JPH0894826A - Ink composition and color filter produced by using that - Google Patents

Abstract

PURPOSE: To obtain an ink compsn. suitable to obtain a color filter at a low cost by an ink-jet method by incorporating a specified anthraquinone compd. or triphenylmethane compd. CONSTITUTION: This ink compsn. contains as a free acid at least one of anthraquinone compds. expressed by formula I or at least one of triphenylmethane compds. expressed by formula II. In formula I, X and Y are independently hydrogen atoms or groups expressed by formula III, n is 0 or 1, m is 1 or 2, and M is H. In formula II, R5 is a hydrogen atom, C1-C5 alkyl group, halogen atom, R6 -R9 are independently hydrogen atoms, C1-C5 alkyl groups which may have substituents, phenyl groups which may have substituents, or benzyl groups which may have substituents, and M is H. In formula III, R1 -R3 are independently hydrogen atoms, C1-C5 alkyl groups, C1-C6 alkoxy groups or the like, and R4 is a hydrogen atom, sulfonate group or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink composition used for producing a color filter having excellent optical properties used in liquid crystal display devices, color separation devices, sensors, etc., and a color filter produced by an inkjet method. Regarding

[0002]

2. Description of the Related Art Conventionally, a method of combining three primary color filters of red, green, blue, or yellow, magenta, and cyan has been used for colorizing a liquid crystal display device or a solid-state image pickup device. Although there are several methods for forming these color filters, the most basic method is the so-called dyeing method. The color filter manufacturing method by this dyeing method is a stripe shape or a mosaic shape (called a pattern) on the surface of the glass or silicon wafer that is the base.
A thin film of a synthetic resin having a transparent cationic group or a film of a protein-based natural polymer substance such as gelatin, casein, and glue is provided as a film to be colored, and this is dyed with a dye (coloring) The basic principle is to do. The concrete manufacturing process of the color filter is as follows.
Two schemes are known.

(1) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer. Then a non-coloring protective coat
A coating film is provided on the entire surface, and a second coating film to be colored is provided thereon by the same operation as above. Hereinafter, if necessary, colored layers are sequentially laminated.

(2) After a film to be colored is provided on the surface of the substrate, the pattern obtained by exposing and developing through a mask is dyed to form a colored layer, and then a dye is fixed with tannic acid or the like. Combined with dye-proof treatment. A second coating to be colored is provided by the same operation. Thereafter, if necessary, a colored layer is formed on the same substrate surface.

(3) A film to be colored (coloring film) is provided on the surface of the substrate. After providing a positive resist layer thereon, the film to be colored is exposed and developed through a mask to dye the exposed film to be colored, and then the positive resist layer is peeled off to form a colored portion. By repeating the operation after providing the positive resist layer, the same colored film is dyed into a desired pattern in a plurality of colors.

Color produced by the above process
Except for special ones, the filters are usually the three primary colors R (red), G (green), B (blue) or the complementary three primary colors Y (yellow), M (magenta), C (cyan). ), (M may be omitted). The most important characteristic required for the color filter is the optical characteristic, and the spectral characteristic of each colored layer greatly controls the value of the final product.

Further, for heat treatment performed in a process of manufacturing a liquid crystal display device having a color filter, for example, for a sputtering process for providing a transparent electrode layer, and for light applied during use as a final product. It must have a high degree of resistance and must not impair certain optical properties. Of course, the dyes applied must also have good solubility and solubility in water and be stable for a long time in acidic dye baths. Further, when a process that requires fixing treatment is involved, it is required that the fixing treatment effect is excellent.

By the way, since the protein type polymer substances such as gelatin, casein and glue have a cationic group, they are dyed (colored) with a water-soluble anionic dye. When a photo-curable synthetic resin substrate is used instead of these, by retaining a cationic group in the resin component, it is dyed with a water-soluble anionic dye like a protein-based natural polymer substance. Become so.

As described above, the dyeing method has a feature that an extremely fine color pattern can be freely formed.
Since many manufacturing processes such as a photolithography process, a dyeing process, and a cleaning / fixing process are performed depending on the number of colors to be dyed, there is a high risk that yield may be reduced due to dust adhesion during manufacturing. Further, since the coloring density is almost proportional to the film thickness of the dyed resin film, the fluctuation of the film thickness causes unevenness of color and deteriorates the quality of the product. Depending on the order of dyeing, color unevenness may occur due to contamination or desorption of other colors. Further, a liquid crystal display device manufacturer has strongly demanded a method of reducing the number of steps for manufacturing a color filter to improve the yield and make the cost lower.

[0010]

SUMMARY OF THE INVENTION According to the present invention, a highly dyeable photosensitive resin thin film is formed on a substrate, and a dye solution is selectively jetted onto the thin film layer by an inkjet method to form a desired colored pattern. Then, it is to provide an ink composition suitable for obtaining a color filter by fixing treatment and a color filter manufactured using the same.

[0011]

Means for Solving the Problems The inventors of the present invention have made extensive studies in order to solve the above-mentioned problems, and as a result, achieved the present invention. That is, the present invention provides the following formula (1) as the free acid (1).

