JP2010243960A - Coloring material composition for manufacturing color filter with high heat resistance, high transmittance, and high contrast - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring material composition for manufacturing a color filter having high heat resistance, high light transmittance, and high contrast. <P>SOLUTION: The coloring material composition is obtained by hydrolyzing and condensing a metal alkoxide in a solvent in the presence of a dyestuff composed of a triphenylmethane-based compound or its salt. The metal alkoxide is a compound expressed by there following general formula (2) or its condensate: M(OR23)<SB>n</SB>(2), wherein R23 represents a lower alkyl group, M represents a trivalent or tetravalent metal, and n represents a valency of the metal M. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a colorant composition and a color filter for producing a color filter.

  There are two methods for producing a color filter: a method using a dye as a colorant and a method using a pigment in which a large number of dye molecules are aggregated to lose solubility.

  Examples of the method using a dye include a dyeing method and a dye dissolving method. Examples of the method using a pigment include a pigment dispersion method and an electrodeposition method.

  When a dye is used as a coloring material, the color developability (chromaticity and light transmittance) is generally superior to that when a pigment is used. However, on the other hand, the dye has a problem that it is inferior in heat resistance as compared with the pigment. In particular, in the color filter manufacturing process, it is necessary to repeat the process of forming a pixel by applying a composition containing a coloring material on a substrate and heating it at 200 ° C. or higher for pixels of three colors, red, green, and blue. Therefore, the colorant composition needs to have high heat resistance that can withstand multiple heat treatments.

  Conventionally, as a method for producing a pixel of a color filter, a method in which a metal alkoxide is hydrolyzed and condensed in the presence of the compound using a compound in which a cyanine dye is covalently bonded to a polymer side chain (Patent Documents 1 and 2). And a sol-gel method using a metal alkoxide chemically bonded with an anthraquinone pigment and a free metal alkoxide not chemically bonded with a pigment (Patent Document 3) has been performed.

  Conventionally, when a triphenylmethane compound or the like is used as a colorant for a color filter, it is used in the form of a pigment in which a large number of dyes are aggregated, and this is directly mixed with a resist polymer and cured to produce a pixel. It was.

  However, the color filters obtained by these methods have insufficient heat resistance, light transmittance, and contrast.

US4948843 US5100970 JP-A-6-308314

  This invention makes it a subject to provide the coloring material composition for manufacture of a color filter which has all high heat resistance, high light transmittance, and high contrast.

  Under the circumstances as described above, as a result of intensive studies, the present inventors have used a triphenylmethane-based dye having a specific structure, and by performing a sol-gel reaction in the presence of the dye, It has been found that heat resistance can be achieved in addition to transparency and contrast. The present invention is based on the above novel findings.

Accordingly, the present invention provides the following sections:
Item 1. A colorant composition for producing a color filter, comprising a triphenylmethane-based compound represented by the following general formula (1) or a salt thereof and a metal alkoxide:

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, a lower alkyl group, or

(In formula, R < ⁹ > -R < ¹³ > is the same or different, and shows a hydrogen atom or a sulfonic acid group. M shows 0 or 1.)
Indicates.
R ³ represents a hydrogen atom or a lower alkyl group.
R ⁴ , R ^5, R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a sulfonic acid group or a hydroxyl group.
R ⁴ and R ⁵ are bonded together with the carbon atom to which they are bonded.

(In formula, R < ¹⁴ > -R < ¹⁷ > is the same or different and shows a hydrogen atom or a sulfonic acid group.)
An unsaturated 6-membered ring represented by
R ⁶ represents a hydrogen atom, a sulfonic acid group, an N-lower alkylamino group or

(In formula, R <^18> , R <^19> , R <^21> and R <^22> are the same or different and show a hydrogen atom or a sulfonic acid group. R < ²⁰ > shows a lower alkyl group.)
Indicates. ]
Item 2. Item 2. The colorant composition according to Item 1, obtained by hydrolyzing and condensing a metal alkoxide in a solvent in the presence of a dye comprising the triphenylmethane compound or a salt thereof.

Item 3. The metal alkoxide is represented by the following general formula (2)
M (OR ²³ ) _n (2)
[Wherein R ²³ represents a lower alkyl group.
M represents a trivalent or tetravalent metal.
n represents the valence of the metal M. ]
Item 3. The colorant composition according to Item 1 or 2, which is a compound represented by the formula (1) or a condensate thereof.

  Item 4. Item 4. The colorant composition according to any one of Items 1 to 3, further comprising a haloalkyltrialkoxysilane or a condensate thereof as a dispersant.

  Item 5. Item 5. The colorant composition according to any one of Items 1 to 4, further comprising at least one polymer selected from the group consisting of polyvinylpyridine, polyvinylpyrrolidone, and polyhydroxyalkyl (meth) acrylate.

