  Moreover, as a compound (b5), the thing similar to the said unsaturated monomer (b1) can be mentioned.

Among these compounds (b5), (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) are preferred because of their reactivity and availability. Acrylate is preferred.
A compound (b5) can be used individually or in mixture of 2 or more types.

Examples of the compound (b6) include those described in paragraph [0042] of JP-A-2006-016545. Of these, (meth) acrylic acid ester having an oxiranyl group is preferable in both cases where it is used for the synthesis of the precursor copolymer (3) and for the synthesis of the resin (B2), and in particular, glycidyl (meth) acrylate. (Meth) acrylic 2-methylglycidyl, (meth) acrylic acid 4-glycidyloxybutyl or (meth) acrylic acid 3,4-epoxycyclohexylmethyl is preferable from the viewpoint that desired effects are easily obtained.
A compound (b6) can be used individually or in combination of 2 or more types.

The compound (b7) is a polymerizable unsaturated compound other than the compounds (b3) to (b6) that can be copolymerized in the precursor copolymers (1) to (3). Those described in paragraphs [0039] to [0042] of JP241241247 can be used alone or in combination of two or more. Among them, as the compound (b7), from the viewpoint of copolymerization reactivity, N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatic vinyl compounds such as styrene and α-methylstyrene; acenaphthylene; methyl ( (Meth) acrylic acid alkyl esters such as meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; (meth) acrylic acid aryl esters such as benzyl (meth) acrylate; allyl (meth) acrylate; , Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate (Meth) acrylic group Acid ester; (meth) acrylic acid ester having an alkylene oxide structure such as 2-ethylhexyl ethylene oxide modified (meth) acrylate and ethylene oxide modified (meth) acrylate of paracumylphenol is preferable.

  Examples of the compound (b8) used for the synthesis of the resin (B4) include a precursor copolymer (3), a novolac epoxy resin, an epoxy compound having a fluorene skeleton, and an epoxy compound having a bisphenol skeleton. Especially, when using for a black radiation sensitive coloring composition, the novolak-type epoxy resin, the epoxy compound which has a fluorene skeleton, and the epoxy compound which has a bisphenol skeleton are preferable from a heat resistant point.

  In addition, the epoxy compound represented by following formula (3) can also be used as an epoxy compound which has the said fluorene skeleton.

Examples of the compound (b9) used for the production of the resin (B4) include those described in paragraph [0016] of JP-A-2004-361455. Among them, dibasic acid anhydrides, polybasic acid dianhydrides higher than tetrabasic acids are preferred, and as dibasic acid anhydrides maleic anhydride, fumaric anhydride, itaconic anhydride, tetrahydrophthalic anhydride, Methyl tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methyl hexahydrophthalic acid anhydride, highmic acid anhydride, phthalic acid anhydride are more preferable. Cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexanetetracarboxylic dianhydride are more preferable.
A compound (b9) can be used individually or in combination of 2 or more types.

Resins (B1) to (B4) can be synthesized by a known method.
Examples of the resin (B1) include JP-A-6-230212 and JP-A-2004-070160, and examples of the resin (B2) include JP-A-5-19467, JP-A-7-325400, and JP-A-9. As the resin (B3), JP-A-6-258830, JP-A-11-326624, JP-A-2002-012607, JP-A-2004-2191979, JP-A-2004-219980, etc. And those disclosed in Japanese Patent Laid-Open No. 2008-181095 and the like.
Examples of the resin (B4) include JP-A-6-093082, JP-A-7-207211, JP-A-11-084126, JP-A-2008-292677, JP-A-7-098409, JP-A-7-098409. Examples thereof include resins disclosed in 2006-312704, JP-A 2005-316449, JP-A 2006-003860, JP-A 11-140144, and the like.

  The binder resin in the present invention has a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran), usually from 1,000 to 100,000. Preferably it is 3,000-50,000. By setting it as such an aspect, heat resistance, a film characteristic, an electrical property, a pattern shape, and the resolution can be made favorable.

  Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here is the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

  In this invention, content of binder 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, More preferably, it is 50-350 mass parts, More preferably, it is 100-250 mass parts. By setting it as such an aspect, alkali developability, the storage stability of a coloring composition, and chromaticity characteristic can be made favorable.

-(C) Polymerizable compound-
In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meta) modified with caprolactone. ) Acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-functional (meth) acrylate and polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group obtained by making a product react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and 3 such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of aliphatic polyhydroxy compounds having a valence higher than that. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dihydrate. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate is at least one selected from bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril and the like.

Among these polymerizable compounds, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethanes (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In this invention, (C) polymeric compound can be used individually or in mixture of 2 or more types.

  The content of the polymerizable compound (C) in the present invention is preferably 10 to 1,000 parts by weight, more preferably 20 to 700 parts by weight, and further 100 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. 200-400 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and alkali developability can be made favorable.

-(D) Photopolymerization initiator-
(D) A photopolymerization initiator is a binder resin having a polymerizable unsaturated bond and a carboxy group in the side chain upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray, (C) It is a compound that generates active species capable of initiating polymerization of a polymerizable compound. The colored composition of the present invention contains the specific compound as a photopolymerization initiator. This makes it possible to form a colored cured film having excellent sensitivity, brightness, resolution, heat resistance, and the like.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and t. -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-dodecyl group and the like can be mentioned.

Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R ¹ and R ² include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, an adamantyl group, and the like. Is mentioned.
As an aryl group having 6 to 30 carbon atoms. A phenyl group, a naphthyl group, a tolyl group, a xylyl group, etc. are mentioned. In the case of phenyl groups, they may be bonded to each other to form a fluorene group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group and a phenethyl group.

The ^R 3, ^{R 4} and an alkyl group having 1 to 20 carbon atoms represented by ^{R 6,} an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 7 to 30 carbon atoms The arylalkyl group is the same as in R ¹ and R ² .
Examples of the heterocyclic group having 4 to 20 carbon atoms include 2-furyl group, furfuryl group, 2-thienyl group, 2-thenyl group, 2-thenoyl group, 2-pyrrolyl group, 2-pyridyl group, piperidino group, A tetrahydrofuryl group, a tetrahydrofurfuryl group, a tetrahydrofuranyl group, etc. are mentioned.

In the above formulas (1) and (2), R ¹ and R ² are each a methyl group, an ethyl group, an n-propyl group, an i-propyl, a cyclohexyl group, and a phenyl group, and R ³ is a methyl group, An ethyl group, a phenyl group, a tolyl group, or a xylyl group; R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group; and R ⁴ is a methyl group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl group. It is preferable. X is preferably a direct bond.
(D) By using the specific compound as a photopolymerization initiator, the sensitivity of the radiation-sensitive colored composition can be improved.

  Examples of the compound represented by the formula (1) and the compound represented by the formula (2) include compounds represented by the following formulas (D-1) to (D-12).

  In the radiation-sensitive colored composition of the present invention, a photopolymerization initiator other than the specific compound (hereinafter also referred to as “other photopolymerization initiator”) can be used in combination. Examples of such other photopolymerization initiators include, for example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds (provided that the compound represented by the formula (1) and Excluding compounds represented by formula (2)), onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like. be able to.

  In this invention, another photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among other preferable photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 2,4-dichlorothioxanthone. 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 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, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as another photoinitiator, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

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

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -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) and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

In the present invention, when the specific compound and another photopolymerization initiator are used in combination, the content ratio of the specific compound is preferably 0.1 to 95% by mass with respect to the total content of the (D) photopolymerization initiator, 1-90 mass parts is especially preferable. Such an embodiment is preferable in that the desired effect of the present invention can be easily obtained.
Moreover, (D) 0.01-120 mass parts is preferable with respect to 100 mass parts of polymerizable compounds, and, as for the total content of a photoinitiator, 1-100 mass parts is especially preferable. By setting it as such an aspect, sclerosis | hardenability and a film characteristic can be made favorable.

-Solvent-
Although the coloring composition of this invention contains the said (A)-(D) component and the other component added arbitrarily, normally, a solvent is mix | blended and it prepares as a liquid composition.
As said solvent, (A)-(D) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has volatility. You can choose to use.

Among such solvents, 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;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

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, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl 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, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl 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, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

  Although content of a solvent is not specifically limited, The quantity from which the total density | concentration of each component except the solvent of the coloring composition becomes 5-50 mass% is preferable, and the quantity used as 10-40 mass% More preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

  Moreover, polyfunctional thiols, such as an aliphatic polyfunctional thiol, a cyclic polyfunctional thiol, a siloxane polyfunctional thiol, a fluorine-containing polyfunctional thiol, can also be mentioned as an additive. In the present invention, the polyfunctional thiol means a compound having two or more sulfanyl groups in the same molecule. The polyfunctional thiol is preferable in that a colored composition having high curability can be obtained.

  The aliphatic polyfunctional thiol is not particularly limited as long as it is a chain compound having two or more sulfanyl groups. For example, hydrocarbons having two or more sulfanyl groups as a substituent, Polyhydric alcohol poly (mercaptoacetate), polyhydric alcohol poly (3-mercaptopropionate), polyhydric alcohol poly (2-mercaptopropionate), polyhydric alcohol poly (3-mercaptobutyrate) Rate). Specific examples thereof include those described in JP-A-10-253816, JP-A-10-282325, JP-A-2004-083857, and the like. The “chain” is a concept including both a straight chain and a branched chain.

The above-mentioned cyclic polyfunctional thiol is not particularly limited as long as it has a cyclic structure in the molecule, for example, a heterocyclic group having two or more sulfanyl groups as substituents, and two substituents. The aromatic hydrocarbon which has the above sulfanyl group can be mentioned. Specific examples thereof include 1,4-benzenedithiol, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6- In addition to dimercapto-s-triazine, 2-mercapto-5-substituted thiadiazole described in JP-A-2-153353 can be exemplified.

The above-mentioned siloxane polyfunctional thiol is not particularly limited as long as it is a polysiloxane having two or more sulfanyl groups. For example, a hydrolyzable silane compound containing a silane compound having a sulfanyl group and a hydrolyzable group is used. Mention may be made of polysiloxanes obtained by hydrolysis condensation. About the specific aspect and manufacturing method, it describes in Unexamined-Japanese-Patent No. 2008-242078, Unexamined-Japanese-Patent No. 2011-128239, etc., for example. Note that silsesquioxane having two or more sulfanyl groups is commercially available from Arakawa Chemical Industries, Ltd. as Composelane (registered trademark) SQ series.

