JP2001207115A - Color coating liquid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a uniform and transparent color coating liquid composition capable of being prepared so as to have optional physical properties without using dispersants. SOLUTION: This color coating liquid composition comprises a metal alkoxide and/or a hydrolyzed condensate of the metal alkoxide and a latent pigment. The color coating liquid composition can be used for a photoabsorption filter for a specific wavelength rage of a display device by coating a material having light transmissivity therewith. Besides, a colored glass bottle capable of being recycled as a transparent cullet can be produced by coating the glass bottle with the color coating liquid composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored paint composition, a colored substrate having the colored paint composition applied on its surface, a display filter, and a display device using the filter. In addition, the present invention relates to a colored glass bottle having a colored coating composition applied to the surface thereof and recyclable as a transparent cullet.

[0002]

2. Description of the Related Art In general, glass products are often used in a colored state. For example, they are used for applications such as a colored filter and a colored glass bottle provided in a liquid crystal display device. This coloring filter is used for absorbing the wavelength of the intermediate color emitted from the liquid crystal display device and improving the contrast. Generally, such a color filter or a color bottle is prepared by blending an organic dye (for example, a dye or a pigment) with silica sol and applying it to the glass surface.
It is obtained by a method of firing and gelling, a so-called sol-gel method. However, in general, in the case of the sol-gel method, when the firing temperature is increased, the obtained colored thin film becomes dense, but when an organic dye is used, the organic dye is decomposed at a high temperature.
Therefore, the firing temperature cannot be increased, and the resulting film has extremely large pores. In particular, when a dye is used, the dye is easily dissolved in water, so that the dye is eluted and the deterioration of the film proceeds rapidly. Further, in the case of a glass bottle, water resistance and chemical resistance are inferior, and there is a problem such as elution of a dye.

A method for improving such a problem is described in Japanese Patent Application Laid-Open No. 5-178623. In this method, a metal alkoxide and an organic pigment of fine particles of 3 to 300 nm (for example, a phthalocyanine pigment, a yellow or red azo pigment such as benzidine yellow or carmine FB, etc.) are dispersed using an alcohol-soluble dispersant. This is a method in which a colored filter is obtained by applying the composition on a glass surface, followed by baking.

However, this method has several problems. For example, there is a problem that the dispersant is limited to those soluble in alcohol. Also compatible with pigments,
In addition, a pigment dispersion must be prepared by selecting a dispersant that is also compatible with the metal alkoxide, and if this is not performed properly, the performance of the resulting thin film will be poor. There is. Further, 3 nm to 300 nm
In order to obtain the fine particles, a great effort is required for adjusting the particle size, and a great effort is required for the uniform dispersion of the pigment. In addition, there is a problem that a transparent colored thin film cannot be obtained unless the particle size adjustment and uniform dispersion are properly performed. Therefore, at present, there is a great technical difficulty in dispersing a pigment using a dispersant and obtaining a transparent colored thin film. This is the same for colored glass bottles.

On the other hand, Japanese Patent Laid-Open No. 9-3362 discloses that
A method is described in which a solution or melt of a latent pigment is applied to a substrate to obtain a colored substrate. Since the colored thin film obtained by this method is only a thin film having the physical properties of the pigment itself, there is a problem that the use is limited to the use suitable for the physical properties. That is, in order to use a colored thin film for various uses, physical properties such as strength, water resistance, and weather resistance of the thin film according to the use and purpose are necessary, but there is a problem that such physical properties are difficult to obtain. .

Accordingly, a colored thin film having excellent uniformity and transparency and having desired coating film properties can be formed, and various uses such as a colored glass bottle which can be used not only as a colored substrate but also as a transparent cullet. There is a demand for a colored coating solution composition that can be used in applications.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a metal alkoxide and / or a hydrolyzed condensation polymer of a metal alkoxide, a latent pigment, To provide a colored coating composition using
It is an object to provide a colored substrate having a colored thin film that is transparent and has excellent weather resistance, and a filter and a display device having the colored substrate. Another object of the present invention is to provide a glass bottle having a colored thin film, which can be recycled as a transparent cullet.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a colored coating composition containing a metal alkoxide and / or a hydrolyzed polycondensate of the metal alkoxide and a latent pigment.

