JPH09211219A - Production of color filter by ink-jet printer containing metal alkoxide in the ink - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a high-quality color filter having a red, green and blue- colored layers in the fine region divided by a black matrix having light fastness and resistance to water and excellent in adhesion by allowing a sol-gel liq. to have a physical property suitable to the ink of an ink-jet printer. SOLUTION: A colored composition consisting of a metal alkoxide or its hydrolytic polycondensate, a pigment and a polar solvent is used to form a colored layer in a transparent glass or metal oxide thin film or plastic film with an ink-let printer. The polar solvent has >=90 deg.C b.p. at atmospheric pressure. The metal oxide is exemplified by M(OR)m Xn , where M is a metallic atom, R is a <=4C alkyl, allyl, aralkyl or thioalkyl or halogen atom, and (m+n) is the valence of M, (m) is an integer of 2 to 4, and (n) is an integer determined by the valence of M and (m).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to R (red) and G (green) in a fine region defined by a grid-like black matrix on a substrate, such as a color filter used in a color liquid crystal display device. , B (blue) transparent colored layers are repeatedly arranged vertically and horizontally.
This method can be applied to the manufacture of any optical filter that requires a fine pattern other than the above.

[0002]

2. Description of the Related Art Conventionally, a color filter, for example, for a color liquid crystal display device has been manufactured mainly by a lithographic method. This involves forming a photoresist layer on a substrate such as glass, irradiating it with UV light through a desired pattern, removing the unnecessary resist layer by etching, and dyeing the remaining resist with a dye or electrodepositing a pigment dispersion. It is a method of dyeing by such means. However, in this method, a color filter is very expensive because it involves a great number of complicated steps of sequentially forming so-called three primary colors of R, G, and B and a black matrix. For this reason, attempts have been made to reduce the cost by using the printing method, but it is difficult to form a fine pattern and align each color with the printing method.Because an organic polymer is used as a binder, it has light resistance. Was not enough to satisfy. As a method for forming a fine pattern, Japanese Laid-Open Patent Publication No. 59-75205 proposes an ink jet printing method, but the feasibility is unclear because there is no specific description about the ink composition and other materials. Japanese Patent Laid-Open Publication No. 4-306619 discloses a method for producing a color filter having a metal alkoxide as a carrier for the purpose of imparting light resistance to a colored layer, but in order to form a colored layer, printing is performed for each color. Since this method is adopted, the manufacturing process is considerably complicated.

[0003]

The object of the present invention is to have physical properties applicable to ink jet printers, light resistance,
It is an object of the present invention to provide a method for producing a color filter having excellent light resistance and adhesion to a substrate by an inkjet printing method using a recording ink composition having excellent adhesion to a substrate, particularly an inorganic material substrate. . Although a method using an inkjet printer for producing a color filter at low cost and a method using a metal alkoxide as a carrier for imparting light resistance to a colored layer have been proposed,
A method of using an ink composition having a metal alkoxide as a carrier and further forming a colored layer on a substrate with an inkjet printer has not been realized yet. this is,
The colloidal dispersion of metal alkoxide or its hydrolyzed polycondensate is required for ink for inkjet printers due to drying or gelation due to the progress of hydrolysis reaction. Was difficult to achieve.

[0004]

Recently, a so-called sol-gel method for obtaining a gel in a thin film or a bulk body from a colloidal dispersion of a hydrolyzed polycondensation product of a metal alkoxide has been actively researched. Has excellent light resistance, water resistance and oil resistance. Applying this sol-gel method to a colloidal dispersion of a hydrolyzed polycondensation product of metal alkoxide, a so-called sol-gel solution, a dye is added to make a coating solution, and a coating film colored by dip coating or spin coating on a substrate such as glass. Although the technology for forming the ink has become quite known, there is still no example of finishing the ink composition applicable to an ink jet printer.