The fluorine-containing polyfunctional thiol is not particularly limited as long as it has a fluorine atom in its molecule. For example, a compound having a poly (perfluoroalkylene ether) chain and two or more sulfanyl groups is used. Can be mentioned. About the specific aspect and manufacturing method, it describes in Unexamined-Japanese-Patent No. 2011-208046 etc., for example.

When the polyfunctional thiol is included in the colored composition of the present invention, the content of the polyfunctional thiol is usually 0.01 to 10% by mass, preferably 0.1 to 7% by mass with respect to the polymerizable compound (C). More preferably, it is 0.5-5 mass%. By setting it as such an aspect, a highly sensitive coloring composition can be obtained and the sclerosis | hardenability of a coating film can be improved.

Colored cured film and method for forming the same The colored cured film of the present invention is formed using the colored composition of the present invention. Specifically, each color pixel used in a display device or a solid-state imaging device, a black matrix , Meaning black spacer.

Hereinafter, the colored cured film used for the color filter which comprises a display element and a solid-state image sensor, and its formation method are demonstrated.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a blue liquid composition of the radiation-sensitive colored composition of the present invention is applied on the substrate, and then pre-baked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which blue pixel patterns (colored cured films) are arranged in a predetermined arrangement.

  Subsequently, using each radiation sensitive coloring composition of green or red, application of each radiation sensitive coloring composition, pre-baking, exposure, development, and post-baking are performed in the same manner as described above to obtain a green pixel array and red color. Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of blue, green and red is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithographic method. However, the radiation sensitive material in which a black colorant is dispersed is used. It can also be formed in the same manner as in the case of forming the above-mentioned pixel using a sexually colored composition. When a black matrix is formed from the radiation-sensitive colored composition of the present invention in which a black colorant is dispersed, the black matrix preferably has an OD value (optical density) per film thickness of 1 μm of 2.3 or more. More preferably, it is 3.1 or more, More preferably, it is 3.5 or more.
In the present invention, the OD value serving as a light shielding index can be obtained from the following relational expression.
OD value = log ₁₀ (I ₀ / I)
Here, I ₀ means the incident light intensity, and I means the transmitted light intensity.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating (slit coating), bar coating, etc. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  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 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of the radiation light source used when forming at least one selected from the pixel and the black matrix include, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, and a low pressure. Examples thereof include a lamp light source such as a mercury lamp, and a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a blue thermosetting coloring composition is discharged into the formed partition wall by an inkjet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a blue pixel pattern.

  Next, using the green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. As a result, a color filter in which the pixel patterns of the three primary colors of blue, green and red are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

In addition, since the partition plays not only a light shielding function but also a function for preventing the color mixing of the thermosetting coloring compositions discharged in the respective sections, it is compared with the black matrix used in the first method described above. The film thickness is thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

  A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer. When the black spacer is formed from the radiation-sensitive colored composition of the present invention in which a black colorant is dispersed, the black spacer preferably has an OD value (optical density) per 1 μm thickness of 0.6 or more. More preferably, it is 1.0 or more, More preferably, it is 1.4 or more, Most preferably, it is 1.8 or more.

The radiation-sensitive colored composition of the present invention can be suitably used in forming any colored cured film such as each color pixel, black matrix, and black spacer used in the color filter.
Since the color filter including the colored cured film of the present invention formed in this way has extremely high luminance and color purity, it can be used in color liquid crystal display elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like. Very useful. In addition, the display element mentioned later should just have at least 1 or more of colored cured films formed using the radiation sensitive coloring composition of this invention.

Display element The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the colored cured film of the present invention may be a transmissive type or a reflective type, and can take an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. Can be taken. Further, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (indium oxide doped with tin) electrode or an IZO (mixture of acid value indium and zinc oxide) electrode It is also possible to adopt a structure in which the substrate on which the substrate is formed faces the liquid crystal layer. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained. When the latter structure is adopted, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed, or on the substrate side on which the ITO electrode or IZO electrode is formed.

  The color liquid crystal display element including the colored cured film of the present invention can include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

  The color liquid crystal display element having the colored cured film of the present invention includes TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, IPS (In-Plane Switching) type, VA (Vertical Alignment) type, OCB (Optical). An appropriate liquid crystal mode such as a Compensated Birefringence type is applicable.

Moreover, the organic EL display element provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
Moreover, the electronic paper provided with the colored cured film of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-2007-41169.

