JP2011128239A - Coloring composition, color filter, and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel coloring composition which exhibits sufficiently firm adhesion with a transparent conductive film and an inorganic film and forms a pixel which is excellent in solvent resistance even in the case of a small light exposure quantity. <P>SOLUTION: The coloring composition contains (A) a colorant, (B) a binder resin, (C) a multifunctional monomer, and (D) a cage-type silsesquioxane having at least one group selected from a group composed of a sulfanyl group and a polymerizable unsaturated group. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing. A method of forming a black matrix using a photopolymerizable composition containing a black material (see, for example, Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an inkjet method using a colored resin composition (for example, see Patent Document 4) is also known.

By the way, in Patent Document 5, an acrylic copolymer having a carboxyl group and an ethylenically unsaturated group in the side chain and a polyfunctional thiol are used as a color filter coloring paste having excellent developability and capable of sharp patterning. There has been proposed a photosensitive composition containing. However, a color filter formed using such a photosensitive composition has insufficient adhesion to a transparent conductive film such as ITO or IZO or an inorganic film such as a SiNx film or SiOx film formed thereon. There was a problem of being.
In recent years, in the technical field of color filters, it has become mainstream to reduce the exposure amount and shorten the tact time. However, in pixels formed using conventional colored radiation-sensitive compositions, The problem of inadequate performance is becoming apparent. In order to meet the recent demands for high contrast, high brightness, and high color purity for color liquid crystal display elements, many of the pigments used in colored radiation-sensitive compositions have been made finer. It is considered that there are treatments and surface treatments, and that the content ratio of the pigment in the colored radiation-sensitive composition tends to be higher.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A Japanese Patent Laid-Open No. 5-281734

  The present invention has been made based on the circumstances as described above, and the problem is that a pixel having excellent adhesion to a transparent conductive film or an inorganic film and having excellent solvent resistance even at a low exposure amount. The object is to provide a novel coloring composition that can be formed.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by including a cage silsesquioxane having a reactive functional group such as a sulfanyl group (—SH) in the coloring composition. The present invention has been completed.

  That is, the present invention comprises (A) a colorant, (B) a binder resin, (C) a polyfunctional monomer, and (D) at least one selected from the group consisting of a sulfanyl group and a polymerizable unsaturated group. The present invention provides a colored composition characterized by containing a cage-type silsesquioxane (hereinafter sometimes referred to as “silsesquioxane (D)”).

  Moreover, this invention also provides the color filter provided with the colored layer formed using this coloring composition, and the liquid crystal display element which comprises this color filter.

According to the coloring composition of the present invention, it is possible to form a pixel having excellent adhesion to a transparent conductive film or an inorganic film and having excellent solvent resistance even at a low exposure amount. Moreover, the colored layer formed using the colored composition of the present invention has a high voltage holding ratio and excellent electrical characteristics.
Therefore, the radiation-sensitive composition of the present invention includes color filters for liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper in the electronic industry. It can be used very suitably for the production of various color filters.

Coloring composition will be described in detail the invention.
-(A) Colorant-
The (A) colorant in the present invention is not particularly limited as long as it has colorability, and the color and material can be appropriately selected according to the use such as a color filter. Specifically, any of pigments, dyes, and natural pigments can be used as the colorant. However, since color filters are required to have heat resistance, organic pigments and inorganic pigments are preferred.

  Examples of the organic pigment include, for example, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C.I. ) Names can be mentioned.

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

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

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

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

  In the present invention, the organic pigment can be 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. The organic pigment may be used by refining primary particles by a method of mechanically kneading together with a water-soluble inorganic salt and a water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt, that is, so-called salt milling. preferable. The salt milling method is disclosed in, for example, Japanese Patent Application Laid-Open No. 08-179111. When an organic pigment having primary particles refined is used, the solvent resistance of the formed colored layer tends to be lowered. However, when the colored composition of the present invention is used, such a problem is solved.

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

These colorants may be used by modifying the particle surface with a resin, if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. 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.
In the present invention, the colorant (A) can be used alone or in admixture of two or more.

When the colored composition of the present invention is used for forming a pixel, since the pixel is required to have high-definition color development, the colorant (A) is preferably a colorant having high color developability, specifically an organic pigment. Is preferably used.
On the other hand, when the colored composition of the present invention is used for forming a black matrix, since the black matrix is required to have a light shielding property, an organic pigment or carbon black is preferably used as the (A) colorant.

  (A) The content of the colorant is preferably 5 to 70% by mass in the total solid content of the coloring composition from the viewpoint of forming a pixel having excellent transparency and color purity or a black matrix having excellent light shielding properties. More preferably, it is 5-60 mass%. Here, solid content is components other than the solvent mentioned later. The coloring composition of the present invention can form a pixel excellent in solvent resistance even when the content of the coloring agent is 30% by mass or more in the total solid content of the coloring composition.

  The colorant in the present invention can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, an acrylic copolymer, polyurethane, polyester, polyethyleneimine, polyallylamine, and the like can be given.

  Such a dispersant is commercially available. For example, as an acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (above, manufactured by BYK Corporation (BYK)), As polyurethane, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.), polyethylene As imine, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) and as polyester, Ajisper PB821, Ajisper PB822, Ajisper PB880 ( Mention may be made of the Moto Fine-Techno Co., Ltd.), and the like.

  These dispersants can be used alone or in admixture of two or more. Content of a dispersing agent is 100 mass parts or less normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 1-70 mass parts, More preferably, it is 10-50 mass parts. When there is too much content of a dispersing agent, there exists a possibility that developability etc. may be impaired.

  Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

-(B) Binder resin-
The binder resin (B) in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group, or a sulfo group. In order to enhance the desired effect of the present invention, it is preferable that the polymer having an acidic functional group and a polymerizable unsaturated group is contained in an amount of 10% by mass or more, further 30% by mass or more in the total binder resin.