The present inventors have focused on the light resistance, water resistance and oil resistance of a colored coating film obtained by a sol-gel method using a hydrolyzed polycondensation product of a metal alkoxide, and have a sol-gel solution suitable for ink for ink jet printers. It has been clarified that high-definition printing with excellent light resistance, water resistance, and oil resistance can be achieved by the inkjet printing method if it has physical properties. In addition, a high-quality color filter having transparent R, G, and B colored layers in a fine region divided by a black matrix, which has excellent light resistance and water resistance and excellent adhesion to a substrate, is produced by using this method. I was able to create it. According to this method, the black matrix and the colored layers of the three primary colors of R, G, and B could be simultaneously formed by one run of the printer head. As a matter of course, in a fine area defined by a black matrix formed in advance, R,
It is also possible to form G and B colored layers. That is, according to the inkjet method, the color filter can be manufactured by an extremely simple process.

The development of ink is the most important for completing the manufacturing method of the color filter by the ink jet printer. The most important property required for ink for inkjet printers is that the ink can be continuously ejected from an extremely thin nozzle. For this purpose, it is required that the ink does not contain coarse particles, is stable for a long time without solidifying, and has an appropriate viscosity and surface tension. The present inventors have used a sol of a hydrolysis-condensation polymer of a metal alkoxide having light resistance, water resistance, and oil resistance as a binder, and appropriately selected an ink composition suitable for an inkjet printer, a solvent type and an ink composition. When we focused on the physical properties of the material, we were able to produce an ink with good ink jet printer suitability only under appropriate conditions. A color filter having excellent light resistance and adhesion to a substrate is formed by forming a transparent colored layer having a fine repeating pattern of R, G, and B on a substrate by an inkjet printing method using the ink composition. I was able to get

The sol-gel method is a method in which a metal alkoxide is added to water and a catalyst in a solvent to cause hydrolysis and polycondensation to form a metal oxide gel on the surface of an adherend from the obtained colloidal dispersion. If you do not strictly control the solvent type, metal alkoxide concentration, hydrolyzed water amount, catalyst type, amount, etc., a precipitate will be generated, the viscosity will increase, and a gel will easily form due to evaporation of the solvent. In order to use it as a component of printer ink, it is necessary to devise it in order to prevent precipitation and gel formation.

When a dye is used as a coloring matter, there is no problem, but in the case of a pigment, it is desirable that the pigment be dispersed in a solvent in the presence of a dispersant in order to prevent nozzle clogging. Even when this dispersion liquid is added, the pigment and the dispersant solidify due to the volatilization of the solvent, so it is necessary to devise a means for preventing this.

The solvent contained in the solvent of the present ink composition is a polar solvent having a boiling point of 90 ° C. or higher at atmospheric pressure, and it is necessary to contain at least one of them. In the sol-gel method, it is usually performed in a low boiling alcohol solvent such as ethanol, but n-propanol, n-butanol, n-pentanol, 2-methylbutanol, benzyl alcohol, hexylene glycol, ethylene glycol monoethyl ether, ethylene glycol. Monoacetate, diethylene glycol dimethyl ether, 2-
Even in a polar solvent having a relatively high boiling point such as pyrrolidone or N-methyl-2-pyrrolidone, the hydrolytic condensation polymerization of metal alkoxide can be carried out without any problem.

The solvent in which the pigment is dispersed is not particularly limited, and the pigment can be dispersed in the solvent without any trouble. When preparing the ink composition, a solvent can be further added, but it is preferable to use the alcohol solvent in consideration of the compatibility with the sol-gel liquid and the pigment dispersion liquid. As the polar solvent contained in the solvent of the present composition, n-propanol,
n-butanol, 2-butanol, isobutanol, n
-Pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, n-hexanol, 4-methyl-2-pentanol , 2-ethylbutanol, n-heptanol, benzyl alcohol, tetrahydrofurfuryl alcohol and other monohydric alcohols,
Ethylene glycol, propylene glycol, triethylene glycol, hexylene glycol, polyethylene glycol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Polyhydric alcohols such as ethylene glycol monobutyl ether, ethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol dimethyl ether, or ethers of polyhydric alcohols, esters, amides such as dimethylformamide, dimethylacetamide, 2
Examples include, but are not limited to, cyclic amides such as -pyrrolidone and N-methyl-2-pyrrolidone.