[0012]

[Chemical 5]

(In the formula (1), X and Y are independently a hydrogen atom or the following formula (2):

[0014]

[Chemical 6]

(In the formula (2), R ₁ , R ₂ and R ₃ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 1 carbon atoms.
6 represents an alkoxy group, a halogen atom, a sulfonic acid group, a hydroxyalkyl group or an alkoxyalkyl group, R
₄ is a hydrogen atom, a sulfonic acid group, the following formula (a) or the following formula (b)

[0016]

[Chemical 7]

(In the formula, R ₁₀ , R ₁₁ and R ₁₂ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a sulfonic acid group and a hydroxyalkyl group. Represents an alkoxyalkyl group (provided that X and Y
One of is a group other than a hydrogen atom), and k is 1 to
Represents an integer of 4 and j represents 1 or 2), n represents 0 or 1, m represents 1 or 2, and M represents H. ) At least one of the anthraquinone compounds represented by

[0018]

[Chemical 8]

(In the formula (3), R ₅ is a hydrogen atom and has 1 carbon atom.
5 represents an alkyl group or a halogen atom, R ₆ ,
R ₇ , R ₈ and R ₉ independently have a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may have a substituent, a phenyl group which may have a substituent or a substituent. Each represents a benzyl group which may be present, and M has the same meaning as described above. (2) An ink composition comprising at least one triphenylmethane compound represented by the formula (2).
An ink composition for producing a color filter, comprising at least one of the compounds described in (1) above,
(3) An ink composition for producing a color filter by an inkjet method, comprising at least one of the compounds described in (1) above, (4) using the ink composition described in (1) above, The present invention relates to a color filter manufactured by coloring by an inkjet method.

In R ₁ , R ₂ and R ₃ of the above formula (2) and in R ₁₀ , R ₁₁ and R ₁₂ of R ₄ of the above formula (2), the alkyl group having 1 to 5 carbon atoms is: Examples thereof include a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isobutyl group, an n-butyl group, a t-butyl group and a pentyl group. As the alkoxy group having 1 to 6 carbon atoms,
For example, methoxy group, ethoxy group, isopropyloxy group, n-propyloxy group, isobutyloxy group, n-
Examples thereof include a butyloxy group, a t-butyloxy group, a pentyloxy group and a hexyloxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. As the hydroxyalkyl group,
Examples thereof include hydroxy (C ₁ -C ₅ ) alkyl groups such as hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group and hydroxypentyl group. Examples of the alkoxyalkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, a pentoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, a methoxybutyl group, and an ethoxypentyl group ( C ₁ ~
C ₅₎ alkoxy (C ₁ ~C ₅₎ alkyl group.

Among R ₁ , R ₂ and R ₃ in the above formula (2), preferable ones are, for example, R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is an alkyl group having 1 to 5 carbon atoms, A sulfonic acid group, a hydroxy (C ₁ -C ₅ ) alkyl group, a halogen atom, a (C ₁ -C ₅ ) alkoxy (C ₁ -C ₅ ) alkyl group, and R ₃ is an alkyl group having 1 to 5 carbon atoms, It is a halogen atom. R _{4 in} the above formula (2) and R in the formula (a)
_{In 10} , preferable examples include a hydrogen atom, a sulfonic acid group, an alkoxy group having 1 to 6 carbon atoms, and (C _{1 to} C ₅ ).
Alkoxy (C ₁ ~C ₅₎ alkyl group. Similarly, in R ₁₁ and R ₁₂ of the formula (b), preferred are, for example, R ₁₁ being a hydrogen atom, a sulfonic acid group and a halogen atom, and R ₁₂ being a hydrogen atom and a halogen atom. Further, in R ₄ of the above formula (2), preferred are, for example, a hydrogen atom, a sulfonic acid group, R ₁₀ is a hydrogen atom, a sulfonic acid group, an alkoxy group having 1 to 6 carbon atoms, and (C _{1 to} C ₅ ). A group of formula (a) which is an alkoxy (C ₁ -C ₅ ) alkyl group, a group of formula (b) in which R ₁₁ is a hydrogen atom, a sulfonic acid group or a halogen atom and R ₁₂ is a hydrogen atom or a halogen atom. Is.

Preferred combinations of X, Y and n in the above formula (1) are as follows, for example. That is, when n is 0 (when the sulfonic acid group is not bonded to the anthraquinone skeleton), both X and Y have the substituent of the formula (2), and preferably both have the same substituent. What you have is better. In this case, R ₄ is a hydrogen atom or a sulfonic acid group, and m is preferably 1. When R ₄ is a sulfonic acid group, each of R ₁ , R ₂ and R ₃ is an alkyl group having 1 to 5 carbon atoms, and R ₁ and R ₂ are alkyl groups having 1 to 5 carbon atoms.
₃ is a halogen atom, R ₁ and R ₃ are alkyl groups having 1 to 5 carbon atoms, R ₂ is a hydroxy (C _{1 to} C ₅ ) alkyl group, R ₁ is an alkyl group having 1 to 5 carbon atoms, and R ₂ , R ₃
Is a halogen atom, R ₁ is an alkyl group having 1 to 5 carbon atoms, R ₂ is a (C ₁ -C ₅ ) alkoxy (C ₁ -C ₅ ) alkyl group, and R ₃ is a halogen atom.
When R ₄ is a hydrogen atom, R ₁ and R ₃ have 1 to 5 carbon atoms.
Is an alkyl group and R ₂ is a sulfonic acid group.