Examples of the acidic functional group include a carboxyl group, a phenolic hydroxyl group, and a sulfo group, and a carboxyl group is preferable from the viewpoint of alkali solubility and storage stability of the resulting colored composition.
Examples of the polymerizable unsaturated group include a vinylaryl group, a (meth) acryloyl group, an allyl group, and the like, and a (meth) acryloyl group is preferable from the viewpoint of enhancing a desired effect. Moreover, it is preferable that the polymer which has an acidic functional group and a polymerizable unsaturated group has a polymerizable unsaturated group in the side chain.

  The polymer having an acidic functional group and a polymerizable unsaturated group is not particularly limited as long as the above requirements are satisfied. For example, (b-1) a polymer of a polymerizable unsaturated compound having a carboxyl group is used. A polymer obtained by reacting a carboxyl group with a polymerizable unsaturated compound having an oxiranyl group (hereinafter sometimes referred to as “binder resin (b-1)”), (b-2) a polymerizable group having a hydroxyl group. A polymer obtained by reacting a polymerizable unsaturated compound having an isocyanato group with a hydroxyl group of a copolymer of an unsaturated compound and a polymerizable unsaturated compound having an acidic functional group (hereinafter referred to as “binder resin (b-2)”) And (b-3) a polymerizable unsaturated compound having a carboxyl group is reacted with the oxiranyl group of the polymer of the polymerizable unsaturated compound having an oxiranyl group. , A polymer obtained by reacting an acid anhydride with a hydroxyl group generated by the reaction (hereinafter sometimes referred to as “binder resin (b-3)”), (b-4) an epoxy group of an epoxy resin with a carboxyl group A polymer obtained by reacting a polymerizable unsaturated compound having a group, and further reacting an acid anhydride with a hydroxyl group produced by the reaction (hereinafter, sometimes referred to as “binder resin (b-4)”). (B-5) A polymer obtained by reacting a copolymer of styrene or a derivative thereof and maleic anhydride or an ester thereof with a polymerizable unsaturated compound having a hydroxyl group (hereinafter referred to as “binder resin (b-5)”) Or the like.).

The polymer of the polymerizable unsaturated compound having a carboxyl group used for the production of the binder resin (b-1) is not particularly limited as long as it has a carboxyl group, and the polymerizable unsaturated compound having a carboxyl group is polymerized. Is obtained.
Examples of the polymerizable unsaturated compound having a carboxyl group include (meth) acrylic acid and maleic acid, unsaturated compounds obtained by adding lactones to (meth) acrylic acid; hydroxyalkyl (meth) acrylate and succinic acid , Unsaturated acid compounds to which dibasic acids such as maleic acid, phthalic acid, or their anhydrides or anhydrides are added. A plurality of these may be used.
Among these, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, and ω-carboxypolycaprolactone mono (meth) acrylate are preferable, and (meth) acrylic acid is more preferable.

  Examples of the polymerizable unsaturated compound having an oxiranyl group used in the production of the binder resin (b-1) include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso ) Unsaturated compounds having a glycidyl group such as crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4-hydroxybutyl (meth) acrylate glycidyl ether, p-vinylbenzyl glycidyl ether; 2 An alicyclic epoxy group such as a 1,3-epoxycyclopentyl group, a 3,4-epoxycyclohexyl group, a 7,8-epoxy [tricyclo [5.2.1.0] dec-2-yl] group, and (meth) Having a polymerizable unsaturated group such as an acryloyl group Saturated compounds. A plurality of these may be used.

The copolymer of the polymerizable unsaturated compound having a hydroxyl group and the polymerizable unsaturated compound having an acidic functional group used for the production of the binder resin (b-2) is particularly limited as long as it has a hydroxyl group and an acidic functional group. However, it is obtained by polymerizing at least a polymerizable unsaturated compound having a hydroxyl group and a polymerizable unsaturated compound having an acidic functional group.
Examples of the polymerizable unsaturated compound having a hydroxyl group and a vinyl group include hydroxyalkyl (such as 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate) ( In addition to (meth) acrylate, N-methylolacrylamide, allyl alcohol and the like can be mentioned. Moreover, as a polymerizable unsaturated compound which has an acidic functional group, the polymerizable unsaturated compound which has the carboxyl group quoted in the said binder resin (b-1), etc. are mentioned. A plurality of these may be used.

  Examples of the polymerizable unsaturated compound having an isocyanato group used in the production of the binder resin (b-2) include 2- (meth) acryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, Examples include 1,1- (bisacryloyloxymethyl) ethyl isocyanate. A plurality of these may be used.

  The polymer of the polymerizable unsaturated compound having an oxiranyl group used for the production of the binder resin (b-3) may be any polymer having an oxiranyl group, but a poly (meth) acrylic acid ester having an oxiranyl group. Examples thereof include a copolymer and a polystyrene copolymer having an oxiranyl group. The poly (meth) acrylic acid ester-based copolymer having an oxiranyl group is a copolymer of a (meth) acrylic acid ester having an oxiranyl group and another polymerizable unsaturated compound. Examples of the (meth) acrylic acid ester having an oxiranyl group include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl (meth) ) Acrylate glycidyl ether and the like. A plurality of these may be used.

  Examples of styrenes having an oxiranyl group constituting a styrenic copolymer having an oxiranyl group include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 2,4-diglycidyloxy. Examples thereof include styrenes having 1 to 3 glycidyl groups such as methylstyrene and 3,4,5-triglycidylmethylstyrene. A plurality of these may be used.

Examples of the polymerizable unsaturated compound having a carboxyl group used in the production of the binder resin (b-3) include (meth) acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and 2- (meth) acryloylethylsuccinate. An acid etc. can be mentioned. A plurality of these may be used.
Examples of the acid anhydride used for the production of the binder resin (b-3) include malonic anhydride, maleic anhydride, citraconic anhydride, succinic anhydride, glutaric anhydride, glutaconic anhydride, itaconic anhydride, and diglycol anhydride. Examples thereof include polybasic acid anhydrides such as acid, phthalic anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, 4-cyclohexene-1,2-dicarboxylic acid anhydride, and diphenic acid anhydride. A plurality of these may be used.