In a preferred embodiment, the metal alkoxide has the following general formula (1): R ¹ _nM (OR ² ) _mn (1) (wherein R ¹ is independently C1 to C6 (Cyclo) alkyl group, C6-C9 aryl group, C7-C10 aralkyl group, C2-C5 alkenyl group, (meth) acryloxy-C1-C4 alkyl group, glycidoxy-C1-
The C4 alkyl group, M is silicon, titanium, zirconium or aluminum, an alkyl group of ^{R 2} is independently C1 -C4, m is 3 or 4 integer, n is an integer of 0 to 2. ).

In a preferred embodiment, the latent pigment is represented by the following general formula (2): A (B) x (2) (wherein X is an integer of 1 to 8, A is quinacridone,
Anthraquinone, perylene, indigo, quinophthalone,
Indanthrone, isoindolinone, isoindoline,
Dioxazine, phthalocyanine, diketopyrrolopyrrole or azo series colorant residue, this residue A
It contains X heteroatoms, which are conjugated or adjacent to at least one carbonyl group, and B is a group of formula (3): -C (= O ^{) -O-R 3 (3)} ( wherein, R ³ is a substituted or unsubstituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group or an aralkyl group.), which is Attached to one of the above heteroatoms).

[0011] The present invention also relates to a colored substrate obtained by applying the colored coating solution composition to a surface and heating the composition.

The present invention further relates to a filter for a display having a light-transmitting colored substrate obtained by applying the colored coating solution composition to a surface of a light-transmitting substrate and heating the composition. In a preferred embodiment, the light transmitting substrate is glass, and selectively absorbs a wavelength in a specific wavelength range.

Further, the present invention relates to a display device having a light transmissive display portion, wherein the display filter is provided on an outer surface of the light transmissive display portion.

[0014] The present invention also relates to a colored glass bottle obtained by applying the above-mentioned colored coating solution composition to the surface of a glass bottle and heating the glass bottle.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is intended to uniformly mix a metal alkoxide and / or a hydrolyzed polycondensate of a metal alkoxide with a solution in which latent pigment is dissolved, and to obtain a mixed solution (colored coating solution composition). Thing is,
It has been completed by finding that a colored thin film which is strong, transparent and excellent in weather resistance can be formed. Conventional, when using a colored coating composition in which pigment fine particles are dispersed,
It is necessary to use a dispersant, and it is necessary to adjust the pigment to an average particle diameter of 3 to 300 nm, which requires a large amount of work for preparation, and the type and amount of the dispersant cannot be arbitrarily changed. In addition, while there is a problem of being limited to alcohol-soluble dispersants, the colored coating composition of the present invention using a solution of latent pigment does not use a dispersant, and uses a metal By changing the type and amount of the alkoxide and / or its hydrolyzed polycondensate, it has the feature that any physical properties can be obtained.

The metal alkoxide used in the colored coating composition of the present invention is represented by the following general formula (A): R ¹ _n M (OR ² ) _m−n (A) (wherein R ¹ is independently substituted or An unsubstituted organic group,
M represents a metal, R ² independently represents a lower alkyl group, m represents the oxidation number of the metal, and n represents an integer of 0 to 2. ).

As the metal (M) of the metal alkoxide,
Silicon (Si), titanium (Ti), zirconium (Z
r), aluminum (Al), zinc (Zn), iron (F
e), cobalt (Co), nickel (Ni), beryllium (Be), magnesium (Mg), calcium (C
a), strontium (Sr), barium (Ba), scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), hafnium (Hf), vanadium (V), niobium (Nb), tantalum ( Ta),
Chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), copper (Cu), boron (B), gallium (Ga), indium (In), thallium (Tl), germanium (Ge), Tin (Sn),
Examples include lead (Pb), phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), sulfur (S), selenium (Se), and tellurium (Te). Among them, silicon, titanium, zirconium and aluminum are preferably used.

The metal alkoxides, organic groups R ¹ substituted or unsubstituted, (cyclo) alkyl group, an aryl group, an aralkyl group, an alkenyl group, and other substituted alkyl group is preferably used. Examples of the (cyclo) alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group. Examples of the aralkyl group include a benzyl group. Examples of the alkenyl group include a vinyl group. Other substituted alkyl groups include
Methacryloxypropyl, glycidoxypropyl group, epoxycyclohexylethyl group, aminopropyl group, aminoethylaminopropyl group, mercaptopropyl group,
Examples include a ureidopropyl group, an isocyanatepropyl group, and a trifluoropropyl group.