When n is 1 (when a sulfonic acid group is bonded to the 2-position of the anthraquinone skeleton), one of X and Y is a hydrogen atom and the other is a substituent of the formula (2). , Or both X and Y are substituents of the formula (2). When one of X and Y is a hydrogen atom and the other is a substituent of the formula (2), R ₁ , R ₂ and R ₃ of the formula (2) are all alkyl having 1 to 5 carbon atoms. It is preferable that the group or R ₁ and R ₃ are alkyl groups having 1 to 5 carbon atoms and R ₂ is a halogen atom. Also, R in equation (2)
₄ , R ₁₀ is a hydrogen atom, a sulfonic acid group, an alkoxy group having 1 to 6 carbon atoms, (C _{1 to} C ₅ ) alkoxy (C ₁ to
A group of the formula (a) which is a C ₅ ) alkyl group, R ₁₁ is a hydrogen atom, a sulfonic acid group or a halogen atom, and a group of the formula (b) in which R ₁₂ is a hydrogen atom or a halogen atom;
The one with 1 is good. In this case, in the formula (a), R ₁₀
Is a sulfonic acid group, the substitution position is preferably m-position or p- with respect to the carbonyl group, and R ₁₀ is an alkoxy group having 1 to 6 carbon atoms, (C _{1 to} C ₅ ) alkoxy (C ₁ to
C ₅₎ When the alkyl group m- position being preferred. Further, in the formula (b), when R ₁₁ is a hydrogen atom, R ₁₂ is preferably a hydrogen atom. When R ₁₁ is a halogen atom, R ₁₂
Is a hydrogen atom and k is preferably 4. When R ₁₁ is a sulfonic acid group, R ₁₂ is a hydrogen atom, a halogen atom and k is 1,
j is preferably 2. Substitution position of R ₁₁ is 2 and 3 position, R
The substitution position of ₁₂ is preferably 1-position and 4-position. Next, when both X and Y are substituents of the formula (2), R of the formula (2)
₁ , R ₂ and R ₃ are all alkyl groups having 1 to 5 carbon atoms, R ₄ is R ₁₀ is a sulfonic acid group, and j is 1
The group of the formula (a) is The substitution position of the sulfonic acid group is preferably m-position or p-position with respect to the carbonyl group.

The compound represented by the above formula (1) as a free acid may be a water-soluble salt. Examples of the counter ion of the water-soluble salt capable of binding include alkali metal ions such as Na, K and Li, inorganic ammonium ions such as NH ₄ , N
H ₃ CH ₂ CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂
Or, an organic ammonium ion such as a mono-, di- or tri (hydroxy (C ₁ -C ₅ ) alkyl) ammonium ion such as NH (CH ₂ CH ₂ OH) ₃ can be used.

Specific examples of the free acid or water-soluble salt of the compound represented by the general formula (1) used in the present invention include:
For example:

[0026]

[Chemical 9]

[0027]

[Chemical 10]

[0028]

[Chemical 11]

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

R ₅ in the general formula (3) has 1 to 1 carbon atoms.
Examples of the alkyl group of 5 include a methyl group, an ethyl group,
Isopropyl group, n-propyl group, isobutyl group, n-
Examples thereof include a butyl group, a t-butyl group and a pentyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom,
Examples thereof include bromine atom and iodine atom. R ₆ , R ₇ , R
Examples of the substituent of the alkyl group having 1 to 5 carbon atoms which may have a substituent of ₈ and R ₉ include, for example, a hydroxy group, a sulfonic acid group, a carboxyl group, a cyano group, a methoxy group, an ethoxy group and a propoxy group. , Butoxy group, etc. (C
_{1 to} C ₅ ) alkoxy group and the like, and examples of the substituent in the phenyl group and benzyl group which may have a substituent include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group. Group, (C ₁ -C ₅ ) alkyl group such as pentyl group, halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom, sulfonic acid group,
Methoxy group, ethoxy group, propoxy group, butoxy group,
(C _{1 to} C ₆ ) such as t-butoxy group and hexyloxy group
A hydroxy (C ₁ -C ₅ ) alkyl group such as an alkoxy group, a hydroxyethyl group, a hydroxypropyl group, a methoxyethyl group, an ethoxyethyl group, an ethoxypropyl group,
(C ₁ -C ₅ ) alkoxy (C ₁ -C ₅ ) alkoxy such as butoxyethyl group
To C ₅ ) alkyl group, hydroxy (C ₁ -C ₅ ) alkoxy group such as 2-hydroxyethoxy group, 2-methoxyethoxy group, 2-ethoxyethoxy group (C ₁ -C ₅ ), etc. alkoxy (C _1- ). Examples include C ₅ ) alkoxy groups, 2-sulfoethyl groups, carboxyethyl groups, cyanoethyl groups and the like. Examples of the alkyl group having 1 to 5 carbon atoms which may have a substituent of R ₆ , R ₇ , R ₈ and R ₉ include, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, Hexyl group, hydroxyethyl group, hydroxypropyl group, 2-sulfoethyl group, carboxyethyl group, cyanoethyl group, methoxyethyl group, ethoxyethyl group,
Examples thereof include ethoxypropyl group and butoxyethyl group.