  Item 6. Item 6. The colorant composition according to Item 5, wherein the polyhydroxyalkyl (meth) acrylate is a polymer having a repeating unit represented by the following general formula (3):

[Wherein, R ²⁵ represents a hydrogen atom or a methyl group. R ²⁶ represents a hydroxy lower alkyl group. ].

  Item 7. A color filter comprising a transparent substrate and a cured product of a composition comprising the colorant composition according to any one of Items 1 to 6 and a resin on the transparent substrate.

  Item 8. A liquid crystal display device comprising the color filter according to claim 7.

  The colorant composition for producing a color filter of the present invention is excellent in heat resistance while having the performance of high light transmittance and high contrast inherent in the dye. Therefore, the colorant composition of the present invention is very useful for producing a color filter obtained through a production process including a plurality of heating steps.

FIG. 1 shows the transmission spectra of the coating films of Examples 1 to 3 measured in the test example of the present application before the heat treatment. It is the schematic which shows an example of the liquid crystal display device of this invention.

1. Colorant Composition The present invention provides a colorant composition for producing a color filter, which contains a triphenylmethane dye represented by the general formula (1) and a metal alkoxide.

Triphenylmethane dyes or salts thereof Specific groups of the triphenylmethane dyes represented by the general formula (1) are as follows.

When R ¹ , R ² , R ³ or R ²⁰ is a lower alkyl group, examples of the lower alkyl group include a straight chain having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 2 carbon atoms. A linear or branched alkyl group can be mentioned. More specifically, methyl, ethyl, n-propyl, and isopropyl are included.

When R ⁶ is an N-lower alkylamino group, examples of the N-lower alkylamino group include a substituent having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 2 carbon atoms. An amino group having one linear or branched alkyl group can be exemplified. More specifically, N-methylamino, N-ethylamino, N- (n-propyl) amino, and N-isopropylamino are included.

Among the triphenylmethane dyes or salts thereof represented by the general formula (1), for example, one of the corresponding R ¹ and R ² represents a lower alkyl group and the other is a lower alkyl or

Indicate
The corresponding R ³ represents hydrogen,
Corresponding R ⁴ , R ⁵ , R ⁷ represents hydrogen and R ⁸ represents a sulfonic acid group, or R ⁴ and R ⁵ are bonded to each other

And R ⁷ and R ⁸ represent hydrogen and the corresponding R ⁶ is hydrogen or

Or a salt thereof is preferred.

  More preferably, examples of the triphenylmethane dye represented by the general formula (1) include Acid Blue 1, Acid Blue 3, Acid Blue 9, Acid Blue 83, and Acid Blue 90.

  The triphenylmethane dye represented by the general formula (1) which is the raw material compound of the present invention may be a suitable salt such as a salt of an inorganic base.

  Examples of such salts include metal salts such as alkali metal salts (for example, sodium salts, potassium salts, and lithium salts), alkaline earth metal salts (for example, calcium salts and magnesium salts), ammonium salts, and the like. be able to.

  These triphenylmethane compounds or salts thereof are used singly or in combination of two or more.

  The colorant composition of the present invention uses the above-mentioned triphenylmethane compound or a salt thereof, and after the metal alkoxide is hydrolyzed and condensed, the dye molecule is soluble in the three-dimensional matrix of metal oxide. A pseudo-crystal bulk in which associated aggregates are dispersed can be formed, thereby achieving both high heat resistance and high permeability.

  In a preferred embodiment of the present invention, the above-described triphenylmethane compound or a salt thereof is subjected to the sol-gel method described later in a dye state in which a large number of these aggregates are dissolved and dispersed in a solvent. By performing the sol-gel method in such a state that the dye is dissolved and dispersed in the solvent, the pseudo-crystal bulk is easily formed.

Metal alkoxide As the metal alkoxide used in the present invention, those used in the sol-gel method can be widely used, and examples thereof include those represented by the following formula (2):
M (OR ²³ ) _n (2)
[Wherein R ²³ represents a lower alkyl group.
M represents a trivalent or tetravalent metal.
n represents the valence of the metal M. ]
Examples of the trivalent or tetravalent metal represented by M include silicon, titanium, zirconium, and aluminum, with silicon being preferred.

Examples of the lower alkyl group represented by R ²⁴ include linear or branched alkyl groups having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 1 carbon atom. More specifically, methyl, ethyl, n-propyl, and isopropyl are included.

  These metal alkoxides are used individually by 1 type or in mixture of 2 or more types.