  In addition, the polymer of the polymerizable unsaturated compound which has a carboxyl group used for manufacture of binder resin (b-1), the polymerizable unsaturated compound which has a hydroxyl group used for manufacture of binder resin (b-2), and an acidic function In the copolymer of the polymerizable unsaturated compound having a group and the polymer of the polymerizable unsaturated compound having an oxiranyl group used for the production of the binder resin (b-3), copolymerization with each polymerizable unsaturated compound Other possible polymerizable unsaturated compounds can be copolymerized.

Examples of such other polymerizable unsaturated compounds include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; and fragrances such as styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, and acenaphthylene. Group vinyl compound; methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2. ^1.02,6 ] (Meth) such as decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol Acrylic acid Ester, and the like. Moreover, the polymer of the polymerizable unsaturated compound which has a carboxyl group used for manufacture of a polymer (b-1), and the weight of the polymerizable unsaturated compound which has an oxiranyl group used for manufacture of a polymer (b-3). In the coalescence, a polymerizable unsaturated compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and glycerol mono (meth) acrylate can be copolymerized. A plurality of these may be used.

  Epoxy resins used in the production of the binder resin (b-4) include bisphenol A type epoxy resins, epoxy resins obtained by the reaction of alcoholic hydroxyl groups of bisphenol A type epoxy resins and epichlorohydrin, bisphenol F type epoxy resins, bisphenol F. Type epoxy resin obtained by reaction of alcoholic hydroxyl group with epichlorohydrin, bisphenol S type epoxy resin, biphenyl glycidyl ether, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triglycidyl isocyanurate, trisphenol methane type epoxy resin Fluorene epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin and the like. A copolymer type epoxy resin can also be used.

  Examples of the polymerizable unsaturated compound having a carboxyl group and the acid anhydride used in the production of the binder resin (b-4) include the same compounds as those used in the production of the binder resin (b-3).

  Examples of the copolymer of styrene or a derivative thereof and maleic anhydride used in the production of the binder resin (b-5) include styrene, m-methoxystyrene, p-methoxystyrene, maleic anhydride, or maleic acid. Maleic acid such as monomethyl acid, monoethyl maleate, mono-n-propyl maleate, mono-iso-propyl maleate, mono-n-butyl maleate, mono-iso-butyl maleate, mono-tert-butyl maleate And a copolymer with a mono-lower alkyl ester.

  Examples of the polymerizable unsaturated compound having a hydroxyl group used in the production of the binder resin (b-5) include hydroxyalkyl (meth) acrylate, N-methylolacrylamide, and allyl alcohol.

  In the present invention, as the binder resin, a polymer having an acidic functional group but not having a polymerizable unsaturated group can be used alone, and used together with a polymer having an acidic functional group and a polymerizable unsaturated group. You can also Specific examples of such binder resins include, for example, JP-A-7-140654, JP-A-9-31444, JP-A-10-31308, JP-A-10-300922, and JP-A-11-174224. Examples thereof include copolymers disclosed in JP-A-11-258415, JP-A-2000-56118, JP-A-2002-296778, JP-A-2004-101728, and the like.

  The acid value of the binder resin in the present invention is preferably 10 to 200 KOH / mg, more preferably 20 to 150 KOH / mg, and still more preferably 30 to 150 KOH / mg.

  The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the binder resin in the present invention is 1,000 to 100,000, and further 3,000. ~ 50,000 is preferred. In this case, if Mw is too small, the remaining film rate of the resulting coating may decrease, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, There is a possibility that the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.

  Further, the ratio (Mw / Mn) of the Mw of the binder resin in the present invention and the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) is Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0.

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method. Further, the above-mentioned polymer having an acidic functional group and a polymerizable unsaturated group can be prepared by a known method, for example, JP-A-5-19467, JP-A-5-61196, JP-A-6-230212, It can be produced by the methods disclosed in Kaihei 7-207211 and JP-A-2008-181095.

In this invention, binder resin can be used individually or in mixture of 2 or more types.
In the present invention, the content of the binder resin is preferably 10 to 1,000 parts by mass, and more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the binder resin is too small, for example, alkali developability may be reduced, or residues or background stains may be generated on the substrate in the unexposed area or on the light shielding layer. Since the pigment concentration relatively decreases, it may be difficult to achieve the target color concentration as a thin film.

-(C) polyfunctional monomer-
The (C) polyfunctional monomer in the present invention is not particularly limited as long as it is a monomer 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 (C) polyfunctional monomer 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 aliphatic polyhydroxy compounds and esters of (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and alkylene oxide-modified polyfunctional compounds. Functional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-containing (meth) acrylate and polyfunctional isocyanate, carboxyl group obtained by reacting hydroxyl-containing (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate etc. which have 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, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. 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. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol , Ethylene oxide and / or propylene oxide modified pen of dipentaerythritol (Meth) acrylate, ethylene oxide dipentaerythritol and / or propylene oxide-modified hexa (meth) can be given 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. In addition, a melamine structure and a benzoguanamine structure are the concept also including a melamine, a benzoguanamine, or those condensates. 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 polyfunctional monomers, trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid esters, caprolactone-modified polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates and carboxyl groups Preferred are polyfunctional (meth) acrylates having N, N, N, N, N, N-hexa (alkoxymethyl) melamine and N, N, N, N-tetra (alkoxymethyl) benzoguanamine. Among esters of trivalent or higher aliphatic polyhydroxy compounds and (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate have many carboxyl groups. Among functional (meth) acrylates, compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride, compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride, the strength of the colored layer is high, It is particularly preferable in that it has excellent surface smoothness of the colored layer and is less likely to cause background contamination and film residue on the unexposed substrate and the light shielding layer.
In the present invention, the polyfunctional monomer (C) can be used alone or in admixture of two or more.

