JP2003107230A - Reaction setting water type ink composition for color filter and manufacturing method for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition for a color filter which hardly causes ink to increase in viscosity at the tip of an ink jet head, can accurately and uniformly be stuck on a specific area on the top surface of a substrate, and is preferable in terms of operation sanitation and to provide a method for manufacturing the color filter by using such an ink composition. SOLUTION: The photosetting water type ink composition for the color filter is formed by dissolving or dispersing at least a binder and a multifunctional, e.g. a two- to three-functional monomer in water. Further, an ink layer is formed by sticking this ink composition selectively on the specific area on the top substrate surface of the color filter by an ink jet system and is made to react to set, thereby forming a setting layer in a specific pattern.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a reaction-curable ink composition used for forming a cured layer having a predetermined pattern such as a pixel portion (colored layer) on a substrate of a color filter, and the reaction. The present invention relates to a method for producing a color filter using a curable ink composition.

[0002]

2. Description of the Related Art In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, especially color liquid crystal displays, has been increasing. However, since the color liquid crystal display is expensive, there is an increasing demand for cost reduction, and in particular, there is a strong demand for cost reduction for color filters having a high specific gravity in terms of cost.

In such a color filter,
Usually, it is provided with a coloring pattern of three primary colors of red (R), green (G), and blue (B), and the liquid crystal serves as a shutter by turning on and off the electrodes corresponding to the respective pixels of R, G, and B. It operates, and light is transmitted through each pixel of R, G, and B, and color display is performed.

As a conventional method for producing a color filter, for example, a dyeing method can be mentioned. In this dyeing method, first, a water-soluble polymer material that is a material for dyeing is formed on a glass substrate, and this is patterned into a desired shape by a photolithography process, and then the obtained pattern is immersed in a dyeing bath. To obtain a colored pattern.
By repeating this three times, a pixel portion composed of R, G, and B is formed.

Another method is a pigment dispersion method. In this method, first, a photosensitive resin layer in which a pigment is dispersed is formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, by repeating this process three times, a pixel portion made of R, G, and B is formed.

[0006] Still other methods include an electrodeposition method, a method of dispersing a pigment in a thermosetting resin, printing three times R, G, and B, and then thermosetting the resin. it can.

However, each of the methods has R, G,
In order to color the three colors of B and B, it is necessary to repeat the same process three times, which causes a problem of high cost and a problem that the yield is reduced because similar processes are repeated.

[0008]

As a method of manufacturing a color filter that solves these problems, there has been proposed a method of forming a colored layer (pixel portion) by spraying a colored ink by an ink jet method (Japanese Patent Laid-Open No. 2000-242242). Sho 59-7520
No. 5). Here, when an ink having good wettability with respect to a glass substrate is used, a method in which a convex portion serving as a boundary is printed in advance with a substance having poor wettability with respect to the ink, or the wettability with respect to glass is poor When using ink, form a pattern in advance with a material that has good wettability with ink,
Methods are disclosed to help the ink set. However, nothing is specifically described about how to separately coat a material having good wettability and a material having poor wettability.

Another method for producing a color filter by spraying a colored ink by an ink jet method to form a colored layer (pixel portion) is disclosed in JP-A-9-20380.
Japanese Patent Publication No. 3 discloses a method of treating recesses with an ink-philic treating agent. In this method, a convex portion is formed on the substrate in advance, the convex portion is made ink-repellent, and then the entire substrate is surface-treated with an ink-philic treating agent. However, this method has a problem that it is necessary to perform the ink repellent treatment and the ink repellent treatment twice, because the convex portion needs to be made ink repellent in advance when the ink repellent treatment is performed.