Since the ink composition of the present invention may finally contain a predetermined solvent, the sol-gel solution, dye solution and pigment dispersion do not necessarily have to be prepared with the solvent. That is, the sol-gel liquid of the present composition is methanol,
It may be prepared in a low boiling point solvent such as ethanol. The same applies to dye solutions and pigment dispersions. When the ink composition does not contain a predetermined solvent, the non-volatile components such as the hydrolyzed polycondensation product of metal alkoxide, dyes, pigments and dispersants solidify and the nozzles are clogged and printing is not possible at all or extremely unclear. I can only print.

When the dye is a pigment, it is necessary that it does not contain coarse particles in order to avoid nozzle clogging. The particle size is preferably 1 micron or less. In particular, transparency is required for the ink used for manufacturing the color filter, and therefore, in the case of a pigment, the particle type is preferably 300 nm or less. The inkjet printing method is
In this method, ink droplets are ejected from the nozzles of the printer head and adhered to the printed material. There is a method of applying pressure with a piezo element, for example, to eject the ink droplets, but the viscosity and surface tension of the ink are important factors in the process of ejecting the ink droplets and adhering them to the printing material. In particular, viscosity is an important key to whether ink can be ejected. As a result of repeated experiments, the inventors of the present invention have confirmed that it is difficult to print unless the viscosity is 30 CPS or less, especially in the case of a piezo type inkjet printer characterized by high-definition printing. Further, in order to obtain a pattern with little bleeding of ink and good dimensional stability, it is necessary that the viscosity of the ink composition is 3 CPS or more. Further, it is generally said that the surface tension is preferably 35 to 55 dyn / cm, but in the composition of the present invention, it is 26 dyn / cm.
I was able to print even in cm.

The ink composition used in the present invention is not only applicable to an ink jet printer, but also a metal oxide gel obtained from a hydrolyzed polycondensation product of a metal alkoxide acts as a binder, and has light resistance and water resistance. It is possible to provide a printed matter having excellent properties and oil resistance. The ink used for an ink jet printer, which has been conventionally used, is basically formed by simply dissolving a water-soluble dye in water, but there is a problem in that the light resistance and water resistance of the printed matter are poor. In the ink composition used in the present invention, since the fine particles of the dye or pigment are fixed in the matrix of the metal oxide gel, not only the water resistance but also the oil resistance is excellent. Further, since the metal oxide gel absorbs ultraviolet rays, even if the dye has insufficient light resistance, the light resistance of the printed matter is remarkably improved. Lightfastness is an essential element in color filters, but this can only be achieved with ink compositions suitable for the present invention.

The ink composition according to the present invention can be prepared by the following method. A colloidal dispersion of a hydrolyzed polycondensation product of a metal alkoxide is added with water for hydrolysis and a catalyst for accelerating the hydrolysis if necessary, and a monomer or oligomer of the metal alkoxide is further added and stirred. Easily obtained. The metal alkoxide in this case is appropriately selected from those described in the scope of claims, and particularly tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, tetraisopropoxytitanium and tetra-n. -Butoxyzirconium, triisopropoxyaluminum monomer or oligomer, etc. are preferably used.

The solvent used in this case is methanol, ethanol, n-propanol, regardless of the scope of the claims.
Isopropanol, n-butanol, isobutanol,
Monohydric alcohols such as n-pentanol, 2-methylbutanol, bezyl alcohol and tetrahydrofurfuryl alcohol, polyhydric alcohols such as ethylene glycol, 1,3-pentanediol and hexylene glycol,
Ethers or esters of polyhydric alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, ethylene glycol monoacetate, ethylene glycol monoethyl ether acetate, 2-pyrrolidone, N-
A polar solvent such as methyl-2-pyrrolidone can be used, but in order to prevent the formation of a gelled product as the polycondensation reaction proceeds, it is desirable to dissolve it in water.

However, when water is consumed due to the progress of hydrolysis or an alcohol formed from a metal alkoxide finally forms a uniform colloidal dispersion liquid and a gel is not formed, the solvent is not necessarily mixed with water. No need to melt. When a catalyst is added to accelerate the hydrolysis, the catalyst is preferably acidic. When the catalyst is basic, the liquid may gel and is not suitable for the use of the present composition. As the acidic catalyst, inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as acetic acid, oxalic acid, succinic acid, maleic acid and lactic acid can be used.