  In the present invention, the content of the (C) polyfunctional monomer is preferably 5 to 500 parts by mass, particularly preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (B) binder resin. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, when the color composition of the present invention is imparted with alkali developability, the alkali developability is lowered, and on the unexposed portion of the substrate or the light shielding layer. There is a tendency that dirt, film residue, etc. are likely to occur.

-Silsesquioxane (D)-
The coloring composition of the present invention contains a silsesquioxane (D), that is, a cage silsesquioxane having at least one selected from the group consisting of a sulfanyl group and a polymerizable unsaturated group. . Although it is known that a sulfanyl group (—SH) is radically or cationically added to an ethylenically unsaturated bond, the present inventors have found that a stereoregular silsesquioxane structure is a sulfanyl group or a polymerized group. It has been found that by incorporating into the cross-linked structure such as the above-mentioned (C) polyfunctional monomer via a polymerizable unsaturated group, extremely excellent adhesion to an inorganic film and solvent resistance are expressed.

  In the present invention, silsesquioxane (D) is represented by the following formula (D-5) together with a perfect cage silsesquioxane as represented by the following formulas (D-1) to (D-4). It is a concept including an incomplete cage-type silsesquioxane in which a portion of the cage represented by (D-6) is open.

(In the above formula, R independently represents a monovalent organic group, provided that at least two of all R are at least one selected from the group consisting of a sulfanyl group and a polymerizable unsaturated group. A group having

In the above formula, the group having a sulfanyl group is not particularly limited, but a hydrocarbon group having 1 to 8 carbon atoms having a sulfanyl group is preferable, and particularly an alkyl group having 1 to 8 carbon atoms having a sulfanyl group. Specific examples thereof include mercaptomethyl group, 2-mercaptoethyl group, 3-methylcaptopropyl group, 1,4-dimethylcapto-2-butyl group, 1,2-dimethylcaptoethyl group, 2-mercapto. Examples thereof include a methyl-3-mercaptopropyl group, and a 3-methylcaptopropyl group is particularly preferable.
In the above formula, the group having a polymerizable unsaturated group is not particularly limited, but a vinyl group, a vinylaryl group, a (meth) acryloxyalkyl group, and an allyl group are preferable, and in particular, (meth) An acryloxyalkyl group is preferred, and specific examples thereof include 3- (meth) acryloxypropyl group, 2- (meth) acryloxyethyl group, (meth) acryloxymethyl group and the like.

In the above formula, examples of the monovalent organic group other than a group having a sulfanyl group and the like include, for example, an optionally substituted alkyl group having 1 to 6 carbon atoms and an optionally substituted carbon. Examples include an aryl group of formula 6-18.
In the present invention, the alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or a pentyl group. Moreover, as said C6-C18 aryl group, a C6-C10 aryl group is preferable and a phenyl group is especially preferable.

Examples of the substituent of the alkyl group having 1 to 6 carbon atoms include an oxiranyl group, a glycidoxy group, a 3,4-epoxycyclohexyl group, an oxetane-3-yl group, an oxetane-3-ylmethyloxy group, and 2,3. -Epithiopropyloxy group, carboxyl group, hydroxyl group, hydroxyphenylcarbonyloxy group, isocyanato group, amino group, ureido group and the like can be mentioned. In the present invention, the alkyl group having 1 to 6 carbon atoms is unsubstituted, or an oxiranyl group, a glycidoxy group, a 3,4-epoxycyclohexyl group, an oxetane-3-yl group, or an oxetane-3-ylmethyloxy group. It is preferable to have it as a substituent. The 3-position carbon of the oxetane-3-yl group or oxetane-3-ylmethyloxy group may be substituted with a C1-C6 alkyl group such as a methyl group, an ethyl group, or an n-propyl group. Good.
Moreover, as a substituent of the said C6-C18 aryl group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, or a C1-C6 alkyl group etc. can be mentioned, for example.

  Silsesquioxane (D) is obtained by, for example, hydrolyzing a silane compound containing a compound represented by the following formula (hereinafter sometimes referred to as “compound (d1)”) in the presence of a basic catalyst. Can be manufactured.

RSix ₃ (d1)

(In the above formula, R represents a sulfanyl group or a group having a polymerizable unsaturated group, and X represents a hydrolyzable group.)

X in the above formula is not particularly limited as long as it is a hydrolyzable group, and examples thereof include an alkoxy group, a cycloalkoxy group, an aryloxy group, an acyloxy group, a halogen atom, and a hydrogen atom. . Of these, alkoxy groups, cycloalkoxy groups, aryloxy groups, and acyloxy groups are preferable from the viewpoint of reactivity, and methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, n-butyl groups, i-butyl groups. Group, t-butyl, cyclohexyloxy group, phenyloxy group and acetoxy group are more preferable, and methoxy group and ethoxy group are particularly preferable.
X may be the same group in the above formula, or two or more different groups.

  Preferable specific examples of the compound (d1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyltributoxysilane, 1,4-dimercapto-2. -(Trimethoxysilyl) butane, 1,4-dimercapto-2- (triethoxysilyl) butane, 1,4-dimercapto-2- (tripropoxysilyl) butane, 1,4-dimercapto-2- (tributoxysilyl) ) Butane, 2-mercaptomethyl-3-mercaptopropyltrimethoxysilane, 2-mercaptomethyl-3-mercaptopropyltriethoxysilane, 2-mercaptomethyl-3-mercaptopropyltripropoxysilane, 2-mercaptomethyl-3-mercapto Ropirtriboxysilane, 1,2-dimercaptoethyltrimethoxysilane, 1,2-dimercaptoethyltriethoxysilane, 1,2-dimercaptoethyltripropoxysilane, 1,2-dimercaptoethyltributoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethyltriethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyl Examples include triethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, p-vinylphenyltrimethoxysilane, p-vinylphenyltriethoxysilane, and the like.