R ² of the metal alkoxide is preferably a lower alkyl group. A C1-C6 alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group is more preferable.

The oxidation number m of the metal is preferably 2 to 8, and 3
To 4 are more preferred.

Preferred metal alkoxides are represented by the following general formula (1): R ¹ _n M (OR ² ) _mn (1) (wherein R ¹ is independently a C ¹ -C 6 (cyclo) alkyl group) , A C6-C9 aryl group, a C7-C10 aralkyl group, a C2-C5 alkenyl group, a (meth) acryloxy-C1-C4 alkyl group, a glycidoxy-C1-
The C4 alkyl group, M is silicon, titanium, zirconium or aluminum, an alkyl group of ^{R 2} is independently C1 -C4, m is 3 or 4 integer, n is an integer of 0 to 2. ).

Specific examples of the above metal alkoxide include:
The following compounds are mentioned. For example, silane alkoxides include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane Silane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, phenylmethyldimethoxysilane, γ-glycidoxypropyl Methyldimethoxysilane and the like can be mentioned.

Examples of the metal alkoxide of titanium include tetraisopropoxytitanium and tetra-n-butoxytitanium.

Examples of the metal alkoxide of zirconium include tetra-n-butoxyzirconium. As the metal alkoxide of aluminum, tri-
s-butoxyaluminum and the like.

Furthermore, homo-oligomers and hetero-oligomers of the above-mentioned metal alkoxides are also used as the metal alkoxide of the present invention.

These metal alkoxides are used alone or in combination of two or more. When two or more silane alkoxides are used in combination, it is preferable that at least one of the silane alkoxides in the general formula (1) is 1. In particular,
When using a silane alkoxide having an aryl group,
As shown in the examples below, the maximum absorption wavelength can be changed by changing the content of the aryl group (phenyl group in the example), and thus it is useful to use two or more metal alkoxides in combination.

In the present invention, a hydrolyzed condensation polymer of a metal alkoxide may be used. The hydrolysis-condensation product of the metal alkoxide can be obtained by a method usually performed by those skilled in the art. For example, it can be obtained by dissolving one kind or two or more kinds of the metal alkoxides in an appropriate solvent, adding a catalyst and water, mixing, stirring and reacting.

First, a metal alkoxide solution is prepared. Examples of the solvent for the metal alkoxide include lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and isobutanol; ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and propylene glycol monomethyl. Glycol derivatives such as ether, ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate; hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and acetylacetone; esters such as ethyl acetate and ethyl acetoacetate; butyl methyl ether; Ether That. These solvents alone,
Alternatively, two or more kinds can be used in combination.

Next, a catalyst and water are added to the metal alkoxide dissolved in the solvent to cause a reaction.

Examples of the catalyst include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, maleic acid and trifluoroacetic acid; potassium hydroxide, sodium hydroxide, calcium hydroxide; Bases such as ammonia; organic tin compounds such as dibutyltin dilaurate and dibutyltin diacetate; aluminum tris (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate) ) And boron compounds such as boric acid butoxide and boron trifluoride. These catalysts may be used alone or in combination of two or more.

The added water affects the degree of polymerization of the resulting polycondensate. It is preferable to add about 0.01 to 3.0 moles to the number of moles of the alkoxy group of the metal alkoxide. The reaction may be performed at room temperature. Heating or cooling may be performed to adjust the reaction. When the concentration of the reaction solution is adjusted, it is used as it is to prepare a composition with a latent pigment.

The latent pigment used in the present invention means a solvent-soluble pigment derivative (pigment precursor) in which a protecting group for promoting solvent solubility is introduced into a parent skeleton constituting the pigment. The introduced protecting group is easily removed by chemical treatment, photolytic treatment, heat treatment, etc.
As a result, a matrix skeleton appears and pigmentation occurs, and the original pigment color develops. For latent pigments, N
Nature, vol. 388, p. 131 (1997). For example, Japanese Patent Application Laid-Open No. 9-3362, International Publication No. 98/32802, International Publication No. 98
No./45757, International Publication No. 98/58027.
Publication, International Publication No. 99/01511, JP-A-11-92695, JP-A-11-310726
In the publication, pigment precursors having various colors and structures are listed.