The dyes used in the present invention include azo type, anthraquinone type, naphthoquinone type, isoindolinone type,
Perylene, indigo, fluorenone, phenazine, phenothiazine, polymethine, polyene, diphenylmethane, triphenylmethane, quinacridone, acridine, phthalocyanine, quinophthalone, organic dye or pigment, or titanium white, Bengal,
It can be selected from inorganic pigments such as cobalt blue and carbon black, but is not limited thereto. When the dye is a pigment, it is usually pulverized into fine particles, but when it is used as a component of an ink for an inkjet printer, it is wet pulverized into ultrafine particles in a solvent in the presence of a dispersant. Can be recommended. The suitability of an ink composition of the present invention for an inkjet printer and the light resistance, water resistance, and oil resistance are apparent in the following examples. It was possible to provide inkjet printing for the first time using this ink composition, and to provide a very simple method for producing a color filter.

[0018]

【Example】

Example 1 23.7 g of isopropanol, 5.2 g of water and 25.7%
0.3 g of nitric acid aqueous solution was mixed, 20.8 g of tetraethoxysilane was added, and the mixture was stirred for 2 hours and left overnight. 16 g of the metal alkoxide colloidal dispersion thus obtained
To a copper phthalocyanine pigment (C.I. pigment blue
16 g of a fine particle dispersion containing 7.5% of 15) in isopropanol was diluted with 32 g of n-butanol and added.
The obtained composition contains 54% of n-butanol. The viscosity was 15.1 CPS. A black ink cartridge of a commercially available inkjet printer (MJ500C manufactured by Seiko-Epson) was washed with this composition and then charged, and a personal computer (FM-produced by Fujitsu-
When a pattern having a line width of 100 microns and a spacing of 500 microns prepared in V) was embossed on a slide glass fixed on plain paper, a bright blue transparent pattern was printed with almost no bleeding. This pattern was not easily peeled off without heat treatment. The printed glass plate was heat-treated at 150 ° C. for 30 minutes and then immersed in water, ethanol, acetone, or dimethylformamide for 24 hours, but no peeling of the colored layer from the glass substrate occurred. Further, this glass plate was irradiated with ultraviolet rays for 24 hours with a sunshine weather meter, but no discoloration occurred.

Example 2 62.8 g of n-butanol, 6.5 g of water and 0.2 g of oxalic acid
Was mixed, 30.5 g of an oligomer of tetramethoxysilane (polymerization degree: about 5) was added, and the mixture was stirred for 2 hours and then left overnight to obtain a sol-gel solution. 10 g of this was taken, and 30 g of a dispersion having a content of 2.5% in which a copper phthalocyanine pigment was dispersed in ethanol was mixed with 60 g of n-butanol. The n-butanol pigment of this composition is 66.3%. The viscosity was 3.7 CPS. When a pattern was printed out from this composition by an ink jet printer in the same manner as in Example 1, a clear blue image was obtained on the glass substrate. The printed image was heat-treated at 150 ° C. for 30 minutes and then immersed in water, ethanol, acetone, and dimethylformamide for 24 hours, but the colored layer did not peel off from the glass substrate (slide glass). Further, the glass substrate on which the colored pattern was formed was irradiated with ultraviolet rays for 120 hours with a sunshine weather meter, but deterioration or discoloration hardly occurred.

Example 3 10 g of the sol-gel solution obtained in Example 2, 30 g of an isopropanol dispersion of copper phthalocyanine (CI Pigment Green 7) (5% dye content) and 60 g of ethylene glycol monomethyl ether were mixed. An ink composition was obtained. The total content of n-butanol and ethylene glycol monomethyl ether contained in this composition was 6
It is 6.3%. The viscosity was 3.5 CPS. In the same manner as in Example 2, a grid pattern having a line width of 100 μm and a spacing of 500 μm was formed on a glass substrate (slide glass) using a personal computer (Fujitsu FM-
V) to inkjet printer (MJ-500C)
The green pattern was clearly printed. The same water resistance, oil resistance, and light resistance tests as in Example 2 were conducted, but the results were the same.