  The silsesquioxane (D) may be a hydrolysis-condensation product of the compound (d1), but the compound (d1) and a silane compound represented by the following formula (hereinafter referred to as “compound (d2)”) It may also be a hydrolytic condensate.

R ¹ SiX ¹ ₃ (d2)

(In the above formula, R ¹ represents an optionally substituted alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group having 6 to 18 carbon atoms, and X ¹ is hydrolyzable. Group.)

  Preferable specific examples of the compound (d2) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane. 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3′-ethyloxetane- 3′-yl) propyltrimethoxysilane, 3- (3′-ethyloxetane-3′-yl) propyltriethoxysilane, (3-ethyloxetane-3-ylmethyloxy) propyltrimethoxysilane, (3-ethyl Oxetane-3-ylmethi Oxy) propyl triethoxysilane, and the like.

  In the silsesquioxane (D), the content of the structural unit derived from the compound (d1) is usually 5 to 100% by weight based on the total of repeating units derived from the compounds (d1) and (d2). , Preferably 10 to 100% by weight, particularly preferably 20 to 100% by weight. By making the content rate of the structural unit induced | guided | derived from a compound (d1) into the said range, the colored layer excellent in adhesiveness with an inorganic film, solvent resistance, and an electrical property can be formed.

  For more specific methods for producing silsesquioxane (D) from compound (d1) and the like, JP-A Nos. 11-29640 and 2004-143449 can be referred to.

  The Mw of the silsesquioxane (D) is usually 300 to 50,000, preferably 500 to 30,000. If Mw is too small, the desired effect of the present invention may be impaired. On the other hand, if Mw is too large, applicability and dispersibility of the colorant may be deteriorated.

  In this invention, content of silsesquioxane (D) becomes like this. Preferably it is 1-50 mass parts with respect to 100 mass parts of (C) polyfunctional monomers, More preferably, it is 2-30 mass parts. . In this case, if the content of silsesquioxane (D) is too small, the desired effect of the present invention may be impaired. On the other hand, if the content is too large, the compatibility with other components may be reduced, or alkali developability may be reduced. There is a tendency that background contamination, film residue, etc. are likely to occur on the unexposed portion of the substrate or the light shielding layer.

-(E) Photopolymerization initiator-
The coloring composition of the present invention can be provided with radiation sensitivity by incorporating a photopolymerization initiator. The term “radiation” as used herein means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
The (E) photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer optionally used by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates an active species capable of initiating polymerization of a functional monomer.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. , Polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like.

  In this invention, a 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. In particular, the O-acyloxime compound is preferably contained in the total photopolymerization initiator, preferably 50% by mass or more, and more preferably 75% by mass or more.

The O-acyloxime compound is not particularly limited as long as it is a photopolymerization initiator having an acyloxime structure (> C═N—O—CO—). For example, International Publication No. WO 2002/100903 Examples include compounds described in pamphlets, pamphlet of International Publication No. 2006/018933, pamphlet of International Publication No. 2008/078678, and the like. Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) ) Methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime). In the present invention, the O-acyloxime compound is preferably a compound having a carbazole structure from the viewpoint of enhancing a desired effect.
In the present invention, the O-acyloxime compounds can be used alone or in admixture of two or more.

  Specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2, Examples include 4-diethylthioxanthone and 2,4-diisopropylthioxanthone.

  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, 1-hydroxy-cyclohexyl phenyl ketone, etc. Can be mentioned.

  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 a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. 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, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the 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.

  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 this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polyfunctional monomers, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-(F) Thermal polymerization initiator-
In the present invention, the adhesion of the colored layer to the inorganic film and the solvent resistance can be further improved by incorporating (F) a thermal polymerization initiator in the colored composition. Examples of the thermal polymerization initiator include azo compounds, organic peroxides, hydrogen peroxide, and the like. Of these, azo compounds are preferred.

  Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-carbonitrile). 2,2′-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2- Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2′-azobis [N-butyl-2-methylpropionamide], 2,2′-a Bis (N-cyclohexyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionate), 2,2 ′ -Azobis (2,4,4-trimethylpentene) and the like, among these, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) ) Is preferred.

  In this invention, content of a thermal-polymerization initiator becomes like this. Preferably it is 0.1-10 mass parts with respect to 100 mass parts of (C) polyfunctional monomers, More preferably, it is 1-5 mass parts.

-Additives-
The coloring composition of the present invention can further contain other additives as required.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anticoagulant such as sodium acrylate; 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 Residue improvers such as 4-amino-1,2-butanediol; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypoly Examples include developability improvers such as caprolactone mono (meth) acrylate.

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

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

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

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

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, 3-ethoxypropion Acid methyl, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate Le, formic acid n- amyl acetate, i- amyl, n- butyl propionate, butyrate ethyl butyrate i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

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

  The content of the solvent is not particularly limited, but from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is usually 5 to 50% by weight, preferably 10 to 40% by weight.

Color filter The color filter of the present invention has a colored layer formed using the colored composition of the present invention.
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, after applying a liquid composition of the colored radiation-sensitive composition of the present invention in which a red colorant is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming 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 red pixel patterns are arranged in a predetermined arrangement.
Then, using the liquid composition of each colored radiation-sensitive composition in which a green or blue colorant is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above. A green pixel array and a blue pixel array are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of the three primary colors of red, green and blue 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.
A 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 photolithography method. A liquid composition of a radiation sensitive composition can be used and formed in the same manner as in the pixel formation.

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 a liquid composition of a radiation sensitive composition to a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, etc. is adopted. In particular, a spin coating method and a slit die coating method are preferable.
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 Pass. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of radiation is preferably 10~10,000J / m ^2. The colored layer formed from the colored radiation-sensitive composition of the present invention has sufficient solvent resistance even with an exposure amount of less than 600 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.
The 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 5.0 μm, preferably 1.0 to 3.0 μm.