Preferred examples of R ₅ in the above formula (3) include a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom and the like. The substitution position is preferably the 2-position with respect to the carbon atom bonded to the phenyl group.
R ₆ is preferably, for example, one having 1 carbon atom.
~ 5 alkyl group, hydroxyethyl group, hydroxypropyl group and other hydroxy (C ₁ -C ₅ ) alkyl groups, cyanoethyl group and other cyano (C ₁ -C ₅ ) alkyl groups, methoxyethyl group, ethoxyethyl group, ethoxy Examples thereof include (C ₁ -C ₅ ) alkoxy (C ₁ -C ₅ ) alkyl groups such as propyl group and butoxyethyl group. Preferred examples of R ₇ include cyano (C ₁ -C ₅ ) alkyl groups such as sulfonylbenzyl group and cyanoethyl group. Preferred examples of R ₈ include a hydrogen atom and an alkyl group having 1 to 5 carbon atoms. Preferred examples of R ₉ include, for example, an alkyl group having 1 to 5 carbon atoms and a substituent (C _{1 to} C
₆ ) alkoxy group, (C ₁ -C ₅ ) alkoxy (C _1- )
Examples thereof include a phenyl group having a C ₅ ) alkyl group.

R ₅ , R ₆ , R ₇ , R _{8 of} the above formula (3),
Examples of preferable combinations of R ₉ are as follows. That is, R ₆ is an alkyl group having 1 to 5 carbon atoms, R ₇
Is a sulfonylbenzyl group, R ₈ is a hydrogen atom, and R ₉ is (C
₁ -C ₆₎ For alkoxyphenyl group, R ₅ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom.
Further, R ₅ is a hydrogen atom, R ₇ is a sulfonylbenzyl group, R
_When both R ₈ and R ₉ are alkyl groups having 1 to 5 carbon atoms, R ₆ is an alkyl group having 1 to 5 carbon atoms, hydroxy (C
₁ -C ₅₎ alkyl group, (C ₁ -C ₅₎ alkoxy (C
₁ -C ₅₎ alkyl group. Also, R ₅ has 1 to ₅ carbon atoms
When R ₆ is a cyano (C ₁ -C ₅ ) alkyl group, R ₇ is a sulfonylbenzyl group, and R ₈ is a hydrogen atom, R ₉ is (C ₁ -C ₅ ) alkoxy (C ₁ -C _5). ) It is an alkylphenyl group. Further, R ₅ is a hydrogen atom, R ₆
Is a (C ₁ -C ₅ ) alkoxy (C ₁ -C ₅ ) alkyl group, R ₇ is a cyano (C ₁ -C ₅ ) alkyl group, R ₈ is a hydrogen atom, and R ₉ is (C ₁ -C _6). ) It is an alkoxyphenyl group. The sulfonyl group in the sulfonylbenzyl group is preferably one bonded to the m-position of the benzyl group.

The compound represented by the above formula (3) as a free acid may be a water-soluble salt. Examples of the counter ion of the water-soluble salt include alkali metal ions such as Na, K and Li, inorganic ammonium ions such as NH ₄ and NH ₃ CH ₂
CH ₂ OH, NH ₂ (CH ₂ CH ₂ OH) ₂ or NH
Examples thereof include organic ammonium ions such as mono-, di- or tri (hydroxy (C ₁ -C ₅ ) alkyl) ammonium ions such as (CH ₂ CH ₂ OH) ₃ .

Specific examples of the free acid or water-soluble salt of the compound represented by the general formula (3) used in the present invention include:
For example:

[0038]

[Chemical 16]

[0039]

[Chemical 17]

[0040]

[Chemical 18]

The liquid medium of the ink composition of the present invention includes
A liquid medium containing at least water or preferably ion-exchanged water and a hydrophilic organic solvent is used. Here, the hydrophilic organic solvent has an effect as a non-drying agent, has a role of preventing the generation of solid matter by drying, and also has a role of adjusting the viscosity of the ink composition, and has the formula (1 )
Alternatively, those which do not prevent the dissolution of the dye shown in (3) must be selected.

Examples of the hydrophilic organic solvent include alcohols such as ethanol and butanol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, alkylene glycols such as ethylene glycol, propylene glycol and butylene glycol, and the like.
Alkyl cellosolves such as methyl cellosolve and ethyl cellosolve, glycerin, N-methyl-2-pyrrolidone,
If necessary, one or more nitrogen-containing heterocyclic ketones such as 1,3-dimethyl-2-imidazolidinone can be mixed and used as a liquid medium component. The content of the hydrophilic organic solvent in the ink composition is generally in the range of 0 to 50% by weight, preferably 3 to 40%, and more preferably 5 to 25% with respect to the total weight of the ink composition. It is preferably contained.