Example 4 65 g of ethylene glycol monoethyl ether and water 6.
To a mixture of 2 g and 0.3 g of maleic acid, 28.5 g of tetramethoxysilane oligomer (polymerization degree of about 5) was added to about 2
After stirring for an hour, it was left overnight. This colloidal dispersion 30
g and 5% isopropanol dispersion solution of dimethylquinacridone 35 g and ethylene glycol monoethyl ether 35
g was mixed to obtain an ink composition. The ethylene glycol monoethyl ether content of this composition is 54.5%. The viscosity was 3.0 CPS. Further, using the obtained composition, printing was performed on a polycarbonate film having an ITO film formed on the surface thereof in the same manner as in Example 1, and as a result, a red pattern was formed. No nozzle clogging occurred even with continuous printing. When this substrate was irradiated with ultraviolet rays for 24 hours, almost no fading occurred.

Example 5 Using the sol-gel solution obtained in Example 2, an ink composition shown in the table below was obtained. The obtained ink composition was washed with three color cartridges of a color printer head of an inkjet printer (MJ800C manufactured by Seiko Epson) and a cartridge of a black monochrome head, and the compositions 1 to 4 were filled in the respective ink cartridges. (IBM Master P
120), a pattern formed by arranging R, G, and B in a region divided by a black matrix as shown in FIG. 2 drawn by using a paint brush of Windows 3.1 is fixed on a plain paper (a glass substrate). When printed on a slide glass), a clear pattern with almost no bleeding was printed. The image that was heat-treated at 150 ° C. did not peel off when wiped with water, ethanol, or acetone. The glass substrate was irradiated with UV light for 120 hours with a sunshine weather meter, but almost no fading was observed.

[Brief description of drawings]

A plan view of a conceptual view of a color filter provided by the present invention is shown in FIG. A sectional view is shown in FIG. In FIG. 1, (1) is a black matrix, (2)
Is a colored pixel area, R is red, G is green, B is blue, A is
---------- A 'is a cutting position for explaining the cut surface. (3) in FIG. 2 is a black matrix, (4) is a colored pixel region, and (5) is a transparent substrate.

Claims (9)

[Claims] 1. A colored composition comprising a metal alkoxide or a hydrolyzed polycondensate thereof, a dye, and a polar solvent is used to form a colored layer on a transparent glass or metal oxide thin film or a plastic film by an ink jet printer. Of manufacturing color filter characterized by 2. The method for producing a color filter according to claim 1, wherein the ink composition is one in which the boiling point of the polar solvent is 90 ° C. or higher under atmospheric pressure. 3. The method for producing a color filter according to claim 1, wherein an ink composition containing at least 30% (by weight) of a polar solvent having a boiling point of 90 ° C. or higher under atmospheric pressure is used. 4. The metal alkoxide has the general formula M (OR) m Xn, where M is a metal atom, R is an alkyl group having 4 or less carbon atoms,
X represents an alkyl group, an allyl group, an aralkyl group or a thioalkyl group, a halogen atom m + n represents a valence number of M,
The method for producing a color filter according to claim 1, wherein m is an integer of 2 to 4, n is an integer selected from the valence number of M and the value of m. 5. The method for producing a color filter according to claim 1, wherein the metal in the metal alkoxide is a transition metal atom. 6. The method for producing a color filter according to claim 1, wherein the transition metal atom is silicon, titanium, aluminum or zirconium. 7. The method for producing a color filter according to claim 1, wherein the dye in the ink composition according to claim 1 is a dye or an organic or inorganic pigment. 8. A color filter comprising a black matrix and the three primary colors of light that is a pixel, R (red), G (green), and B (blue). A method for producing a color filter, characterized in that the steps are performed simultaneously by one run. 9. An ink composition for an ink jet printer, comprising as a carrier a hydrolytic condensation polymer of a metal alkoxide selected from silicon, titanium, aluminum and zirconium, as a dye, a dye or an organic or inorganic pigment or carbon. Include at least 3 polar solvents with boiling point of 90 ℃ or more under atmospheric pressure
A method for producing a color filter by an inkjet method using an ink composition characterized by comprising 0% (weight) or more