As a second method for producing a color filter, a method for obtaining pixels of each color by an ink jet method, which is disclosed in JP-A-7-318723, JP-A-2000-310706, and the like, is also known. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the liquid composition of the colored composition of the present invention in which, for example, a red colorant is dispersed in the formed partition wall is discharged by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.
Next, using a liquid composition of each coloring composition in which a green or blue colorant is dispersed, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.
In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. 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. Thus, the film thickness of the pixel formed by the ink jet method is approximately the same as the thickness of the black matrix.

A protective film is formed on the color filter thus obtained as necessary, and then a transparent conductive film is formed by sputtering. Examples of the transparent conductive film include a NESA film made of tin oxide (registered trademark of PPG, USA), an ITO film made of indium oxide-tin oxide, an IZO film made of indium oxide-zinc oxide, and the like. Moreover, as a protective film, inorganic films, such as an organic film formed from a thermosetting resin composition, a SiNx film | membrane, a SiOx film | membrane, can be mentioned.
The color filter formed using the colored composition of the present invention is excellent in adhesiveness with an inorganic film such as a transparent conductive film, SiNx film, or SiOx film.
The color filter of the present invention is extremely useful for a color liquid crystal surface element, a color imaging tube element, a color sensor, an organic EL display element, electronic paper, and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have 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. In addition, 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 a substrate in which a transparent electrode is formed are opposed to each other with a liquid crystal layer interposed therebetween. You can also. 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.
The color liquid crystal display element of the present invention is excellent in long-term reliability.

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

Preparation of colorant dispersion Preparation Example 1
(A) C.I. I. Pigment green 58 / C.I. I. Pigment Yellow 150 = 60/40 (mass ratio) mixture 15.0 parts by mass, BYK-LPN21116 (produced by BYK) as a dispersant, 11.2 parts by mass (solid content concentration 40% by mass), and propylene as a solvent Using 73.8 parts by mass of glycol monomethyl ether acetate, the mixture was dispersed and dispersed by a bead mill for 12 hours to prepare a colorant dispersion (A-1).

Preparation Example 2
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 60/40 (mass ratio) mixture 15.0 parts by mass, BYK-LPN21116 (produced by BYK) as a dispersant, 11.2 parts by mass (solid content concentration 40% by mass), and propylene as a solvent Using 73.8 parts by mass of glycol monomethyl ether acetate, the mixture was dispersed and dispersed by a bead mill for 12 hours to prepare a colorant dispersion (A-2).

Preparation Example 3
(A) C.I. I. Pigment red 242 / C.I. I. Pigment red 177 / C.I. I. Pigment Yellow 139 = 22/72/6 (mass ratio) mixture 15.0 parts by mass, Solsperse 76500 (manufactured by Lubrizol Co., Ltd.) as a dispersant, 4.0 parts by mass (in terms of solid content), and propylene glycol as a solvent A mixture of monomethyl ether acetate / propylene glycol monoethyl ether = 80/20 (mass ratio) was mixed and dispersed for 12 hours by a bead mill using a solid content concentration of 19 mass%, and a colorant dispersion (A-3 ) Was prepared.

  (A) C.I. I. Pigment Blue 15: 4 / C.I. I. Pigment Violet 23 = 85/15 (mass ratio) mixture 12.0 parts by mass, BYK-LPN21116 (manufactured by BYK) as a dispersant, 11.2 parts by mass (solid content concentration 40% by mass), and propylene as a solvent A colorant dispersion (A-4) was prepared by using 76.8 parts by mass of glycol monomethyl ether acetate and mixing and dispersing for 12 hours with a bead mill.

Synthesis of binder resin Synthesis Example 1
In a flask equipped with a condenser and a stirrer, 44 parts by mass of p-vinylbenzyl glycidyl ether, 40 parts by mass of N-phenylmaleimide, and 16 parts by mass of benzyl methacrylate are dissolved in 300 parts by mass of propylene glycol monomethyl ether acetate. 8 parts by mass of '-azobisisobutyronitrile and 8 parts by mass of α-methylstyrene dimer were charged and purged with nitrogen. Thereafter, the reaction solution was heated to 80 ° C. while gently stirring and nitrogen bubbling, and polymerization was carried out for 5 hours while maintaining this temperature.
Next, 17 parts by mass of methacrylic acid, 0.5 parts by mass of p-methoxyphenol and 4.4 parts by mass of tetrabutylammonium bromide were added to the reaction solution, and the reaction was performed at a temperature of 120 ° C. for 9 hours. Furthermore, after adding 18.5 parts by mass of succinic anhydride and reacting at a temperature of 100 ° C. for 6 hours, the reaction solution temperature was maintained at 85 ° C. and washed twice with water, followed by concentration under reduced pressure to obtain a binder. A resin solution (solid content concentration = 33.0 mass%) was obtained. The obtained binder resin was Mw = 7,800 and Mn = 5,000. This binder resin solution is referred to as “binder resin solution (B-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 200 parts by mass of propylene glycol monomethyl ether acetate, followed by 15 parts by mass of methacrylic acid and 30 parts by mass of N-phenylmaleimide. , 35 parts by mass of benzyl methacrylate, 20 parts by mass of styrene and 5 parts by mass of α-methylstyrene dimer (chain transfer agent) were charged, and after nitrogen substitution, the reaction solution was heated to 80 ° C. while gently stirring. The polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobisisobutyronitrile was added, and polymerization was continued for an additional hour, whereby a binder resin solution (solid content concentration) was obtained. = 32.5 wt%). The obtained binder resin was Mw = 12,000 and Mn = 5,800. This binder resin solution is referred to as “binder resin solution (B-2)”.