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

<Synthesis of binder resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 80 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 15 parts by mass of 2-hydroxyethyl methacrylate, 28 parts by mass of 2-ethylhexyl methacrylate, N- 12 parts by mass of phenylmaleimide, 15 parts by mass of mono (2-acryloyloxyethyl) succinate, 20 parts by mass of propylene glycol monomethyl ether acetate and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 Part by mass of the mixed solution was added dropwise over 2 hours, and polymerization was performed for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C., and further polymerized for 1 hour to obtain a binder resin solution (B-1) (solid content concentration = 40% by mass). The obtained binder resin was Mw = 10500, Mn = 5900, Mw / Mn = 1.78.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 194.4 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heated to 90 ° C., at the same temperature, 60 parts by mass of propylene glycol monomethyl ether acetate, 60 parts by mass of methacrylic acid, 30 parts by mass of methyl methacrylate, 2-ethylhexyl EO-modified acrylate (manufactured by Toagosei Co., Ltd., M-120) A mixed solution of 30 parts by mass and 18 parts by mass of propylene glycol monomethyl ether acetate, and a mixed solution of 45.6 parts by mass of propylene glycol monomethyl ether and 10.8 parts by mass of 2,2′-azobisbutyronitrile over 2 hours. Each was dropped and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a resin (1) solution. Obtained resin (1) was Mw = 8300, Mn = 4500, Mw / Mn = 1.84.
A flask equipped with a condenser and a stirrer was charged with 374.0 parts by mass of the resin (1) solution, 1.91 parts by mass of tetrabutylammonium bromide, and 0.43 parts by mass of 4-methoxyphenol, and air bubbled. The mixture was heated to 110 ° C., and 56.1 parts by mass of glycidyl methacrylate (68 mol% with respect to the number of moles of methacrylic acid) was added dropwise at the same temperature over 15 minutes. The addition reaction was carried out for 5 hours while maintaining this temperature. I did it. Next, this solution was cooled to room temperature, and propylene glycol monomethyl ether acetate was added so that the non-volatile content was 40% by mass to obtain a binder resin solution (B-2) (solid content concentration = 40% by mass). . The obtained binder resin was Mw = 1200, Mn = 6000, Mw / Mn = 2.03, and the iodine value was 43.5 g / 100 g.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 1216 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. At 90 ° C., 160 parts by mass of cyclohexanone, 160 parts by mass of butyl methacrylate, 160 parts by mass of 2-ethylhexyl EO-modified acrylate (manufactured by Toa Gosei Co., Ltd., M-120) and 480 parts by mass of glycidyl methacrylate. And a mixed solution of 224 parts by mass of cyclohexanone and 56 parts by mass of 2,2′-azobisbutyronitrile were added dropwise over 2 hours, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a resin (2) solution. Obtained resin (2) was Mw = 7200, Mn = 4000, Mw / Mn = 1.80.
A flask equipped with a condenser and a stirrer was charged with 921 parts by mass of the resin (2) solution, 6.15 parts by mass of tetrabutylammonium bromide, and 1.04 parts by mass of 4-methoxyphenol, and air bubbled. The mixture was heated to 110 ° C., and 109.2 parts by mass of methacrylic acid (1.0 equivalent with respect to the number of moles of glycidyl methacrylate) was added dropwise at the same temperature over 15 minutes to obtain a resin (3) solution. Obtained resin (3) was Mw = 9600, Mn = 5500, Mw / Mn = 1.75.
A flask equipped with a condenser and a stirrer was charged with 414.9 parts by mass of the resin (3) solution and 10.32 parts by mass of tetrahydrophthalic anhydride (0.13 equivalents relative to the number of moles of methacrylic acid), and air bubbling was performed. Under the conditions, the mixture was heated and stirred at 100 ° C. for 6 hours to carry out an addition reaction, thereby obtaining a binder resin solution (B-3) (solid content concentration = 45% by mass). The obtained binder resin was Mw = 11300, Mn = 6300, Mw / Mn = 1.79, and the iodine value was 53.6 g / 100 g.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 144 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 48 parts by mass of propylene glycol monomethyl ether acetate, 28.8 parts by mass of methacrylic acid, 18 parts by mass of butyl methacrylate, 18 parts by mass of methyl methacrylate, 2-ethylhexyl EO-modified acrylate (Toa A mixed solution of 18 parts by mass of M-120) and 37.2 parts by mass (0.232 mol) of glycerol methacrylate, and 48 parts by mass of propylene glycol monomethyl ether acetate and 2,2′-azobisbutyronitrile 8.4 parts by mass of the mixed solution was added dropwise over 2 hours, and polymerization was performed for 1 hour while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 90 ° C. and further polymerized for 1 hour to obtain a resin (4) solution (solid content concentration = 33%). Obtained resin (4) was Mw = 10700, Mn = 5600, Mw / Mn = 1.91.
Into a flask equipped with a condenser and a stirrer, the whole amount of the resin (4) solution was added and the temperature of the solution was raised to 90 ° C., and then 2-isocyanuryl ethyl methacrylate (Karenz MOI, Showa Denko KK) 34.3. A mixed solution of parts by mass (0.95 equivalents relative to the number of moles of glycerol methacrylate) and 0.36 parts by mass of 4-methoxyphenol was added dropwise over 15 minutes under air bubbling conditions. By performing an addition reaction for 5 hours, a binder resin solution (B-4) (solid content concentration = 36%) was obtained. The obtained binder resin was Mw = 1800, Mn = 6000, Mw / Mn = 2.13, and the iodine value was 36.0 g / 100 g.