Similarly, as a method for producing a color filter by forming a colored layer by an ink jet method,
JP-A-8-230314 and JP-A-8-22
Japanese Patent No. 7012 describes a method of forming a colored layer (pixel portion) by providing an ink absorbing layer on a substrate and changing the ink absorbency of the absorbing layer between an exposed portion and a non-exposed portion. There is. However, in this method, since the absorbing layer is formed and the coloring layer is formed by absorbing the ink in the absorbing layer, there is a difference in coloring between the central portion and the peripheral portion of the ink dot, and color unevenness occurs. There is a problem that color loss occurs. In addition, there is a problem that the absorbing layer must have a predetermined thickness because of its function of absorbing ink.

Further, Japanese Patent Laid-Open No. 11-295520 discloses a method for producing a color filter by forming a colored layer (pixel portion) by spraying a colored ink by an ink jet method, and a method of radiation curing by visible light or ultraviolet rays. It is described that a resin composition (colored ink) having a may be used. However, if the conventional UV curable ink is used as it is in the inkjet method, the ink is dried at the tip of the inkjet head while the colored ink is being sprayed, the viscosity gradually increases, and the ejection property deteriorates. As a result, the ejection amount and ejection direction of the colored ink may become unstable, and the inkjet head may be clogged.

Further, conventionally proposed ink jet inks for color filters use an organic solvent, but from the viewpoint of work hygiene in the ink manufacturing process or in the color filter manufacturing process, the use of an organic solvent is preferable. Absent.

The present invention has been accomplished in view of the above circumstances, and a first object thereof is to increase the viscosity of ink at the tip of an inkjet head when the ink is sprayed onto a color filter substrate by an inkjet method. Another object of the present invention is to provide a reactive curable ink composition that is hard to cause, maintains good ejection properties, and does not easily cause head clogging.

A second object of the present invention is to form an ink-philic ink layer forming region having a different wettability from the surroundings on the surface of the color filter substrate and selectively ink to the ink layer forming region. When applied to the color filter, it has a high affinity for the ink layer formation area and a large repulsion property for the surrounding ink repellent area, and it can be attached accurately and uniformly only to a predetermined area on the color filter substrate. An object is to provide an ink composition.

A third object of the present invention is to provide an ink composition for a color filter in which the amount of organic solvent used is reduced from the viewpoint of work hygiene.

A fourth object of the present invention is to provide the above-mentioned first,
By the inkjet method using a photocurable ink composition that can achieve the second or third object, a cured layer having a predetermined pattern such as a pixel portion (colored layer) can be accurately and uniformly formed, and It is to provide a method for manufacturing a filter.

[0017]

A reaction-curable water-based ink composition for a color filter according to the present invention for solving the above-mentioned problems comprises at least a binder and a bifunctional to trifunctional reaction-curable monomer. And a water-soluble organic solvent that is dissolved or dispersed in a water-soluble solvent.

Since the above water-based ink composition uses a reactive curable monomer having a relatively small number of bifunctional or trifunctional functional groups, it is difficult for the viscosity of the head to increase during the spraying operation of the ink jet system, and the head is less likely to rise. Clogging does not occur, and the ink dischargeability during work is stable. Therefore, the ejection amount and the ejection direction of the ink are kept constant, and the ink can be accurately and uniformly adhered onto the substrate in a predetermined pattern.

Further, since the above water-based ink composition uses a water-soluble solvent containing water as a main component, the wettability of a part of the surface of the wettability variable layer is changed so that the wettability is increased. It is possible to make a large difference between the wettability of the photocurable ink composition with respect to the ink layer forming region of the pattern and the wettability of the photocurable ink composition with respect to the surrounding region. Therefore, the reaction curable ink composition for color filters of the present invention, accurately in the ink layer forming region, and
It can be applied uniformly. Therefore, the reaction curable ink composition of the present invention is not limited to the pixel portion forming ink,
Excellent suitability for inkjet system.

Further, in the present invention, by using a water-soluble solvent mainly containing water, it is possible to reduce the amount of the organic solvent used and to avoid volatilization of the organic solvent in the ink manufacturing process or the color filter manufacturing process. It is preferable in terms of work hygiene and environmental hygiene.