In the ink composition of the present invention, a solubilizing agent can be added so that the dye does not precipitate in the composition. Examples of such solubilizing agents include urea and ε-caprolactam. If necessary, these solubilizing agents may be contained in the composition in an amount of 1 to 30% by weight,
It is preferable to contain 1 to 20%. The dye used in the present invention has the structure of the above formula (1) or (3), but inorganic salts such as sodium chloride and sodium sulfate are generally mixed during the dye synthesis. Further, calcium ions, magnesium ions, etc. contained in general water are mixed in in a trace amount. These inorganic components not only significantly deteriorate the solubility and storage stability of the dye, but also cause corrosion and wear of the printer head, and therefore they are preferably removed. In order to remove these inorganic salts, methods such as an ultrafiltration method, a reverse osmosis method and an ion exchange method are used, and it is desirable to remove the inorganic salts as much as possible. It should be at least 1% by weight, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less based on the dye.

After removing the inorganic salts, the desired dye concentration is obtained by diluting or concentrating. The ink composition of the present invention can contain a dye content of 1 to 40% by weight, and practically 5 to 35%. Weight percent is preferred. After being prepared from such components, it is preferable to perform liquid filtration using a cellulosic filter aid in order to remove dust, foreign matters and other impurities, and then perform microfiltration with a membrane filter. Microfiltration with a membrane filter is preferably performed twice or more using filters having different pore sizes, for example, a pore size of 1
It is preferable to carry out microfiltration with a micron membrane filter, and then microfiltration with a pore diameter of 0.45 micron.

Among the various characteristics, the ink composition of the present invention mixed and prepared as described above is particularly excellent in stability and long-term storage stability, and is characterized in that it does not clog the ejection orifice. In addition, a stabilizer for the ink composition (for example, sodium polyacrylate such as Kayakerator C manufactured by Nippon Kayaku Co., Ltd.)
-1000 etc.) and antibacterial / antifungal agents (for example, Deltop manufactured by Takeda Pharmaceutical Co., Ltd.), it is advisable to add them before the microfiltration.

The color filter of the present invention can be manufactured, for example, as follows. That is, a coating film is formed by a spin coating method or the like using a protein-based natural polymer substance by the method described below, or a highly dyeable photosensitive resin is dissolved in a solvent such as methylcellosolve acetate, and the spin coating method or the like is used. The substrate is coated with the photosensitive resin liquid by a method, and the substrate is dried and then exposed to light to cure the photosensitive resin. The film thickness of the photosensitive resin thin film is preferably 0.2 to 5 μm, particularly 0.5 to 1.5 μm.
m is preferred. The photosensitive resin thin film may be exposed to a predetermined pattern through a mask, or may be exposed to the front surface without a pattern and cured. When a pattern is provided, a partition may be formed as a black matrix in the gap between the patterns.

A predetermined amount of the ink composition of the present invention is attached to a predetermined place of the photosensitive resin thin film thus obtained by a method such as an ink jet method or a bubble jet method. Coloring by the inkjet method may be performed for each color or for multiple colors simultaneously. After coloring, heat drying treatment is performed for 3 to 15 minutes on a hot plate or oven at 70 to 180 ° C. After that, in order to prevent the dye from being eluted, a fixing treatment is carried out in an aqueous solution of tannic acid and tartarite to wash. Further, for the purpose of protecting the color filter layer, a transparent protective layer may be coated on the entire surface of the colored thin film.

The substrate used in the present invention is not particularly limited as long as it is a colorless and transparent plate, and examples thereof include plates made of glass, polyester, polycarbonate, polyacrylate, polyether sulfone and the like. Its thickness is 0.5
About 1.5 mm is preferable.

The protein-based natural polymer substance such as gelatin, casein, and glue as the film to be colored in the present invention will be described. Gelatin is an animal protein in which collagen is boiled with water to irreversibly convert it to water-soluble. It is extracted from animal bones, skin, tendons and the like by boiling with water.
Casein is a phosphoprotein that is the main component of milk. A dichromate such as ammonium dichromate is added to an aqueous solution of these natural proteins, and the spin coat method and roller coat method are used.
When the composition is uniformly coated on a substrate such as glass by a coating method or the like and then irradiated with ultraviolet rays, the coating layer is cured and a water-insoluble film is formed.

Further, as an example of the synthetic resin having a cationic group as the material to be colored used in the present invention, a polymer having a photoreactive unsaturated group in the side chain and a quaternary ammonium salt group is photopolymerized. A resin composition comprising an initiator and a solvent, or a photo-crosslinking group such as a chalcone group, a cinnamic acid group, an azide group, a stilbazol group or an epoxy group is previously polymerized.
A resin composition in which a cationic group-containing polymer introduced therein is dissolved in water or an organic solvent, or a nitrogen-containing monomer
As one of the essential constituents, a polymer obtained by polymerization is added with a photocrosslinking agent such as a diazo compound, an azide or a diazide compound, and a resin composition diluted with an organic solvent. Such a photoreactive resin composition is applied to the surface of a substrate and cured by irradiation with actinic rays such as ultraviolet rays to obtain a film. Specific examples of the resin composition suitable for obtaining the color filter of the present invention include CFR633L1 (manufactured by Nippon Kayaku Co., Ltd.), CFR-3 (manufactured by Nippon Kayaku Co., Ltd.), C
FR-5 (Nippon Kayaku Co., Ltd.), R-102 (Nippon Kayaku Co., Ltd.), JDS-509 (Nippon Synthetic Rubber Co., Ltd.)
Etc.