  The metal alkoxide may be blended in the raw material composition as a monomer (metal alkoxide itself), or as a raw material of the colorant composition of the present invention as a partially condensed metal oxide such as an oligomer such as a dimer or trimer. After blending into the composition, it may be carried out before hydrolysis and condensation, or a part thereof may be blended in the raw material mixture as a polymer. When blended as an oligomer or polymer such as a dimer or trimer, these may be oligomers or polymers obtained by condensing the metal alkoxide of the general formula (2) by a sol-gel method or the like. One kind of alkoxysilane compound (silane coupling agent), alkoxytitanium compound (titanium coupling agent), alkoxyzirconium compound (zirconium coupling agent), alkoxyaluminum compound (aluminum coupling agent), etc. The compound which the above compound and the metal alkoxide of General formula (2) condensed may be sufficient. In addition, the oligomer or polymer which condensed the metal alkoxide of General formula (2) by the sol-gel method etc. may condense the same metal alkoxide of General formula (2), and 2 or more types contained in General formula (2) The metal alkoxide may be condensed. Examples of the condensation method include a sol-gel method performed in the presence of an acid catalyst or an alkali catalyst in a solvent such as alcohol.

  In the colorant composition of the present invention, the mixing ratio of the metal alkoxide and the dye is 40 to 95 parts by weight of the metal alkoxide and 5 to 60 parts by weight of the dye, preferably metal alkoxide, when the total of these is 100 parts by weight. 50-90 weight part and 10-40 weight part of dye are mentioned.

In the colorant composition of the present invention such as a dispersant, a dispersant may be added to improve the dispersibility of the dye. However, care should be taken because durability may be impaired depending on the amount and type of addition. The dispersant is used to uniformly disperse the dye in the medium and stabilize the state at the time of mixing the dye and the sol-gel. Examples of the type of dispersant include a surfactant and a silane coupling agent. The term “surfactant” as used herein refers to a substance having a structure in which a hydrophilic part and a lipophilic part are linked by a covalent bond in one molecule, and it may be a low molecule or a polymer. The hydrophilic portion includes an anion type (acid), a cation type (base, onium salt (NR ⁴⁺ )), and a nonion type. The nonionic type is generally polyethylene oxide (PEO) or polyol having no ion dissociation properties, and these oxygen atoms are hydrated by hydrogen bonding and show hydrophilicity regardless of pH. A silane coupling agent is an organosilicon compound having a functional group reactively bonded in a molecule and a functional group reactively bonded to an inorganic material. A silane coupling agent is preferably used, and specific examples include glycidyloxyalkyltrialkoxysilane, methacryloxytrialkoxysilane, haloalkyltrialkoxysilane, aminoalkyltrialkoxysilane, and the like. In particular, haloalkyltrialkoxysilane is preferable in terms of improving dispersibility of the dye in the medium and imparting stability.

  Here, the haloalkyl group in the haloalkyltrialkoxysilane may have, for example, 1 to 3, preferably 1 halogen atom, 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, More preferable examples include a linear or branched alkyl group having 3 carbon atoms. Specifically, fluoromethyl, chloromethyl, bromomethyl, 2,2-difluoroethyl, 2-fluoroethyl, 2-chloroethyl, 3,3,3-trichloropropyl, 3-chloropropyl, 2-chloropropyl, 3- Bromopropyl, 4,4,4-trifluorobutyl, 4-chlorobutyl, 4-bromobutyl, 2-chlorobutyl, 5-chloropentyl, 6,6,6-trifluorohexyl, 6-chlorohexyl and the like, Preferably, 3-chloropropyl can be illustrated.

  Examples of the alkoxy group in the haloalkyltrialkoxysilane include linear or branched alkoxy groups having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms, and more preferably 1 carbon atom. More specifically, methoxy, ethoxy, n-propoxy, and isopropoxy are included. In the present invention, the three alkoxy groups in the haloalkyltrialkoxysilane may be the same or different.

  In this embodiment, the blending ratio of the metal alkoxide and the dispersant is usually 0.001 to 1 part by weight, preferably 0.005 to 0.5 parts by weight, with respect to 1 part by weight. More preferably, it is 0.01-0.3 weight part.

  The colorant composition of the present invention contains a polymer such as polyvinyl acetate and a hydrolyzate thereof, polyvinyl pyridine, polyvinyl pyrrolidone, polyhydroxyalkyl (meth) acrylate, in addition to the above-described dye and a dispersant as required. Furthermore, what is obtained by hydrolyzing and condensing a metal alkoxide in a solvent in the presence is also included.

  Examples of polyvinyl pyridine include poly (2-, 3- or 4-vinyl pyridine).

  Examples of polyvinylpyrrolidone include poly [N-vinyl- (2 or 3-) pyrrolidone], poly [2-vinyl- (3-, 4- or 5-) pyrrolidone], and poly [3-vinyl- (2 -, 4- or 5-) pyrrolidone].