Synthesis of silsesquioxane (D) Synthesis example 3
Under a nitrogen atmosphere, 27.1 parts by mass of propylene glycol monomethyl ether acetate and 23.2 parts by mass of 3-mercaptopropyltrimethoxysilane were charged into a three-necked flask and heated to 60 ° C. while stirring. To this solution, 9.6 parts by mass of a 0.2% by mass aqueous solution of malonic acid was added and reacted at 60 ° C. for 2 hours. Thereafter, water and methanol were distilled off under reduced pressure, and propylene glycol monomethyl ether acetate was added to the obtained product until the total amount became 75 parts by mass. Next, a solution obtained by mixing 4.5 parts by mass of triethylamine and 70.5 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 1 hour using a dropping funnel. Furthermore, reaction was performed at 60 ° C. for 2 hours, and water and triethylamine were distilled off under reduced pressure to obtain silsesquioxane having a sulfanylpropyl group. As a result of GPC measurement of the obtained silsesquioxane, it was Mw = 5,200 and Mn = 2500. Moreover, it confirmed that the obtained silsesquioxane contained the cage silsesquioxane by liquid chromatograph mass spectrometry (LC-MS). This cage silsesquioxane is referred to as “silsesquioxane (D-1)”.

Synthesis example 4
In accordance with the description in paragraph [0030] of JP-A-2004-143449, a compound in which R is a 3-methacryloxypropyl group in the above formula (D-1), R in the above formula (D-2) is 3-methacryloxy A compound in which R is a 3-methacryloxypropyl group in the above formula (D-3), a compound in which R is a 3-methacryloxypropyl group in the above formula (D-5), and the above formula (D A mixture of cage-type silsesquioxane containing a compound in which R is a 3-methacryloxypropyl group in -6) was obtained. This cage silsesquioxane is referred to as “silsesquioxane (D-2)”.

Synthesis example 5
Under a nitrogen atmosphere, 27.1 parts by mass of propylene glycol monomethyl ether, 12.6 parts by mass of 3-mercaptopropyltrimethoxysilane and 5.3 parts by mass of 3-methacryloxypropyltrimethoxysilane were charged into a three-necked flask while stirring. And heated to 50 ° C. To this solution, 5.8 parts by mass of a 0.2% by mass aqueous solution of oxalic acid was added and reacted at 50 ° C. for 1 hour. Then, water and methanol were distilled off under reduced pressure, and propylene glycol monomethyl ether was added to the obtained product until the total amount became 90 parts by mass. Next, this solution is heated to 70 ° C. with stirring, and 4.7 parts by mass of a 25% by weight tetramethylammonium hydroxide aqueous solution, 2.3 parts by mass of pure water, and 6.3 parts by mass of propylene glycol monomethyl ether are mixed. The solution was added and reacted at 70 ° C. for 3 hours. The obtained product was cooled to 10 ° C. or lower, and 14 g of a 10 mass% propylene glycol monomethyl ether solution of maleic acid was added while stirring. Next, butyl acetate is added, washed with water three times with a separatory funnel, dehydrated with a desiccant, and then water and butyl acetate are distilled off under reduced pressure to have a sulfanylpropyl group and a methacryloxypropyl group. Silsesquioxane was obtained. As a result of GPC measurement of the obtained silsesquioxane, it was Mw = 2150 and Mn = 1750. Moreover, it confirmed that the obtained silsesquioxane contained the cage silsesquioxane by liquid chromatograph mass spectrometry (LC-MS). This cage silsesquioxane is referred to as “silsesquioxane (D-3)”.

Synthesis Example 6
Under a nitrogen atmosphere, 42.2 parts by mass of propylene glycol monopropyl ether, 4.5 parts by mass of pure water and 3.2 parts by mass of triethylamine were charged in a three-necked flask and heated to 55 ° C. while stirring. A solution obtained by mixing 4.9 parts by mass of 3-mercaptopropyltrimethoxysilane, 3.0 parts by mass of n-butyltrimethoxysilane and 42.2 parts by mass of propylene glycol monopropyl ether was added using a dropping funnel over 2 hours. And dripped. The reaction was further carried out at 55 ° C. for 1 hour, and methanol, water and triethylamine were distilled off under reduced pressure to obtain silsesquioxane having a sulfanylpropyl group and an n-butyl group. As a result of GPC measurement of the obtained silsesquioxane, it was Mw = 3,250 and Mn = 1,900. Moreover, it confirmed that the obtained silsesquioxane contained the cage silsesquioxane by liquid chromatograph mass spectrometry (LC-MS). This cage silsesquioxane is referred to as “silsesquioxane (D-4)”.

Synthesis of non-cage silsesquioxane Comparative Synthesis Example 1
In a three-necked flask under nitrogen atmosphere, 32.6 parts by mass of 3-mercaptopropyltrimethoxysilane and 31.9 parts by mass of n-butyltrimethoxysilane were added and dissolved by adding 100 parts by mass of methyl isobutyl ketone. The solution was heated to 60 ° C. while stirring with a magnetic stirrer. To this solution, 8.6 parts by mass of an oxalic acid aqueous solution containing 1% by mass of oxalic acid was continuously added over 1 hour, and the reaction was performed at 60 ° C. for 4 hours. Thereafter, water, methanol and methyl isobutyl ketone were distilled off under reduced pressure. The obtained product is dissolved in toluene, washed with water three times with a separatory funnel, dehydrated with a desiccant, and then distilled off under reduced pressure to have a sulfanylpropyl group and an n-butyl group. Silsesquioxane was obtained. It was confirmed by GPC measurement that the obtained silsesquioxane was a random type or a ladder type. This silsesquioxane is referred to as “silsesquioxane (d-2)”.