The latent pigment used in the present invention is represented by the following general formula (2): A (B) x (2). A is the residue of a quinacridone, anthraquinone, perylene, indigo, quinophthalone, indanthrone, isoindolinone, isoindoline, dioxazine, phthalocyanine, diketopyrrolopyrrole or azo series colorant. This residue A contains X heteroatoms, which are conjugated or adjacent to at least one carbonyl group, and B is a group of formula (3) : —C (＝ O) —O—R ³ (3), which is bonded to one of the above heteroatoms.
R ³ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group or aralkyl group.

The alkyl group is preferably a C1 to C24 alkyl group. As the alkenyl group, C3 to C2
4 alkenyl groups are preferred. Alkynyl groups include C
An alkynyl group of 3 to C24 is preferred. As the cycloalkyl group, a C4 to C12 cycloalkyl group is preferable. As the cycloalkenyl group, a C4-C12 cycloalkenyl group is preferable. Aralkyl groups include C
7 to C24 aralkyl groups are preferred. Examples of the substituent include a halogen atom, an ether group, an amino group, a thioether group, a cyano group, and a nitro group.

Hereinafter, the latent pigment used in the present invention will be described. In the structural formula, E represents hydrogen or a group B, and at least one E is B.

Examples of the latent pigment having a quinacridone residue include derivatives of a compound represented by the following general formula (Ia).

[0037]

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Wherein R ¹¹ and R ¹² independently of one another are hydrogen, halogen, a C1-C18 alkyl group, C1
Represents a C4 alkoxy group or a phenyl group. Preferably, it is a hydrogen, chlorine, or methyl group.

Further, as a latent pigment having a quinacridone residue, derivatives of the following compounds (Ib), (Ic) or (Id) are also used.

[0040]

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The latent pigment having an anthraquinone residue is represented by the following general formula (IIa) or (IIb)
The compound represented by is used.

[0042]

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In the formula, R ¹³ and R ¹⁴ are each independently hydrogen, a C1-C12 alkyl group, or C6
An aryl group -C12, the aryl group, halogen, C1 -C6 alkyl, C1 -C6 alkoxyl group, a nitro group, _acetyl, optionally substituted with -SO 2 NHC1~C6 alkyl group or _-SO 2 NH Is also good. R ¹⁵ and R ¹⁶ are each independently hydrogen,
Halogen, C1 -C6 alkyl, C1 -C6 alkoxyl group, a nitro group, a cyano group, -CONH _2, -SO ₂
NHC1~C6 alkyl _group, -SO ₂ NH _2, -SO ₃
H, —SO ₃ Na, or a C6-C12 aryl group, wherein the aryl group is a halogen, a C1-C6 alkyl group, a C1-C6 alkoxyl group, a nitro group, an acetyl,
-SO ₂ NHC1~C6 alkyl group or _-SO 2 NH
May be substituted. R ¹⁷ is hydrogen, halogen,
It is a nitro group, a cyano group, a hydroxy, or a C1-C6 alkoxyl group.

As the latent pigment having an anthraquinone residue, a derivative of an anthraquinonoid compound represented by the following formula (IIc) or (IId) is further used.

[0045]

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Wherein R ¹⁸ is hydrogen or halogen.

Examples of the latent pigment having a perylene residue include perylene carboximide derivatives represented by the following general formula (IIIa) or (IIIb).

[0048]

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In the formula, R ¹⁹ represents hydrogen, a C 1 -C 6 alkyl group, a phenyl group, a benzyl group or a phenethyl group, which is unsubstituted or substituted by halogen or a C 1 -C 4 alkyl group.

The latent pigment having an indigo residue includes an indigo derivative represented by the following general formula (IVa).

[0051]

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In the formula, R ²⁰ represents hydrogen, a cyano group, C 1
Represents a C6 alkyl group, a C1-C6 alkoxyl group, or halogen.

Examples of the latent pigment having a quinophthalone residue include derivatives of compounds represented by the following formulas (Va) and (Vb).

[0054]

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Wherein R ²¹ is H or OE;
R ^{22 to} R ²⁵ are each independently hydrogen, halogen, —COO—C 1 to C 6 alkyl group or —CONH
—C1 to C6 alkyl group. E is the same as above.

Examples of the latent pigment having an indanthrone residue include a derivative of the compound represented by the following formula (VIa).