  The weight average molecular weight of these polymers is usually 3,000 to 1,000,000, preferably 5,000 to 700,000, more preferably 10,000 to 500,000.

  Among these polymers, a polymer having a repeating unit represented by the following general formula (3) is preferable:

[Wherein, R ²⁵ represents a hydrogen atom or a methyl group. R ²⁶ represents a hydroxy lower alkyl group. ]
Here, as the hydroxy lower alkyl group represented by R ²⁶ , for example, it may have 1 to 3, preferably 1 hydroxyl group, having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferable examples include linear or branched alkyl groups having 2 to 3 carbon atoms. Specifically, hydroxymethyl, 2,2-dihydroxyethyl, 2-hydroxyethyl, 3,3,3-trihydroxypropyl, 3-hydroxypropyl, 2-hydroxypropyl, 4,4,4-trihydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl, 6,6,6-trihydroxyhexyl, 6-hydroxyhexyl and the like are included, preferably 2-hydroxyethyl, 2-hydroxypropyl and the like. It is done.

  These polymers are used individually by 1 type or in mixture of 2 or more types.

These polymer monomers may be mixed and polymerized in the system.
In the embodiment, the blending ratio of the metal alkoxide and the polymer is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 1 part by weight relative to the 1 part by weight. 0.1 to 3 parts by weight.

  Use of the above polymer is preferable because the heat resistance can be further improved.

  Moreover, in addition to the said dye and the dispersing agent as needed, you may add an aryl alkoxysilane to the coloring agent composition of this invention.

  Here, the arylalkoxysilane has a structure in which, for example, 1 to 2 (preferably 1) aryl groups and 2 to 3 (preferably 3) alkoxy groups are bonded to silicon, for a total of four. When two or more aryl groups are bonded to silicon, each aryl group may be the same or different. The same applies when two or more alkyl groups are bonded to silicon.

  Examples of the aryl group in the arylalkoxysilane include a phenyl group, a naphthyl group, a biphenyl group, and a terphenyl group, and a phenyl group is particularly preferable.

Here, the aryl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, hydroxy (OH), amino (NH ₂ ), Examples include alkylamino, dialkylamino, acyloxy, alkoxyalkyl, methylenedioxy and the like. The number of substituents is 1 to 3, preferably 1 to 2, especially 1. When the substituent is a halogen atom, the number of substituents is preferably 1 or 2, particularly preferably 1.

  When the aryl group has a halogen atom as a substituent, examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

  When the aryl group has an alkyl group as a substituent, examples of the alkyl group include linear or branched alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, Examples thereof include n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like.

  When the aryl group has an alkoxy group as a substituent, examples of the alkoxy group include linear or branched alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, n-propoxy, isopropoxy 1-methylpropoxy, n-butoxy, isobutoxy, 2-methyl-butoxy, neopentyloxy, pentan-2-yloxy and the like.

  When the aryl group has an alkylthio group as a substituent, the alkylthio group preferably represents a linear or branched alkylthio having 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, Examples include n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio and the like.

  When the aryl group has an aryloxy group as a substituent, examples of the aryloxy group include phenoxy and naphthoxy.

  When the aryl group has a mono- or dialkylamino group as a substituent, the mono- or dialkylamino group is mono-substituted or di-substituted by the alkyl group having 1 to 6 carbon atoms or a straight chain or branched chain. Examples thereof include amino groups such as methylamino, dimethylamino, ethylamino, diethylamino, and methylethylamino.

  When the aryl group has an acyloxy group as a substituent, the acyloxy group includes formyloxy, acetyloxy, propionyloxy, n-butyryloxy, isobutyryloxy, valeryloxy, isovaleryloxy, pivaloyloxy, benzoyloxy, etc. Examples thereof include a linear or branched acyloxy group having 1 to 7 carbon atoms.

  When the aryl group has an alkoxyalkyl group as a substituent, examples of the alkoxyalkyl group include methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, and the like.

  Examples of the alkyl group bonded to silicon in the arylalkoxysilane include a methyl group, ethyl, and n-propyl, preferably methyl or ethyl.

These arylalkoxysilanes are used singly or in combination of two or more.
In this embodiment, the mixing ratio of the metal alkoxide and the arylalkoxysilane is usually 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, with respect to 1 part by weight. Preferably, it is 0.3 to 10 parts by weight.

  Addition of arylalkoxysilane is preferable because heat resistance and light resistance are improved.

  When an aryl dialkoxysilane is used as the arylalkoxysilane, the dialkoxide is used in proportion to the trialcoside and tetraalkoxide compounded in the colorant composition of the present invention (the above metal alkoxide, aryltrialkoxysilane and silane coupling agent). The latter is usually used in an amount of 0.001 to 1 mol, preferably 0.005 to 1 mol, and more preferably 0.01 to 0.5 mol.