The ink composition of the present invention is used as it is, or after being diluted to a desired concentration, as an ink liquid loaded in an ink jet dyeing apparatus. The dye concentration in the ink solution is preferably 0.5 to 20%, particularly preferably 3 to 10
%. The diluent solvent for the ink composition of the present invention,
For example, water or an aqueous organic solvent solution that can be mixed with water is used. As the organic solvent, methyl alcohol, ethyl alcohol, butyl alcohol, methyl cellosolve, ethyl cellosolve, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dimethylformamide, dimethyl Examples include acetamide and N-methylpyrrolidone. When preparing the ink liquid, it is possible to add and mix a dye other than the dye represented by the general formula (1) or (3). As the dye other than the dye represented by the general formula (1) or (3),
Examples thereof include acid dyes, direct dyes, reactive dyes, etc., and acid dyes are preferable.

The compound represented by the general formula (1) or (3) is produced, for example, by the following method. That is, the method for synthesizing the anthraquinone compound represented by the general formula (1) is as follows, using a compound of the following formula (4) derived from leucoquinizarin or a bromamic acid derivative of the formula (5) as a starting material by a known synthesis method. Manufactured by the method.

[0053]

[Chemical 19]

(In the formula, R ₁ , R ₂ , R ₃ and M have the same meanings as described above.) When the compound of formula (4) is used as a starting material, the anthraquinone compound of formula (4) is used. Sulfonation is carried out by reacting in a 3 to 100 times amount (weight ratio) of 0 to 30% fuming sulfuric acid at a temperature of 0 to 80 ° C. for about 0.5 to 10 hours, or by using a compound of the formula (5) as a starting material. When used as
It can be synthesized according to the method described in JP-B-60-58260, and can be obtained by reacting a bromamic acid derivative of formula (5) with a compound having a hydroxyalkyl group at the terminal. This reaction is usually carried out in an acidic medium, preferably concentrated sulfuric acid, under the reaction conditions of 10 to 50 ° C. and 5 to 30 hours.

Next, the method for synthesizing the triphenylmethane compound represented by the general formula (3) can be obtained by a known synthesis of a general triphenylmethane acid dye. That is, it is synthesized by direct sulfonation of a basic dye such as a dye containing an N-benzyl group, condensation with benzylanilinesulfonic acid or benzaldehyde sulfonic acid, condensation of tetraalkylaminobenzhydrol with naphthalene or naphtholsulfonic acid, and the like. It As the solvent used in the condensation reaction, water, alcohols, or a cellosolve-based aqueous organic solvent is used, and the reaction is performed at 80 ° C. to 150 ° C. for 5 to 30 hours.

The water-soluble salt of the compound of the general formula (1) or (3) is prepared by adding a base corresponding to the water-soluble salt, for example, an alkali metal hydroxide such as NaOH, KOH or LiOH to the obtained aqueous solution of sulfonic acid. , Ammonia, organic amines (eg,
NH ₂ CH ₂ CH ₂ OH, NH (CH ₂ CH ₂ OH) ₂
Alternatively, mono (-di- or tri (hydroxy (C ₁ -C ₅ ) alkyl) amine) such as N (CH ₂ CH ₂ OH) ₃ is added for neutralization, and then salt is added with a salt of the corresponding cation component. It is obtained by analysis.

Next, specific synthesis examples of the compound represented by the general formula (1) or (3) will be described below. In the text, parts and% are based on weight. (Synthesis Example 1) 2.2 parts of a compound represented by the following formula (6) was dissolved in 30 parts of 95% concentrated sulfuric acid, and 0.8 part of benzoylaminohydroxymethane was gradually added at 30 ° C. or lower with stirring. And react at a temperature of 10 to 30 ° C. for 24 hours. The reaction product is poured into 300 parts of ice water, and the formed precipitate is separated by filtration.
Then, the precipitate separated by filtration was suspended in 100 parts of water, and 1
The pH value is 7.0 with a 0% aqueous sodium hydroxide solution.
Adjust to 8.0 to dissolve completely and salt out with sodium chloride. The crystals obtained were filtered off and dried at 60 ° C. 1
2.7 parts of compound 1 are obtained.

[0058]

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(Synthesis Example 2) 20.0 parts of ethylbenzylanilinesulfonic acid was added to 47.6 parts of water, and the pH value was adjusted to about 4.5 with a 10% aqueous caustic solution at a temperature of 50 ° C. Add 4.8 parts of p-chlorobenzaldehyde to give 9
The reaction is carried out at a temperature of 8 to 105 ° C. for 26 hours. After cooling down, 80
The crystals formed at around C were filtered off and dried to obtain 23.7 parts of the compound of formula (8). Next, 10.5 parts of the compound of formula (8) was suspended in 80 parts of water, and P was added with 2.1 parts of sodium carbonate.
The H value is adjusted to 8.5 to 8.8, liquid filtration is performed, and ice is added to the obtained filtrate to adjust the temperature to about 10 ° C. Next, 25 parts of an aqueous solution containing 1.7 parts of sodium dichromate, 3.7 parts of oxalic acid, and 1.5 parts of concentrated sulfuric acid is added dropwise for oxidation. After reacting at 10 to 20 ° C. for 1 to 2 hours, salting out with sodium chloride and the generated crystals are separated by filtration. The crystals obtained are then suspended in 50 parts of water, 10.3 parts of phenetidine are added and the temperature of 98-
After reacting at 104 ° C. for 8 hours, acid precipitation is performed with 45 parts of concentrated hydrochloric acid.
The crystals obtained were dried to give No. 27 compounds 10.5
I got a part.