Synthesis example 5
Into a 500 mL three-necked flask, 200 g of propylene glycol monomethyl ether acetate, 235 g of bisphenolfluorene epoxy compound represented by the above formula (3) (epoxy equivalent 235 g / eq), 110 mg of tetramethylammonium chloride, 2,6-di-tert-butyl-4 -100 mg of methylphenol and 72.0 g of acrylic acid were charged, and this was heated and dissolved at 110 ° C while blowing air at a flow rate of 25 mL / min. The acid value was titrated with a 0.1 mol / L KOH solution every hour, and heated and stirred until the acid value was less than 1.0 mg KOH / g to obtain the desired bisphenolfluorene epoxy acrylate.
To 307 g of this bisfluorene epoxy acrylate, 400 g of propylene glycol monomethyl ether acetate, 80.5 g of benzophenone tetracarboxylic dianhydride, and 1 g of tetraethylammonium bromide were mixed, and the mixture was heated and stirred at 100 ° C. for 4 hours. Thereafter, 38 g of tetrahydrophthalic anhydride was added, and the mixture was heated and stirred at 100 ° C. for 4 hours for end-capping to obtain a binder resin solution (B-5) (solid content concentration = 40%). The disappearance of the acid anhydride was confirmed using an IR spectrum. The obtained binder resin was Mw = 8000, Mn = 3500, Mw / Mn = 2.28.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. Pigment Red 177, 5.20 parts by mass, C.I. I. 7.80 parts by mass of Pigment Red 254, 11.5 parts by mass (solid content concentration = 40% by mass) of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant, and 11 of the binder resin solution (B-1) 0.0 parts by weight, 63.0 parts by weight of propylene glycol monomethyl ether acetate and 1.5 parts by weight of propylene glycol monomethyl ether as a solvent were mixed and dispersed by a bead mill to prepare a red pigment dispersion (r-1) did.

Preparation Example 2
As a coloring agent, C.I. I. Pigment Green 58 is 9.10 parts by mass, C.I. I. 3.90 parts by mass of Pigment Yellow 138, 10.74 parts by mass (solid content concentration = 40% by mass) of BYK-LPN21116 (manufactured by BYK Corporation) as a dispersant, 0.20 parts by mass of a dispersion aid (quinophthalone) Pigment derivative), 13.33 parts by mass of the binder resin solution (B-1) (solid content concentration = 40% by mass), 61.0 parts by mass of propylene glycol monomethyl ether acetate and 1.73 parts by mass of propylene glycol monomethyl ether as solvents. A green pigment dispersion (g-1) was prepared by mixing and dispersing with a bead mill.

Preparation Example 3
As a coloring agent, C.I. I. Pigment Blue 15: 6 is 12.0 parts by mass, BYK167 (manufactured by BYK (BYK)) as a dispersant is 9.23 parts by mass (solid content concentration = 52% by mass), and binder resin solution (B-1) is 12 Using 0.5 parts by mass and 66.27 parts by mass of propylene glycol monomethyl ether acetate as a solvent, a blue pigment dispersion (b-1) was prepared by mixing and dispersing with a bead mill.

Preparation Example 4
6. Carbon black 20 parts by weight as a colorant, 10.0 parts by weight (solid content concentration = 40% by weight) of BYK-LPN21116 (manufactured by BYK (BYK)) as a dispersant, and binder resin solution (B-1) 7. 5 parts by mass and 62.5 parts by mass of methoxybutyl acetate as a solvent were mixed and dispersed by a bead mill to prepare a black pigment dispersion (Bk-1).

Preparation Example 5
12.0 parts by mass of perylene black, 12.3 parts by mass of SOLPERSE 76500 (manufactured by Lubrizol Co., Ltd.) as a dispersant, 7.5 parts by mass of a binder resin solution (B-1) solution (solid content concentration = 50% by mass) Then, 65.8 parts by mass of methoxybutyl acetate and 2.4 parts by mass of butyl acetate as a solvent were mixed and dispersed by a bead mill to prepare a black pigment dispersion (Bk-2).

Preparation Example 6
Pigment Red 177 is 10.22 parts by mass, Pigment Yellow 138 is 1.45 parts by mass, Pigment Blue 15: 6 is 3.14 parts by mass, and BYK-LPN6919 (manufactured by BYK Corporation (BYK)) is used as a dispersant. A bead mill using 10.0 parts by mass of the binder resin solution (B-1), 52.52 parts by mass of methoxybutyl acetate and 16.0 parts by mass of ethoxypropanol as a solvent. The black pigment dispersion (Bk-3) was prepared by mixing and dispersing according to the above.

<Preparation of dye solution>
Preparation Example 1
20 g of an acidic dye represented by the following formula (α) was dissolved in 180 g of propylene glycol monomethyl ether acetate to obtain a dye solution (b-2).

Preparation Example 2
20 g of an acidic dye represented by the following formula (β) was dissolved in 180 g of propylene glycol monomethyl ether acetate to obtain a dye solution (b-3).