[0057]

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As a latent pigment having an isoindolinone residue, the following general formula (VIIa) or (VIIa)
Derivatives of the compound of b).

[0059]

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In the formula, R ³⁰ and R ³¹ each independently represent hydrogen, halogen, or a C1-C4 alkyl group.

The latent pigment having an isoindoline residue includes the following formulas (VIIIa), (VIIIb) and (VIIIc).

[0062]

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Wherein R ³³ is the following formula:

[0064]

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Wherein R ³⁴ is hydrogen, C 1 -C 2
4 alkyl groups, benzyl groups, or the following formula:

[0066]

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R ³⁵ is hydrogen, E or R
Is ^{33, R 36, R 37,} R 3 8 and ^{R 39} are,
Each is independently hydrogen, a C1-24 alkyl group, a C1 to C6 alkoxyl group, a halogen, or a trifluoromethyl group.

The latent pigment having a dioxazine residue includes a derivative represented by the following general formula (IXa).

[0069]

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In the formula, R ⁴¹ represents hydrogen, halogen, or a C1 to C24 alkyl group.

Further, as a latent pigment having a dioxazine residue, a derivative of the following general formula (IXb) can be mentioned.

[0072]

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In the formula, R ⁴² and R ⁴³ are each independently a C1 to C4 alkyl group.

The latent pigment having a phthalocyanine residue includes a compound represented by the following formula (X).

[0075]

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In the formula, M is H ₂ or Cu (II), Z
n (II), Fe (II), Ni (II), Ru (II), Rh
(II), Pd (II), Pt (II), Mn (II), Mg
(II), Be (II), Ca (II), Ba (II), Cd
(II), Hg (II), Sn (II), Co (II) or Pb (II), preferably Cu (II), Zn (I
A divalent metal selected from the group consisting of I), Fe (II), Ni (II) or Pd (II), or V (O),
A divalent metal oxide selected from the group consisting of Mn (O) and Ti (O), wherein T ₁ is -CHR ^52- , -C
O— or —SO ₃ —, and R ⁵¹ represents hydrogen, C 1
C6 alkyl group, -N (E) ^R52 , -N (E) ₂ ,-
NHCOR ⁵³ , —COR ⁵³ , or the following formula:

[0077]

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R ⁵² is hydrogen or C1
-C6 alkyl group, R ⁵³ is a C1-C6 alkyl group, and R ⁵⁴ is hydrogen, halogen, C1
A -C6 alkyl group or a C1-C6 alkoxyl group, z is 0 or 1, and y is an integer of 1-8.

Examples of the latent pigment having a diketopyrrolopyrrole residue include compounds represented by the following general formulas (XIa) and (XIb).

[0080]

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Wherein G and L are each independently
The following formula:

[0082]

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Any of the groups

In the formula, R ⁶¹ and R ⁶² are each independently hydrogen, halogen, a C1-C24 alkyl group,
1-C6 alkoxyl group, C1-C18 alkyl mercapto group, C1-C18 alkylamino group, cyano group, nitro group, phenyl group, trifluoromethyl group, C5-C
6 cycloalkyl group, -C = N- (C1-C24 alkyl group), the following formula

[0085]

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[0086] the group, imidazolyl group, pyrazolyl group, triazolyl group, a piperazinyl group, a pyrrolyl group, oxazolyl group, benzoxazolyl group, benzothiazolyl group, benzimidazolyl group, a morpholinyl group, a piperidinyl group or Pirorojiniru group,, T ₂ is -CH
_{2 -, - CH (CH 3} ) -, - C (CH 3) 2 -, - C
H = N-, -N = N-, -O-, -S-, -SO-,-
SO ₂ — or —NR ⁶⁷ —, and R ⁶³ and R ^63
64 is each independently hydrogen, halogen, C1 to C
6 alkyl group, C1-C6 alkoxyl group, or cyano group, R ⁶⁵ and R ⁶⁶ are each independently hydrogen, halogen, or C1-C6 alkyl group, and R ⁶⁷ is hydrogen or C1 ~ C6 alkyl group.

Examples of the latent pigment having an azo series residue include the following azo compounds (XIIa) to (XIIf).