[0060]

[Chemical 21]

(Synthesis Example 3) In 106 parts of butanol, 37.2 parts of leucoquinizarin and 60 parts of 2,4-xylidine were added.
8 parts and boric acid 18.75 parts are added, and the reaction is carried out at a temperature of 135 to 140 ° C. for 10 hours while distilling off the solvent. The resulting reaction product is then dissolved in acetic acid and brominated with bromine to give 98.0 parts of compound of formula (10). Formula (10)
5.0 parts of the above compound is added to 30 parts of concentrated sulfuric acid at a temperature of 10 ° C. or lower, and the sulfonation reaction is performed while gradually adding 30% fuming sulfuric acid. After the reaction is complete, pour the reaction solution into ice water,
The precipitated crystals were separated by filtration, washed with water and dried to give No. 6.2 parts of compound 2 are obtained.

[0062]

[Chemical formula 22]

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the text, parts and% are based on weight. Example 1 No. After adjusting the pH of the reaction solution containing 6 parts of the compound of 11 to 6 to 8, the insoluble matter is removed by filtration. Next, the salt was desalted by the reverse osmosis method to make the inorganic salts 0.5% or less with respect to the pigment, and 2 parts of ε-caprolactam and 1 part of Kayachelator C were added to this solution.
Add 1000, 0.3 parts deltop. After liquid filtration of this liquid again, it was further microfiltered with a membrane filter with a pore size of 1 micron and with a membrane filter of 0.45 micron, and ion-exchanged water (filtered with a membrane filter of 0.45 micron: the same below). Was adjusted so that the total amount would be 100 parts, and the ink composition for a color filter of the inkjet printing system of the present invention was obtained. The color filter ink composition obtained in this example showed good stability at room temperature and low temperature (−5 ° C.) for one month or longer.

Example 2 No. The pH of the reaction solution containing 5 parts of the compound of 21 is adjusted to 6 to 8 and then filtered to remove insoluble matter. Next, the salt was desalted by the reverse osmosis method to make the inorganic salts 0.5% or less with respect to the dye, and 2 parts of N-methyl-pyrrolidone, 1 part of Kayakylator C-1000 and 0.3 part of Deltop were added to this solution. Is added. After this liquid is filtered again, it is further microfiltered with a membrane filter having a pore size of 1 micron and a membrane filter having a pore size of 0.45 micron, and adjusted with ion-exchanged water so that the total amount becomes 100 parts, and then the ink jet print of the present invention. An ink composition for a color filter of the type was obtained. The color filter ink composition obtained in this example showed good stability at room temperature and low temperature (−5 ° C.) for one month or longer.

Example 3 Dyeable photosensitive resin liquid CFR-3 (manufactured by Nippon Kayaku Co., Ltd.) 1
00 parts and 0.05 part of silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. This is coated on a glass plate by a spin coating method, dried at 110 ° C. for 3 minutes, and then exposed through a belt conveyor type UV irradiator and cured. The exposure amount was about 150 mJ / cm ² . The glass substrate having the thin film to be dyed thus formed is accurately positioned by an optical prescription and set in an inkjet printer. The blue ink composition described in Example 1 (4% aqueous solution of the compound of No. 11) is jetted as a dyeing solution by an ink jet through a 0.2 μm membrane filter to color the dyed thin film blue. Attach to the part. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, as dye fixation treatment, 3 g of tannin and 1 tartrate in 1 liter of water.
g, a dyed glass substrate was immersed in a solution containing 3 g of acetic acid, treated at 70 ° C. for 7 minutes, washed with water, and then at 130 ° C. for 1 minute.
After drying for 0 minutes, a color filter having a blue pattern was obtained. The blue color filter thus obtained has a substantially square pattern of about 150 μm, and has the same performance as a color filter formed by a conventional so-called dyeing method.

Example 4 Dyeable photosensitive resin liquid CFR-3 (manufactured by Nippon Kayaku Co., Ltd.) 1
00 parts and 0.05 part of silane coupling agent KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) are mixed. This is coated on a glass plate by a spin coating method, dried at 110 ° C. for 3 minutes, and then exposed through a belt conveyor type UV irradiator and cured. The exposure amount was about 150 mJ / cm ² . The glass substrate having the thin film to be dyed thus formed is accurately positioned by an optical prescription and set in an inkjet printer. The blue ink composition described in Example 2 (4% aqueous solution of the compound of No. 21) was jetted as a dyeing solution by an ink jet through a 0.2 μm membrane filter to color the thin film to be dyed green. Attach to the part. This is dried by heating on a hot plate heated to 150 ° C. for 10 minutes. Next, as dye fixation treatment, 3 g of tannin and 1 tartrate in 1 liter of water.
g, a dyed glass substrate was immersed in a solution containing 3 g of acetic acid, treated at 70 ° C. for 7 minutes, washed with water, and then at 130 ° C. for 1 minute.
After drying for 0 minutes, a color filter having a blue pattern was obtained. The blue color filter thus obtained has a substantially square pattern of about 150 μm, and has the same performance as a color filter formed by a conventional so-called dyeing method.