<Preparation and evaluation of radiation-sensitive coloring composition>
Example 1
Preparation of Colored Composition (A) 1552 parts by mass of pigment dispersion (r-1) as colorant, (B) 51 parts by mass of binder resin solution (B-1) as binder resin, (C) pentaerythritol as polymerizable compound 50 parts by mass of pentaacrylate (Aronix M-450, manufactured by Toagosei Co., Ltd.), (D) 6.85 parts by mass of the compound represented by the formula (D-3) as a photopolymerization initiator, and 2-benzyl-2- 22 parts by mass of dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by BASF), and 5 of Megafac F-554 (manufactured by DIC Corporation) as a fluorosurfactant 14 parts by mass of a propylene glycol monomethyl ether acetate solution by mass and propylene glycol monomethyl ether acetate as a solvent DOO 635 parts by weight, 3-methoxybutyl acetate 500 parts by mass of ethyl 3-ethoxypropionate 100 parts by mass were mixed and red colored composition (S-1) was prepared.

(1) Evaluation of chromaticity The coloring composition (S-1) was applied on a glass substrate at a different rotation speed using a spin coater, and then pre-baked on a hot plate at 90C for 1 minute. Thus, three coating films having different film thicknesses were formed.
Next, after cooling these substrates to room temperature, the coating film on the substrate was irradiated with radiation including each wavelength of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp without passing through a photomask at an illuminance of 35 mW, 600 J / m. The exposure was performed at an exposure amount of ² . Then, shower development was performed by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) onto the coating film on the substrate. . Thereafter, these substrates were washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 20 minutes to produce a red cured film.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. From the measurement results, the chromaticity coordinate value y and the stimulus value (Y) when the chromaticity coordinate value x = 0.640 were obtained. The evaluation results are shown in Table 2. It can be said that the larger the stimulus value (Y), the higher the luminance.

(2) Adhesion evaluation The colored composition (S-1) was applied on a glass substrate using a spin coater, air-dried, and then coated with a film thickness of 2.5 m without pre-baking. Formed. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp is used for the coating film on the substrate, and a photomask having dot patterns having different sizes in 5 μm increments from 5 μm to 50 μm is used. Radiation including each wavelength was exposed at an illuminance of 17 mW and an exposure amount of 600 J / m ² . Then, shower development was performed by discharging the developing solution which consists of 0.04% potassium hydroxide aqueous solution of 23 degreeC with respect to the coating film on a board | substrate with the developing pressure of 1 kgf / cm < ² > (nozzle diameter 1mm). Thereafter, these substrates were washed with ultrapure water and air-dried.
This board | substrate was observed with the optical microscope, and the magnitude | size of the minimum dot pattern resolved without peeling from a board | substrate was confirmed. The evaluation results are shown in Table 2. It can be said that the smaller the size, the better the adhesion.

(3) Sensitivity evaluation The colored composition (S-1) was spin-coated on two soda glass substrates having a diameter of 4 inches on which SiO ₂ film for preventing elution of sodium ions was formed on the surface. Each was applied. These substrates were air-dried without pre-baking to prepare two substrates on which a 2.5 μm thick coating film was formed.
Using a high-pressure mercury lamp on a single substrate that was prepared, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm through a photomask having a stripe pattern of 100 μm, and an exposure amount of illuminance of 35 mW and 600 J / m ² . And exposed. Thereafter, a developing solution consisting of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. is completely applied to the coating film on the substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Shower development was performed by discharging until 15 seconds passed after peeling. Next, post-baking was performed at 230 ° C. for 20 minutes to form a stripe pattern on the substrate.
A stripe pattern was formed on the substrate in the same manner as above except that the other substrate was exposed with an illuminance of 35 mW and an exposure amount of 400 J / m ² .
The pattern width (μm) of the strike pattern on the obtained substrate was measured using an optical microscope. The evaluation results are shown in Table 2. Here, it can be said that the wider the pattern line width, the higher the sensitivity.
Further, the line width change amount (μm) was calculated by the following formula. A smaller line width change is preferable because a process margin is wider.
Line width change (μm) = (Pattern width when exposed at 600 J / m ² ) − (Pattern width when exposed at 400 J / m ² )

Examples 2-8 and Comparative Examples 1-2
In Example 1, red colored compositions (S-2) to (S-10) were prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Table 1. Subsequently, evaluation was performed in the same manner as in Example 1 except that the colored compositions (S-2) to (S-10) were used instead of the colored composition (S-1). The results are shown in Table 2. In the red colored compositions (S-1) to (S-10), each colored composition was prepared so that the oxime bond content was equimolar.

In Table 1, each component is as follows.
C-1: Pentaerythritol pentaacrylate (manufactured by Toa Gosei Co., Ltd., Aronix M-450)
C-2: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)
D-1: Compound represented by Formula (D-3) D-2: Compound represented by Formula (D-9) D-3: Adeka Arkles NCI-831 (manufactured by ADEKA Corporation)
D-4: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)] (trade name IRGACURE OXE02, manufactured by BASF)
D-5: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by BASF)
D-6: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name IRGACURE 907, manufactured by BASF)
D-7: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.)
D-8: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Hodogaya Chemical)
D-9: 2-mercaptobenzothiazole (manufactured by Wako Pure Chemical Industries, Ltd.)
E-1: 5% by mass propylene glycol monomethyl ether acetate solution of MegaFac F-554 (manufactured by DIC Corporation)