[0088]

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[0089]

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[0090]

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In the formula, R ^{71 to} R ⁷⁵ each independently represent hydrogen, halogen, a C 1 to C 6 alkyl group, C 1 to C
6 alkoxyl, nitro, acetyl, or SO2
An NHC1-C6 alkyl group, and R ⁷⁶ is
Hydrogen, halogen, C1-C6 alkyl group, or C1-
It is a C6 alkoxyl group.

More preferred latent pigments are the following (A1) to (A13).

[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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These latent pigments may be used alone or in combination of two or more.

The colored coating composition of the present invention can be obtained by mixing a metal alkoxide and / or a hydrolyzed condensation polymer of a metal alkoxide with a latent pigment. As the solvent for dissolving the metal alkoxide, the solvent used when preparing the above-mentioned metal alkoxide hydrolyzed condensation polymer is used. As the hydrolysis-condensation polymer of the metal alkoxide, the hydrolysis-condensation polymer prepared by the above method is used as it is or after being diluted with the above-mentioned solvent. The concentration of the metal alkoxide and / or the hydrolyzed condensation polymer of the metal alkoxide is preferably adjusted to about 0.1 to 80% by weight. More preferably, 1 to
50% by weight.

On the other hand, the latent pigment is dissolved in a suitable solvent. For example, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, cyclohexanol, glycidol, furfuryl alcohol, benzyl alcohol,
Glycol derivatives such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, o-xylene, and toluene ,
Hydrocarbons such as cyclohexane, ethyl acetate, acetic acid-n
Esters such as -propyl, n-butyl acetate, butyrolactone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl n-pentyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, etc. Ketone.

The concentration of the latent pigment is not particularly limited, but is preferably 0.1 to 50% by weight, more preferably 1 to 20% by weight.

With respect to the obtained solution of the metal alkoxide and / or the hydrolyzed condensation polymer of the metal alkoxide,
It is prepared by adding a solution of latent pigment. The mixing ratio is not particularly limited, but the composition contains 0.1 to 50% by weight, preferably about 1 to 20% by weight of a metal alkoxide and / or a hydrolyzed condensation polymer of the metal alkoxide.
% By weight, latent pigment is 0.01 to 10% by weight,
Preferably, it is contained in an amount of 0.1 to 5% by weight. In consideration of transportation, storage, etc., a metal alkoxide and / or a hydrolyzed polycondensate solution of the metal alkoxide and a latent pigment solution are separately prepared,
At the time of use or during the production of the composition, the colored coating liquid composition of the present invention may be produced by mixing so as to have the above concentration.

The colored coating composition of the present invention may contain, if necessary, an ultraviolet absorber, an infrared absorber, a light stabilizer,
Additives such as leveling agents may be included. Further, in order to improve the physical properties of the coating film, a polymer such as a polyol resin, a polyisocyanate compound, or a silicone resin may be contained.

The thus-obtained colored coating liquid composition is applied to a substrate by a method appropriately used by those skilled in the art, such as roller coating, spin coating, and dipping. The thickness of the colored thin film is not particularly limited, and may be determined according to the purpose.

The substrate to be coated is not particularly limited, but heating (100 to 30) for pigmenting the latent pigment is used.
(0 ° C.). Substrates include metal substrates, glass plates, glass fibers,
Examples include glass tubes, ceramics, and plastics. When used for a display device or the like, a light-transmitting material such as glass is particularly preferable.

After application, drying is performed. The drying temperature is not particularly limited, but is preferably performed between room temperature and 100 ° C.
It is more preferable to carry out at about 50 ° C.

After drying, the substrate on which the composition for coloring paint is applied is heated. The heating removes the protecting group of the latent pigment, and the color of the original pigment (pigment) is developed. The heating temperature is not particularly limited as long as it is at least the temperature at which the protecting group of the latent pigment used is eliminated, but is generally 100 to 300 ° C, preferably 150 to 250 ° C.
It is. If the temperature is too low, the elimination of the protecting group becomes insufficient, and if it is too high, thermal decomposition of the pigment occurs.

The substrate thus obtained is a uniform, transparent and strong colored thin film.
Used for applications such as color filters and optical recording. When a colored thin film is formed on a light-transmitting material (for example, glass), the obtained thin film selectively absorbs a wavelength in a specific wavelength range by a contained pigment. Used for display devices. For example, as shown in Example 1 described below, a violet pigment (Pigment Violet 37) has a maximum absorption around 570 nm. Therefore, it is necessary to select a colored thin film substrate in consideration of the wavelength of light for the purpose of absorption.