  Tertiary amine is mentioned as a catalyst used for a sol-gel method, mainly a polycondensation catalyst. For example, there are N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like, and NN-dimethylbenzylamine is particularly preferable. The amount used is 0.01 to 1 part by weight, preferably about 0.03 part by weight, per 100 parts by weight of the total amount of alkoxide and each coupling agent.

  In the production of the colorant composition according to the present invention, the condensation reaction may be performed in the presence of an acid instead of the tertiary amine or together with the tertiary amine. The acid is used as a sol-gel catalyst, mainly as a catalyst for hydrolysis of alkoxides, silane coupling agents and the like. As the acid, mineral acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as acetic acid and tartaric acid are used. The amount of the acid used is 0.001 to 0.05 mol, preferably about 0.01 mol, based on the total molar amount of the alkoxide and the alkoxide content (for example, silicate moiety) of the silane coupling agent.

  In the colorant composition of the present invention, as long as at least a part of the metal alkoxide is hydrolyzed and condensed, the sol form, the gel form (ink composition), the solid form (coloring composition), and the metal oxidation Any state in which the dye is retained in the product matrix to form particles and the product is dispersed in a solvent, sol, or gel is included. In addition, the colorant composition of the present invention includes those containing solvent molecules in a dispersed state and those containing the solvent molecules in an associated state to the extent that they are soluble.

2. Color Filter The color filter of the present invention can be produced by using the colorant composition of the present invention instead of a conventional dye or pigment according to a conventional method.

  For example, a method for producing a color filter for liquid crystal display using a color resist containing a colorant composition, a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent of the present invention includes a binder resin and a photopolymerizable monomer. And a photosensitive solution obtained by dispersing or mixing the colorant composition of the present invention in a transparent photosensitive resin containing a photopolymerization initiator is applied onto a transparent glass substrate to form a photosensitive resin layer. Next, a mask having an opening pattern of a predetermined shape is placed on the photosensitive resin layer, and exposure and development are performed to form a first colored layer. Similarly, a second colored layer and a third colored layer can be formed to obtain a color filter having R, G, and B colored layers.

  The binder resin used in the present invention is preferably a linear organic high molecular polymer that is compatible with the photopolymerizable monomer and is soluble in a solvent and developable. Specifically, use of methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, polyimide resin, etc. Can do.

  The photopolymerizable monomer used in the present invention preferably has at least one addition-polymerizable ethylenically unsaturated group and has a boiling point of 100 ° C. or higher at room temperature. Specifically, monofunctional acrylates and methacrylates, those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols and then methacrylates can be used. Furthermore, polyfunctional acrylates such as polyester acrylates, epoxy acrylates which are reaction products of epoxy resins and methacrylic acid, methacrylates, photocurable monomers and oligomers, butyral resins, styrene-maleic acid copolymers, Polyvinyl acetate, phenol resin, and the like can be used, but it is preferable to use a polyfunctional acrylate monomer for the reason of reactivity.

Photopolymerization initiators used in the present invention include vicinal polyketoaldonyl compounds, α-carbonyl compounds, acioin ethers, multi-quinone compounds, triallylimidazole dimer / p-aminophenyl ketone combinations, trioxadiazoles Examples thereof include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (Irgacure 369: trade name, manufactured by Ciba Specialty Chemicals).
As the solvent used in the present invention, glycol ether solvents, acetate solvents thereof, acetate esters solvents and ketone solvents can be appropriately used. In particular, cyclohexanone and propylene glycol monomethyl ether acetate can be preferably used.

  Examples of the solvent used in the present invention include alcohol solvents, ether solvents, ester solvents and the like.

  The alcohol solvent used in the present invention is not particularly limited as long as it is an organic solvent that does not react with each component in the color material composition and can dissolve or disperse them. Specifically, alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, and i-propyl alcohol, cellosolve solvents such as methoxy alcohol and ethoxy alcohol, and carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol Etc. can be used suitably.

These solvents may be used alone or in combination of two or more.
The transparent substrate used in the present invention is not particularly limited as long as it is a substrate transparent to visible light. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.

  The coating method is not particularly limited, and examples thereof include a spray coating method, a dip coating method, a bar coating method, a roll coating method, and a spin coating method.

  Hereinafter, a liquid crystal display device will be described as an application of the color filter of the present invention, but the color filter of the present invention can also be used in combination with an organic EL such as a white light-emitting organic EL.

3. Next, the liquid crystal display device of the present invention will be described. The liquid crystal display device of the present invention has the above color filter.

  Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic view showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, the liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.

  According to the present invention, the use of the color filter makes it possible to obtain a liquid crystal display device with high quality such as high contrast and excellent productivity.