E-2: 25 mass% propylene glycol monomethyl ether acetate solution of silsesquioxane polyfunctional thiol (trade name: Composelan (registered trademark) HBSQ105-9, manufactured by Arakawa Chemical Co., Ltd.)
E-3: 3-glycidoxypropyltrimethoxysilane (manufactured by JNC Corporation)
F-1: Propylene glycol monomethyl ether acetate F-2: 3-methoxybutyl acetate F-3: Ethyl 3-ethoxypropionate F-4: Propylene glycol monomethyl ether F-5: Ethyl lactate

Examples 9-16 and Comparative Examples 3-4
In Example 1, green colored compositions (S-11) to (S-20) were prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Table 3. Next, evaluation was performed in the same manner as in Example 1 except that the green colored compositions (S-11) to (S-20) were used instead of the red colored composition (S-1). However, regarding chromaticity evaluation, chromaticity coordinate value x and stimulus value (Y) when chromaticity coordinate value y = 0.613 were evaluated. The results are shown in Table 4. In addition, in the green coloring composition (S-11)-(S-20), each coloring composition was prepared so that content of an oxime bond might become equimolar.

In Table 3, the symbol of each component is the same as in Table 1.

Examples 17-23 and Comparative Examples 5-7
In Example 1, blue colored compositions (S-21) to (S-30) were prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Table 5. Next, evaluation was performed in the same manner as in Example 1 except that the blue colored compositions (S-21) to (S-30) were used instead of the red colored composition (S-1). However, regarding the chromaticity evaluation, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.046 were evaluated. The results are shown in Table 6. In the blue colored compositions (S-21) to (S-30), each colored composition was prepared so that the oxime bond content was equimolar.

In Table 5, the symbol of each component is the same as in Table 1.

In the chromaticity evaluation of Table 4, the y values of Examples 9 to 16 and Comparative Examples 3 to 4 are the same, but the x value of Comparative Examples 3 to 4 is higher than that of Examples 9 to 16, and the stimulation value Y is It turns out that it is low. Therefore, the green coloring composition which does not contain a photoinitiator (D-1) or (D-2) becomes a green coloring composition which contains a photoinitiator (D-1) or (D-2). It can be seen that the degree of yellowing is large and the luminance is low.
Similarly, in the chromaticity evaluation of Table 6, the y values of Examples 17 to 23 and Comparative Examples 5 to 7 are the same, but the x value of Comparative Examples 5 to 7 is higher than that of Examples 17 to 23. It can be seen that the value Y is low. Therefore, the blue coloring composition which does not contain a photoinitiator (D-1) or (D-2) becomes a blue coloring composition which contains a photoinitiator (D-1) or (D-2). It can be seen that the degree of yellowing is large and the luminance is low.

Example 24
A black colored composition (S-31) was prepared in the same manner as in Example 1, except that the type and amount of each component were changed as shown in Table 7.

(4) Formation of black spacer The black colored composition (S-31) prepared above was applied on a non-alkali glass substrate using a spinner, and then on a hot plate at 100C for 3 minutes. Pre-baking was performed to form a film having a thickness of 3.5 μm (coating method).
Next, the obtained film was exposed using a high-pressure mercury lamp (Type 1 light source) having a Type 1 spectral distribution shown in FIG. Then, after developing at 25 ° C. using a 0.05% by weight aqueous solution of potassium hydroxide, washing with pure water for 1 minute, and further heating (post-baking) in an oven at 230 ° C. for 30 minutes, Formed.

(5) Measurement of OD value Using the black spacer formed in (4) above, an OD value was calculated from the transmission spectrum using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) according to the following formula. The results are shown in Table 8.
OD = -Log ₁₀ Y
Y represents the total light transmittance.

(6) Evaluation of sensitivity Radiation sensitivity (J / m < ² >) was evaluated from the remaining film rate represented by the following formula.
Residual film ratio (%) = (film thickness after post-baking / film thickness after exposure) × 100
The minimum exposure amount at which the remaining film ratio is 90% or more was defined as sensitivity. The results are shown in Table 8. When the sensitivity was 600 J / m ² or less, it was judged that the radiation sensitivity was good.

(7) Evaluation of elastic recovery rate About the black spacer obtained at the exposure amount corresponding to the sensitivity investigated in the above (6), using a micro compression tester (Fischer Scope HM2000Xyp, Fisher Instruments), 50 μm × 50 μm With a flat indenter, the loading speed and unloading speed are set to 2.5 mN / sec, a load up to 50 mN is loaded and held for 5 seconds, then unloaded, and the load-deformation curve during loading and the load during slow loading -A deformation curve was created. At this time, the difference between the deformation amount at the load of 50 mN at the load and the deformation amount at the unload is L1, and the difference between the deformation amount at the load of 50 mN and the deformation amount at the unload is L2. The elastic recovery rate was calculated by the following formula.
Elastic recovery rate (%) = (L2 / L1) × 100
When the deformation amount L1 is 0.20 μm or more, the flexibility is good, and when the elastic recovery rate is 65% or more, the elastic recovery rate is high.