By adding a colorant to the above water-based ink composition, a colored pattern such as a pixel portion of a color filter or a black matrix can be formed.

As the above-mentioned bifunctional or trifunctional reaction-curable monomer, a photopolymerization-reactive or heat-polymerization-reactive monomer can be used.

The bifunctional to trifunctional photopolymerization reactive monomer includes an acryloyloxy group as a functional group, and /
Alternatively, those having a methacryloyloxy group can be used. Specifically, ethylene glycol diacrylate, tripropylene glycol diacrylate,
1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, 1,3-butylene glycol At least one selected from dimethacrylate can be used.

As the bifunctional or trifunctional thermopolymerization reactive monomer, one having an epoxy group as a functional group can be used. Specifically, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, 2,3-diglycidyloxystyrene, 3,4- Diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene,
2,6-diglycidyloxystyrene, 5-vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethyl Styrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5
-Dihydroxymethylstyrene diglycidyl ether,
Use at least one selected from 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, and 1,3,5-trihydroxymethylstyrene triglycidyl ether. You can

In the above water-based ink composition, 100 parts by weight of the bifunctional or trifunctional reaction curable monomer is added to the bifunctional or trifunctional reaction curable monomer and a polymerizable tetrafunctional or higher functional curable monomer. It is preferable to contain it in a ratio of 1 to 50 parts by weight. Sufficient film strength and adhesiveness can be imparted to the pattern of the cured layer by blending a proper amount of a tetrafunctional or higher polyfunctional monomer together with the above-mentioned difunctional or trifunctional monomer.

As the above-mentioned water-soluble organic solvent, JIS
Using the standard solution shown in the wetting test specified in K6768, the contact angle (θ) was measured after 30 seconds from contacting the droplets, and the critical surface tension determined by the graph of Zisman plot was 30 mN / m. The contact angle to the surface of the test piece is 1
It is preferable to use one that exhibits a contact angle of 10 ° or less with respect to the surface of a test piece having a critical surface tension of 70 mN / m, which is 0 ° or more and which is obtained by the same measurement method. The same applies to a bifunctional to trifunctional reactive curable monomer and a tetrafunctional or higher functional curable monomer.

By using a material satisfying the above-mentioned wettability, it becomes possible to make a large difference in wettability of the reaction curable ink composition before and after changing the wettability of the wettability variable layer.

A water-soluble glycol is preferably used as the water-soluble organic solvent. When a water-soluble glycol is used as the water-soluble organic solvent, evaporation of the ink composition can be suppressed, and the ink can be prevented from drying and clogging in the inkjet head.

The first method for producing a color filter according to the present invention is: (1) An ink layer is formed by selectively adhering the water-based ink composition according to the present invention to a predetermined region on a substrate by an inkjet method. The method is characterized by including a step of forming and a step (2) of reacting and curing the ink layer to form a cured layer having a predetermined pattern.

The second method for producing a color filter according to the present invention comprises (1) a step of forming a wettability variable layer on the substrate, the wettability variable layer of which wettability can be changed in the direction of increasing hydrophilicity. (2) a step of selectively changing the wettability within a predetermined area of the surface of the wettability variable layer to form an ink layer forming area having a hydrophilicity larger than that of the surrounding area,
(3) a step of selectively adhering the water-based ink composition according to the present invention to the ink layer forming region to form an ink layer, and (4) reacting and curing the ink layer to form a predetermined pattern. And a step of forming a hardened layer.