  The liquid crystal display device of the present invention uses at least the color filter according to the present invention.

  Hereinafter, the liquid crystal display device of the present invention will be described.

  The liquid crystal display device of the present invention is characterized in that the color filter is used. Accordingly, the color filter used in the present invention is the same as that described in the above section “2. Color filter”, and thus the description thereof is omitted here.

  The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for a liquid crystal display device can be adopted. Examples of such a drive method include a TN method, an IPS method, an OCB method, and an MVA method. In the present invention, any of these methods can be preferably used.

  Further, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.

  The liquid crystal layer in the present invention is provided between the color filter and the counter substrate. As the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.

  As shown in FIG. 2, the liquid crystal display device of the present invention usually includes a color filter using the color filter, the counter substrate, and the liquid crystal layer. Is not limited to such a configuration, and can be a configuration known as a liquid crystal display device in which a color filter is generally used.

  As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method.

  In the vacuum injection method, for example, a liquid crystal cell is prepared in advance using a color filter and a counter substrate, and the liquid crystal is heated to obtain an isotropic liquid, and the liquid crystal is applied to the liquid crystal cell using the capillary effect. The liquid crystal layer can be formed by injecting in this state and sealing with an adhesive. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

  In the liquid crystal dropping method, for example, a sealant is applied to the periphery of the color filter, the color filter is heated to a temperature at which the liquid crystal becomes isotropic, and the liquid crystal is dropped in an isotropic liquid state using a dispenser or the like. Then, the color filter and the counter substrate are overlapped with each other under a reduced pressure, and bonded through a sealant, whereby a liquid crystal layer can be formed. Thereafter, the sealed liquid crystal can be aligned by slowly cooling the liquid crystal cell to room temperature.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, it cannot be overemphasized that this invention is not limited to these Examples.

Example 1
Sol-gel-dye coloring material composition 1
To the reaction vessel, 13.2 parts by weight of methanol, 1.07 parts by weight of the dye Acid Blue 90, 1.92 parts by weight of tetramethoxysilane, 0.68 parts by weight of pure water and 0.23 parts by weight of 0.5N hydrochloric acid were added. The mixture was further stirred at room temperature for 20 hours. This was filtered using a membrane filter to remove insolubles.

  The obtained filtrate was applied to a 0.7 mm thick glass substrate (NA Techno Glass Co., Ltd., NA35) by spin coating. Then, it heat-dried for 2 minutes on a 150 degreeC hotplate, and obtained the coating film of the said sol-gel-dye coloring material composition 1 with a thickness of 0.6 micrometer +/- 0.1 micrometer.

Example 2
Sol-gel-dye coloring material composition 2
A coating film of the sol-gel-dye colorant composition 2 was obtained in the same manner as in Example 1 except that 1.04 parts by weight of the dye Acid Blue 9 was used instead of 1.07 parts by weight of Acid Blue 90.

Example 3
Sol-gel-dye coloring material composition 3
A coating film of the sol-gel-dye colorant composition 3 was obtained in the same manner as in Example 1 except that 0.67 part by weight of the dye Basic Blue 7 was used instead of 1.07 part by weight of Acid Blue 90.

Example 4
Sol-gel-dye coloring material composition 4
13.2 parts by weight of methanol, 1.07 parts by weight of the dye Acid Blue 90 and 0.25 parts by weight of chloropropyltrimethoxysilane were mixed and stirred at room temperature for 20 hours. To this was added 1.72 parts by weight of tetramethoxysilane, 0.61 part by weight of pure water, and 0.2 part by weight of 0.5N hydrochloric acid, and the mixture was further stirred at room temperature for 20 hours. This was filtered using a membrane filter to remove insolubles.
The obtained filtrate was applied to a 0.7 mm thick glass substrate (NA Techno Glass Co., Ltd., NA35) by spin coating. Then, it heat-dried for 2 minutes on a 150 degreeC hotplate, and obtained the coating film of the said sol-gel-dye coloring material composition 4 with a thickness of 0.6 micrometer +/- 0.1 micrometer.

Example 5
Sol-gel-dye coloring material composition 5
A coating film of the sol-gel-dye colorant composition 5 was obtained in the same manner as in Example 4 except that 1.04 parts by weight of the dye Acid Blue 9 was used instead of 1.07 parts by weight of Acid Blue 90.

Example 6
Sol-gel-dye coloring material composition 6
A coating film of the sol-gel-dye coloring material composition 6 was obtained in the same manner as in Example 4 except that 0.33 part by weight of bromopropyltrimethoxysilane was used instead of 0.25 part by weight of chloropropyltrimethoxysilane. .