(8) Evaluation of rubbing resistance AL3046 (trade name, manufactured by JSR Corporation) as a liquid crystal aligning agent on a substrate on which a black spacer was formed with an exposure amount corresponding to the sensitivity investigated in (6) above. Was applied by a printing machine for applying a liquid crystal alignment film, and then heated at 180 ° C. for 1 hour to form a coating film of a liquid crystal aligning agent having a thickness of 0.05 μm.
Thereafter, the coating film was subjected to a rubbing treatment with a rubbing machine having a roll around which a polyamide cloth was wound, with a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, the presence or absence of pattern peeling was evaluated. The results are shown in Table 8.

(9) Evaluation of adhesion A cured film was formed at an exposure amount corresponding to the sensitivity investigated in (6) above, in the same manner as in the formation of the black spacer except that no photomask was used. . This cured film was evaluated by the 8.5 / 2 cross-cut tape method in the adhesion test of JIS K-5400 (1900) 8.5. The values shown in Table 8 are the number of remaining grids out of 100 grids.

(10) Evaluation of heat resistance A cured film was formed at an exposure amount corresponding to the sensitivity examined in the above (6) in the same manner as in the formation of the black spacer except that no photomask was used. . This cured film was further heated in an oven at 240 ° C. for 60 minutes. The film thickness before and after the additional heating was measured, and the heat resistance was evaluated by determining the remaining film ratio represented by the following formula. The results are shown in Table 8. It can be said that the higher the remaining film ratio, the better the heat resistance.
Residual film ratio (%) = (film thickness after additional heating × 100 / film thickness before additional heating)

(11) Sensitivity evaluation based on change in exposure wavelength In the above (6), instead of the Type 1 light source, the high-pressure mercury lamp having the respective spectral distributions of Type 2, Type 3 and Type 4 shown in FIGS. The sensitivity was evaluated in the same manner as in the above (6) except that the light sources of Type 2 to Type 4 were used. The results are shown in Table 9. As the light source changes from Type 1 to Type 2, Type 3, and Type 4, light in the short wavelength region is gradually cut. Even when these light sources are used, the sensitivity is good when the sensitivity is 600 J / m ² or less.

Examples 25-29 and Comparative Examples 8-9
In Example 24, black colored compositions (S-32) to (S-38) were prepared in the same manner as in Example 24 except that the type and amount of each component were changed as shown in Table 7. Subsequently, evaluation was performed in the same manner as in Example 24 except that the black colored compositions (S-32) to (S-38) were used instead of the black colored composition (S-31). The results are shown in Tables 8-9. In the black colored compositions (S-31) to (S-38), each colored composition was prepared so that the oxime bond content was equimolar.

In Table 7, the symbol of each component is the same as in Table 1.

Claims (6)

A radiation-sensitive colored composition comprising (A) a colorant, (B) a binder resin, (C) a polymerizable compound, and (D) a photopolymerization initiator,
The radiation sensitive coloring composition in which the (D) photopolymerization initiator contains at least one selected from the compound represented by the following formula (1) and the compound represented by the formula (2) [ However, the case where the combination of (A) colorant, (B) binder resin, (C) polymerizable compound, and (D) photopolymerization initiator is the following (i) or (ii) is excluded .
(I) (A) The colorant is carbon black, (B) the binder resin is a cardo resin, (C) the polymerizable compound is dipentaerythritol hexaacrylate, and (D) the photopolymerization initiator is When it is any one fluorene compound selected from compound group α
(Ii) (A) The colorant is carbon black or Pigment Red177, and (B) the binder resin is methacrylic acid, glycidyl methacrylate, methyl methacrylate and dicyclopentanyl acrylate 20: 20: 40: 20, respectively. And (C) the polymerizable compound is dipentaerythritol hexaacrylate, and (D) the photopolymerization initiator is the following compound 9] .
[In Formula (1),
R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. An alkyl group, or R ¹ and R ² are bonded to each other to represent a fluorene group,
R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an alkyl group having 4 to 20 carbon atoms. A heterocyclic group,
X represents a direct bond or a carbonyl group. ]
[In Formula (2),
R ^1, R ^2, R ³ and R ⁴ have the same meanings as R ^1, R ^2, R ³ and R ⁴ in Formula (1),
R ⁵ is —R ⁶ , —OR ⁶ , —SR ⁶ , —COR ⁶ , —CONR ⁶ R ⁶ , —NR ⁶ COR ⁶ , —OCOR ⁶ , —COOR ⁶ , —SCOR ⁶ , —OCSR ⁶ , —COSR. ⁶ , -CSOR ⁶ , -CN, halogen, hydroxyl group,
R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms,
X represents a direct bond or a carbonyl group,
a represents an integer of 0 to 4. ]
  Furthermore, the radiation sensitive coloring composition of Claim 1 containing a dispersing agent.   The radiation-sensitive colored composition according to claim 1 or 2, wherein the (B) binder resin has a polymerizable unsaturated bond and a carboxy group in a side chain.   The (B) binder resin is a resin obtained by further reacting a polybasic acid anhydride with a reaction product obtained by reacting an unsaturated carboxylic acid with a resin having two or more oxiranyl groups. The radiation sensitive coloring composition of any one of Claims 1-3.   The colored cured film formed using the radiation sensitive coloring composition of any one of Claims 1-4.   A display element comprising the colored cured film according to claim 5.