Example 1
(A) 200 parts by mass of a colorant dispersion (A-1) as a colorant, (B) 90 parts by mass of a binder resin solution (B-1) as a binder resin, and (C) caprolactone modification as a polyfunctional monomer 30 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPCA-60) and a polyfunctional acrylate mainly composed of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD MAX-3510) 30 parts by mass, 5 parts by mass of silsesquioxane (D-1) as component (D) (in terms of solid content), (E) 2-benzyl-2-dimethylamino-1- (4-morphol as a photopolymerization initiator Linophenyl) butan-1-one (Ciba Specialty Chemicals, trade name Irgacure 369) 25 parts by mass, 2 2 parts by weight of 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (trade name B-CIM, manufactured by Hodogaya Chemical Co., Ltd.), 2,4 -Diethylthioxanthone (Nippon Kayaku Co., Ltd., trade name CAYACURE DETX-S) 2 parts by mass, and propylene glycol monomethyl ether acetate as a solvent are mixed to prepare a liquid composition (S-1) having a solid content concentration of 20% by mass. Prepared.

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

Adhesion evaluation The liquid composition (S-1) was applied on a soda glass substrate having a diameter of 4 inches on the surface of which a SiO2 film for preventing elution of sodium ions was formed using a spin coater, and then applied to a hot plate. Was pre-baked at 90 ° C. for 1 minute to form a coating film having a thickness of 2.5 μm. Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 600 J / m ² without using a photomask. Thereafter, a 0.04% sodium carbonate aqueous solution at 23 ° C. was discharged onto the coating film at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm) to perform shower development, followed by post-baking at 230 ° C. for 20 minutes. A green cured film was formed on the substrate.
On the obtained cured film, an ITO film is produced using an ITO sputtering apparatus (manufactured by ULVAC) so that the film thickness becomes 500 mm, and according to JIS K5400 standard, it is cross-cut into 100 grids. An adhesion test was performed. When the number remaining without peeling off the grid was 90 or more, it was evaluated as ◯, when it was 80 or more and less than 90, Δ, and when it was less than 80, it was evaluated as ×. The evaluation results are shown in Table 2. It can be said that it is satisfactory if the number of remaining grids without peeling off is 90 or more.

Evaluation of solvent resistance After applying the liquid composition (S-1) on a soda glass substrate having a diameter of 4 inches on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater, Pre-baking was performed at 90 ° C. for 1 minute on a hot plate to form a coating film having a thickness of 2.5 μm. Next, after cooling the substrate to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 600 J / m ² through a photomask using a high-pressure mercury lamp. Thereafter, a developing solution composed of a 0.04 wt% sodium carbonate aqueous solution at 23 ° C. is discharged to the substrate at a developing pressure of 1 kgf / cm ² (nozzle diameter: 1 mm) to perform shower development, and then further to 230 ° C. Was post-baked for 20 minutes to form a 200 × 200 μm dot pattern on the substrate.
The obtained substrate was immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes, and the dot pattern before and after immersion was observed with a scanning electron microscope. The pattern did not change, and the film thickness ratio before and after immersion (after immersion) (Film thickness × 100 / film thickness before immersion) is 95% or more, and the film thickness ratio before and after immersion is less than 95%, or a case where a part of the pattern is chipped is Δ The case where all the patterns were peeled off from the substrate after immersion was evaluated as x. The evaluation results are shown in Table 2.

Evaluation of voltage holding ratio On a soda glass substrate on which a liquid composition (S-1) is formed with a SiO2 film on its surface to prevent elution of sodium ions, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape After applying using a spin coater, pre-baking was performed in a clean oven at 90 ° C. for 10 minutes to form a coating film having a thickness of 2.0 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 600 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer composed of a 0.04 wt% sodium carbonate aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 20 minutes. The coating film was cured to form green pixels on the substrate.
Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.018 mm glass beads, and then liquid crystal MLC6608 (trade name) manufactured by Merck is injected. Thus, a liquid crystal cell was produced.
Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica. The applied voltage at this time is a square wave of 5.0 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). The evaluation results are shown in Table 2.

Examples 2-14 and Comparative Examples 1-3
Liquid compositions (S-2) to (S-17) were prepared in the same manner as in Example 1 except that the types and amounts of the components of the liquid composition were as shown in Table 1.
Subsequently, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (S-2) to (S-17) were used instead of the liquid composition (S-1). The results are shown in Table 2.

In Table 1, each component is as follows.
C-1: Caprolactone-modified dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPCA-60)
C-2: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD MAX-3510)
D-5: Commercially available basket-type silsesquioxane having a sulfanyl group (sulfanyl group equivalent = 206 g / eq)
d-1: Pentaerythritol tetrakis (3-mercaptopropionate)
E-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (product name: Irgacure 369, manufactured by Ciba Specialty Chemicals)
E-2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by Ciba Specialty Chemicals, Product name Irgacure OXE02)
E-3: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (trade name B-CIM, manufactured by Hodogaya Chemical Co., Ltd.)
E-4: 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd., trade name CAYACURE DETX-S)
E-5: 1-hydroxy-cyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, trade name Irgacure 184)
F-1: Azoisobutyronitrile (trade name AIBN, manufactured by Otsuka Chemical Co., Ltd.)

  From Table 2, a pixel formed using the colored composition of the present invention containing (D) a cage silsesquioxane having a sulfanyl group and / or a polymerizable unsaturated group is a transparent conductive film or an inorganic film. The adhesiveness was excellent, the solvent resistance was excellent even at low exposure, and the voltage holding ratio was high.

Claims (6)

  (A) a colorant, (B) a binder resin, (C) a polyfunctional monomer, and (D) a cage silsesquioxy having at least one selected from the group consisting of a sulfanyl group and a polymerizable unsaturated group A coloring composition containing sun.   (B) The colored composition according to claim 1, wherein the binder resin contains a polymer having an acidic functional group and a polymerizable unsaturated group.   Furthermore, (E) The coloring composition of Claim 1 or 2 containing a photoinitiator.   The coloring composition according to claim 3, wherein the (E) photopolymerization initiator contains an O-acyloxime compound.   The color filter provided with the colored layer formed using the coloring composition of any one of Claims 1-4.   A liquid crystal display device comprising the color filter according to claim 5.