Example 7
Sol-gel-dye coloring material composition 7
A mixture of 3.6 parts by weight of methanol and 0.32 parts by weight of the dye Acid Blue 90 was mixed with 1.0 part by weight of a methanol solution of 10% by weight poly (hydroxyethyl methacrylate) (weight average molecular weight 300,000 produced by Aldrich). In addition, well stirred. To this were added 2.69 parts by weight of tetramethoxysilane, 0.68 parts by weight of pure water and 0.23 parts by weight of 0.5N hydrochloric acid, and the mixture was further stirred at room temperature for 20 hours. Filtration was performed using a membrane filter to remove insoluble matters.

  The obtained filtrate was applied to a 0.7 mm thick glass substrate (NA Techno Glass Co., Ltd., NA35) by spin coating. Then, it heat-dried for 2 minutes on a 150 degreeC hotplate, and obtained the coating film of the said sol-gel-dye coloring material composition 7 of thickness 0.6 micrometer +/- 0.1 micrometer.

Example 8
Sol-gel-dye coloring material composition 8
Coating film of the sol-gel-dye coloring material composition 8 in the same manner as in Example 7 except that poly (2-hydroxypropyl methacrylate) (weight average molecular weight 200,000, manufactured by Aldrich) was used instead of polyhydroxyethyl methacrylate. Got.

Example 9
Sol-gel-dye coloring material composition 9
A coating film of the sol-gel-dye colorant composition 9 was formed in the same manner as in Example 7 except that poly (4-vinylpyridine) (weight average molecular weight 200,000 manufactured by Aldrich) was used instead of polyhydroxyethyl methacrylate. Obtained.

Example 10
Sol-gel-dye coloring material composition 10
In the same manner as in Example 7 except that poly (N-vinyl-2-pyrrolidone) (Aldrich weight average molecular weight 55,000) was used instead of polyhydroxyethyl methacrylate, the sol-gel-dye coloring material composition 10 A coating film was obtained.

Comparative Example 1
Dye polymer dispersion composition 1
Poly (hydroxyethyl methacrylate) (Aldrich weight average molecular weight 300,000) 0.3 parts by weight is dissolved in methanol 4.5 parts by weight, and Acid Blue 90 0.2 part by weight is added to this, and it is room temperature for 20 hours. Stir. Filtration was performed using a membrane filter to remove insoluble matters.

  The obtained filtrate was applied to a 0.7 mm thick glass substrate (NA Techno Glass Co., Ltd., NA35) by spin coating. Then, it heat-dried for 2 minutes on a 150 degreeC hotplate, and obtained the coating film of the polymer dispersion composition 1 of the said dye with a thickness of 0.6 micrometer +/- 0.1 micrometer.

Comparative Example 2
Dye polymer dispersion composition 2
In the same manner as in Comparative Example 1 except that poly (2-hydroxypropyl methacrylate) (weight average molecular weight 200,000 manufactured by Aldrich) was used instead of polyhydroxyethyl methacrylate, a coating film of the polymer dispersion composition 2 of the above dye was applied. Obtained.

Comparative Example 3
Dye polymer dispersion composition 3
A coating film of the sol-gel-dye colorant composition 3 was formed in the same manner as in Comparative Example 1 except that poly (4-vinylpyridine) (weight average molecular weight 200,000 manufactured by Aldrich) was used instead of polyhydroxyethyl methacrylate. Obtained.

Comparative Example 4
Dye polymer dispersion composition 4
In the same manner as in Comparative Example 1 except that poly (N-vinyl-2-pyrrolidone) (weight average molecular weight 55,000 manufactured by Aldrich) was used instead of polyhydroxyethyl methacrylate, A coating film was obtained.

Test Example The obtained coating film was subjected to a heat resistance test.
In the heat resistance test, a sample of the coating film is placed in a holder and placed in an oven heated to 230 ° C. for 30 minutes. Measurement was performed using a microspectroscope OSP-SP200. This operation was repeated three times, and the reduction rate of the transmittance peak and ΔEab were calculated from the obtained values and are summarized in Table 1.

Here, the reduction rate of the transmittance peak and ΔE can be calculated from the following equations.
Reduction rate of transmittance peak = [transmittance peak value measured before first heat treatment (initial peak transmittance) −transmittance peak value measured after each heat treatment] / initial peak transmittance × 100 (%)
ΔE = (Δa ² + Δb ² + ΔL ² ) ^1/2
Here, Δa, Δb, and ΔL indicate differences between a, b, and L after each heat treatment and a, b, and L before the first heat treatment.

In the above table, the heat resistance is higher when the decrease rate is smaller and the color difference ΔE is smaller.
In Examples 1 to 10 and Comparative Examples 1 to 4, a high transmittance of 80% or more indicating the high permeability of the dye was exhibited. As an example, the transmission spectra of Examples 1 to 3 are shown in FIG.