The display device to which the light-absorbing filter of the present invention is applied includes a liquid crystal display device, a color picture tube, a black and white picture tube, a plasma display device, an organic electroluminescence display device, and the like. The colored thin film substrate of the present invention is used as a filter in the light transmissive display section of such an apparatus. Further, a projection type liquid crystal display device is also used. In this case, a colored thin film may be provided on the projection screen.

[0110]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to this embodiment.

Examples 1 to 6 Tetramethoxysilane 3
0.8 g, 62.6 g of ethanol, 0.1 g of nitric acid, and 6.5 g of water were mixed, and the mixture was stirred at room temperature for 4 hours to obtain 100 g of a hydrolyzed condensate of a silane alkoxide.

On the other hand, 100 g of a cyclohexanone solution (latent pigment solution) containing 5 g of each of the latent pigments described in Examples 1 to 6 in Table 1 was prepared.

100 g of the silane alkoxide hydrolyzed condensate (silica sol) was added to the latent pigment solution 1
00 g and 300 g of isopropanol were mixed to obtain a coating composition.

The coating composition was spin-coated on a glass substrate at a speed of 1000 rpm. The obtained coating film was dried at 50 ° C. for 10 minutes. Then 150
It heated for 10 minutes at 180 degreeC, 250 degreeC, respectively. Table 1 shows the maximum absorption wavelength and the transmittance at each of these temperature treatments. Each thin film obtained by heating at each temperature was transparent and uniform, and had a thickness of about 300 nm.

In Table 1, A5 represents the dioxazine series, A7 and A9 represent the azo series, A2 represents the diketopyrrolopyrrole series, and A11 and A13 represent the phthalocyanine series.

[0116]

[Table 1]

The results in Table 1 show that the protective pigment was removed from each latent pigment by heating, the original color tone of the pigment appeared, and the maximum absorption wavelength λmax also changed. FIGS. 1 and 2 show this change as a change in wavelength. FIGS. 1 and 2 show Example 1 respectively.
The absorption spectra after drying at 50 ° C. (before heat treatment) and after heat treatment at 250 ° C. are shown, indicating that the maximum absorption wavelength was shifted by heating, and that the protecting group of the latent pigment was detached by heating. Was done.

Further, in each of the examples, the tendency that the protective group was eliminated at a temperature lower than the actual pigment regeneration temperature was observed. This is because the acid ( Nitric acid). That is,
This shows that film formation is possible at a considerably low temperature using the composition of the present invention.

(Examples 7 to 9) Tetramethoxysilane and phenyltrimethoxysilane were mixed in the proportions shown in Table 2 and dissolved in the amount of ethanol shown in Table 2, and water and nitric acid were added. In the same manner as in Examples 1 to 6, a hydrolysis-condensation polymer of a metal alkoxide was obtained. To 100 g of the hydrolyzed polycondensate of the obtained metal alkoxide, 100 g of the solution of latent pigment A5 prepared in Example 1 and 300 g of isopropanol were mixed to prepare a colored coating composition. The colored coating composition is applied on a glass substrate by a spin coating method, dried at 50 ° C. for 10 minutes, and dried at 250 ° C. for 2 minutes.
Heat for 0 minutes to give a colored, clear, uniform, about 300
A thin film having a thickness of nm was obtained. Table 2 shows the results.

[0120]

[Table 2]

In Examples 7 to 9, the maximum absorption wavelength λ
Although the value of max differs from that of Example 1, it is considered that this is a result of the interaction between the pigment and the phenyl group because the metal alkoxide used contains a phenyl group. By changing the types of metal alkoxides and the mixing ratio thereof, light of different wavelengths can be absorbed, and it was suggested that a filter capable of absorbing any specific wavelength can be produced.