Example 5 A glass substrate having a black stripe formed by a conventional method was spin-coated with a spinner a photosensitive resin composed of a mixture of a water-soluble nylon resin and a stilbazolium resin in a thickness of 1 μm, at 90 ° C. After drying for 15 minutes, the entire surface of the glass was exposed. Then, it was immersed in water for 2 minutes and developed to obtain a dyeable resin film having a black stripe on the substrate. This glass substrate was set in an inkjet printer in the same manner as in Example 3, and the ink composition described in Example 1 was used to eject the glass substrate to form a color filter.

Examples 6 to 34 Nos. 1-No. The compound of 29 was synthesized, an aqueous ink composition was prepared according to Examples 1 to 5, and a color filter was prepared by an inkjet method using the composition. Tables 1 to 5 show the structure of the dye used and its content by weight, the additive composition (the type of organic solvent and / or the dissolution aid and its content by weight), the hue of the colored film, and the color on the colored film. The maximum transmission wavelength λ _Tmax (nm) is shown. still,
In the table, EG is ethylene glycol, DG is diethylene glycol, TG is triethylene glycol, PEG is polyethylene glycol, PG is propylene glycol, M
E is methyl cellosolve, EE is ethyl cellosolve, NM
P means N-methylpyrrolidone and CR means ε-caprolactam.

[0069]

Table 1 Table 1 Example Compound No. Additive composition Colored film Transmission maximum wavelength (wt%) (wt%) Hue (nm) 6 1 (5) EE (10) Blue 625 7 2 (4) EG (5) Blue 624 8 3 (6) Urea ( 2) Blue 625 9 4 (4) PEG (5) Blue 622 10 5 (6) DG (5) Blue 626 11 6 (4) EE (10) Blue 626 12 7 (8) DG (5) Blue 626 NMP ( 5) 13 8 (5) PG (5) Blue 624 14 9 (6) Urea (2) Blue 623 TG (10) 15 10 (4) ME (10) Blue 624 16 11 (8) Urea (5) Blue 634 EE (10) 17 12 (4) Urea (2) Blue 635 PG (15) 18 13 (6) EE (20) Blue 634 19 14 (5) NMP (5) Blue 635 EE (25) 20 15 (4) Urea (5) Blue 632 PG (10) 21 16 6) CR (5) Blue 636 EE 15 22 17 (4) NMP (2) Blue 634 EE 25 23 18 (5) Urea (5) Blue 634 TG (5) 24 19 (3) CR (5) Blue 634 PEG (25) 25 20 (4) TG (25) Blue 633 26 21 (8) EE (40) Blue 634 27 22 (5) Urea (5) Blue 632 EE (20) 28 23 (6) CR (5) Blue 634 PEG (25) 29 24 (4) Urea (5) Blue 630 DG (20) 30 25 (4) CR (5) Blue 634 EE (20) 31 26 (5) Urea (5) Blue 632 PG (15) 32 27 (6) NMP (3) Blue 634 EE (20) 33 28 (4) ME (20) Blue 635 34 29 (5) EE (30) Blue 630

[0070]

EFFECT OF THE INVENTION By using an ink composition containing a specific compound represented by the general formula (1) or (3) to produce a color filter by an inkjet method, an inexpensive and high-quality color filter can be obtained. Became.
Moreover, these ink compositions are advantageous because they have high chemical and physical stability.

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Claims (4)

[Claims] 1. A free acid represented by the following formula (1): (In the formula (1), X and Y are independently a hydrogen atom or the following formula (2): (In the formula (2), R ₁ , R ₂ , and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a sulfonic acid group, or a hydroxyalkyl group. Represents a group or an alkoxyalkyl group, R ₄ is a hydrogen atom, a sulfonic acid group, the following formula (a) or the following formula (b): (In the formula, R ₁₀ , R ₁₁ , and R ₁₂ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a sulfonic acid group, a hydroxyalkyl group, or an alkoxyalkyl group. Represents a group, k represents an integer of 1 to 4,
j represents 1 or 2) (wherein one of X and Y is a group other than a hydrogen atom), n represents 0 or 1, and m represents 1 or 2. And M represents H. ) At least one of the anthraquinone-based compounds represented by the following formula or the following formula (3): (In the formula (3), R ₅ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and R ₆ , R ₇ , R ₈ and R ₉
Are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms which may have a substituent, a phenyl group which may have a substituent or a benzyl group which may have a substituent. And M has the same meaning as described above. ) An ink composition comprising at least one triphenylmethane compound represented by the formula (1). 2. An ink composition for producing a color filter, which comprises at least one of the compounds according to claim 1. 3. An ink composition for producing a color filter by an inkjet method, which comprises at least one of the compounds according to claim 1. 4. Using the ink composition according to claim 1,
Color filter manufactured by inkjet method.