  In Example 1 in which Acid Blue 90 was dispersed in a sol-gel, the rate of decrease in peak transmittance was significantly lower than in Comparative Examples 1 to 4 in which the same dye was dispersed in an organic polymer, and the heat resistance was high.

  Examples 2 and 3 using Acid Blue 9 and Basic Blue 7 as dyes also showed higher heat resistance than Comparative Examples 1 to 4. This shows that the heat resistance is improved by this method regardless of whether the dye is an acidic dye or a basic dye.

  Examples 4 and 5 using chloropropyltrimethoxysilane as a dispersant have higher heat resistance than Examples 1 and 2 using the same dye. This is presumably because the dispersing agent contributed to further fixing the quasicrystalline bulk structure formed while uniformly dispersing the association state of the dye.

  Example 6 using bromopropyltrimethoxysilane as a dispersant showed high heat resistance equivalent to or higher than Example 4 using the same dye. The reason why heat resistance has improved slightly is that the interaction capacity of the dispersant is higher in bromo groups than in chloro groups, and as a result, the aggregated state of the dye is uniformly dispersed and the resulting pseudocrystalline bulk structure is further fixed. It is thought that it contributed to doing.

  In Examples 7 to 10 in which an organic polymer was mixed with a sol-gel-dye composition, heat resistance was greatly improved as compared with Comparative Examples 1 to 4 in which the same dye was dispersed only in the organic polymer. Furthermore, even when compared with Example 1 in which the same dye was used and dispersed in sol-gel, high heat resistance was exhibited. In addition to the ability of the inorganic silica binder to uniformly disperse and fix the dye in the associated state, the flexibility of the organic polymer is added, and as a result, the thermal motion of the dye-associated state is relaxed, thereby improving the heat resistance. It is thought to have improved. It is also considered that the organic polymer and the inorganic sol-gel silica interact and disperse closely to form an organic-inorganic hybrid bulk, and the associated dye is uniformly dispersed and immobilized.

DESCRIPTION OF SYMBOLS 1 ... Transparent substrate 2 ... Light-shielding part 3 ... Colored layer 10 ... Color filter 20 ... Opposite substrate 30 ... Liquid crystal layer 40 ... Liquid crystal display device

Claims (8)

A colorant composition for producing a color filter, comprising a triphenylmethane-based compound represented by the following general formula (1) or a salt thereof and a metal alkoxide:

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, a lower alkyl group, or

(In formula, R < ⁹ > -R < ¹³ > is the same or different, and shows a hydrogen atom or a sulfonic acid group. M shows 0 or 1.)
Indicates.
R ³ represents a hydrogen atom or a lower alkyl group.
R ⁴ , R ^5, R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom, a sulfonic acid group or a hydroxyl group.
R ⁴ and R ⁵ are bonded together with the carbon atom to which they are bonded.

(In formula, R < ¹⁴ > -R < ¹⁷ > is the same or different and shows a hydrogen atom or a sulfonic acid group.)
An unsaturated 6-membered ring represented by
R ⁶ represents a hydrogen atom, a sulfonic acid group, an N-lower alkylamino group or

(In formula, R <^18> , R <^19> , R <^21> and R <^22> are the same or different and show a hydrogen atom or a sulfonic acid group. R < ²⁰ > shows a lower alkyl group.)
Indicates. ]   The colorant composition according to claim 1, which is obtained by hydrolyzing and condensing a metal alkoxide in a solvent in the presence of a dye comprising the triphenylmethane compound or a salt thereof. The metal alkoxide is represented by the following general formula (2)
M (OR ²³ ) _n (2)
[Wherein R ²³ represents a lower alkyl group.
M represents a trivalent or tetravalent metal.
n represents the valence of the metal M. ]
The coloring material composition according to claim 1, which is a compound represented by the formula (1) or a condensate thereof.   Furthermore, the coloring material composition as described in any one of Claims 1-3 containing a haloalkyl trialkoxysilane or its condensate as a dispersing agent.   Furthermore, the coloring material composition as described in any one of Claims 1-4 containing the at least 1 type of polymer selected from the group which consists of polyvinyl pyridine, polyvinyl pyrrolidone, and polyhydroxyalkyl (meth) acrylate. The colorant composition according to claim 5, wherein the polyhydroxyalkyl (meth) acrylate is a polymer having a repeating unit represented by the following general formula (3):

[Wherein, R ²⁵ represents a hydrogen atom or a methyl group. R ²⁶ represents a hydroxy lower alkyl group. ].   A color filter provided with the hardened | cured material of the composition containing a transparent substrate and the coloring material composition and resin as described in any one of the said Claims 1-6 on the said transparent substrate.   A liquid crystal display device comprising the color filter according to claim 7.

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