Examples 10 to 17 Colored coating compositions were applied to glass bottles and colored. The metal alkoxides shown in Table 3 were mixed in the proportions shown in Table 3 and dissolved in the amounts shown in Table 3 in isopropanol (IPA), ethyl acetoacetate or ethylene glycol monoisopropyl ether, and water and nitric acid were added. In the same manner as in Examples 1 to 6,
A hydrolysis-condensation polymer of the metal alkoxide was obtained. As shown in the lower part of Table 3, a latent pigment solution obtained by dissolving 5 g each of latent pigments A13 and A2 in 90 g of cyclohexanone and 100 g of isopropanol in 100 g of the obtained hydrolyzed polycondensation product of the metal alkoxide.
g to prepare a colored coating composition. Apply the colored coating composition to the surface of the glass bottle by spin coating,
After drying at 0 ° C. for 10 minutes and heating at 250 ° C. for 20 minutes, a colored, transparent and uniform thin film having a thickness of about 300 nm was obtained.

The following tests were conducted on the obtained colored glass bottles. 1) Hot water test: The bottle was immersed in hot water of 90 ° C for 60 minutes. 2) Alkali resistance test: The bottle was immersed in a 2.5% aqueous sodium hydroxide solution at 60 ° C. for 30 minutes. The evaluation criteria for the water resistance test and the alkali resistance test result are as follows:
It is as follows. A: There is no change in appearance after immersion (there is no peeling or whitening of the film). ：: Whitening and the like are slightly observed after immersion, but there is no practical problem. C: Peeling of the film, whitening, etc. are observed after immersion. Table 3 shows the results.

[0124]

[Table 3]

As a result, in each of Examples 10 to 17, a colored glass bottle having excellent hot water resistance and excellent alkali resistance was obtained.

[0126]

The colored coating liquid composition of the present invention containing a metal alkoxide and / or a hydrolyzed polycondensate of the metal alkoxide and a latent pigment does not use a dispersant, and uses the metal alkoxide and / or Alternatively, by changing the type and amount of the hydrolyzed polycondensate, it has an effect that any physical properties can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing an absorption spectrum before a heat treatment.

FIG. 2 is a diagram showing an absorption spectrum after heat treatment.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // G02F 1/1335 505 G02F 1/1335 505 F-term (Reference) 2H048 BA45 BA47 BB02 BB42 2H091 FA02X FA02Y FA02Z FB02 FB13 GA01 LA15 LA16 4G059 AA01 AA04 AA06 AC08 EA05 EB05 FA01 FA28 FB03 4J038 DM021 JA23 JA34 JB27 KA08

Claims (9)

[Claims] 1. A colored coating composition comprising a metal alkoxide and / or a hydrolyzed polycondensate of the metal alkoxide and a latent pigment. 2. The metal alkoxide is represented by the following general formula (1): R ¹ _n M (OR ² ) _mn (1) (wherein R ¹ is independently a C1-C6 (cyclo) alkyl Group, C6-C9 aryl group, C7-C10 aralkyl group, C2-C5 alkenyl group, (meth) acryloxy-C1-C4 alkyl group, glycidoxy-C1-
The C4 alkyl group, M is silicon, titanium, zirconium or aluminum, an alkyl group of ^{R 2} is independently C1 -C4, m is 3 or 4 integer, n is an integer of 0 to 2. The colored coating liquid composition according to claim 1, which is represented by the formula: 3. The latent pigment is represented by the following general formula (2): A (B) x (2) (wherein X is an integer of 1 to 8, A is quinacridone,
Anthraquinone, perylene, indigo, quinophthalone,
Indanthrone, isoindolinone, isoindoline,
Dioxazine, phthalocyanine, diketopyrrolopyrrole or azo series colorant residue, this residue A
It contains X heteroatoms, which are conjugated or adjacent to at least one carbonyl group, and B is a group of formula (3): -C (= O ) -OR ³ (3) wherein R ³ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group or aralkyl group. Attached to one of the above heteroatoms)
The colored coating solution composition according to claim 1. 4. A colored substrate obtained by applying the colored coating solution composition according to any one of claims 1 to 3 to a surface and heating the composition. 5. A display filter having a light-transmitting colored substrate obtained by applying the colored coating solution composition according to claim 1 to a surface of a light-transmitting substrate and heating the composition. 6. The display filter according to claim 5, wherein the light-transmitting substrate is glass. 7. The display filter according to claim 5, which selectively absorbs a wavelength in a specific wavelength range. 8. A display device having a light transmissive display unit, wherein the display filter according to claim 5 is provided on an outer surface of the light transmissive display unit. . 9. A colored glass bottle obtained by applying the colored coating solution composition according to claim 1 to a surface of the glass bottle and heating the glass bottle.