As the wettability variable layer, it is possible to use a layer that changes the wettability in the direction in which the hydrophilicity is increased by irradiation with light rays. In the case of using the wettability variable layer, as a water-soluble organic solvent of the ink composition, J
Using the standard solution shown in the wetting test specified in IS K6768, the contact angle (θ) was measured after 30 seconds from contacting the droplets, and the critical surface tension determined by the graph of Zisman plot was 30 mN / m. It is preferable to use a test piece having a contact angle with the surface of the test piece of 10 ° or more and a contact angle with the surface of the test piece having a critical surface tension of 70 mN / m obtained by the same measurement method of 10 ° or less. . Bifunctional to trifunctional reaction curable monomers, and 4
The same applies to a reaction curable monomer having a functionality or higher.

The wettability variable layer is made of JIS K676.
Using the standard solution shown in the wetting test specified in 8,
The critical surface tension obtained by measuring the contact angle (θ) after 30 seconds from contacting the droplets with the graph of Zisman plot is
It shows 20 to 50 mN / m before the wettability is changed, and 40 to 8 after the wettability is changed.
Those exhibiting 0 mN / m are preferable.

The water-based ink composition according to the present invention is suitable for an ink jet system. Moreover, the water-based ink composition according to the present invention is particularly preferably used for forming the pixel portion of the color filter.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a reaction curable water-based ink composition for a color filter according to the present invention and a method for producing a color filter using the ink composition will be described.

The reaction-curable water-based ink composition for a color filter according to the present invention comprises at least a binder and a bifunctional to trifunctional reaction-curable monomer as essential components, a water-soluble solvent comprising water and a water-soluble organic solvent. It is characterized by being dissolved or dispersed therein. If necessary, the ink composition of the present invention may contain a colorant, a dispersant, a polymerization initiator, or other additives. Further, in the reaction curable ink composition of the present invention, a bifunctional or trifunctional reaction curable monomer may be used in combination with a tetrafunctional or higher functional reaction curable monomer.

The first method for producing a color filter according to the present invention is: (1) The reaction curable ink composition for a color filter according to the present invention is selectively applied to a predetermined region on a substrate by an inkjet method. The method is characterized by including a step of adhering the ink layer to form an ink layer, and a step (2) of reacting and curing the ink layer to form a cured layer having a predetermined pattern.

Further, the second method for producing a color filter according to the present invention comprises: (1) a step of forming a wettability variable layer on the substrate, the wettability variable layer of which wettability can be changed in the direction of increasing hydrophilicity; (2) a step of selectively changing the wettability within a predetermined area of the surface of the wettability variable layer to form an ink layer forming area having a hydrophilicity larger than that of the surrounding area;
(3) A step of selectively adhering the reaction curable water-based ink composition for a color filter according to the present invention to the ink layer forming region to form an ink layer, and (4) reacting the ink layer. And a step of curing to form a cured layer having a predetermined pattern.

(Solvent) The reaction curable water-based ink composition for color filters of the present invention uses a water-soluble mixed solvent containing water as a main component and a water-soluble organic solvent as a solvent.

When a solvent mainly composed of water is used as the solvent for the reaction curable ink composition, a large repulsion property is exerted on the surface of the wettability variable layer before changing the wettability of the wettability variable layer described later. After changing the wettability of the wettability variable layer to increase the hydrophilicity, the wettability variable layer shows a high affinity for the surface of the wettability variable layer. Therefore, the wettability of the reaction curable ink composition with respect to the ink layer forming region formed in a predetermined pattern by changing the wettability of a part of the surface of the wettability variable layer in the direction of increasing hydrophilicity, and its surroundings. It becomes possible to obtain a large difference in the wettability of the reaction curable ink composition with respect to the area.

Further, by using water as at least a part of the solvent of the reaction curable ink composition, the amount of the organic solvent used is reduced to avoid volatilization of the organic solvent in the ink manufacturing process or the color filter manufacturing process. This is preferable from the viewpoints of work hygiene and environmental hygiene.

However, if the solubility or dispersibility of the binder, the reaction curable monomer and the like is insufficient when only water is used as a solvent, water may be mixed with a water-soluble organic solvent. The water-soluble organic solvent mixed with water is not particularly limited as long as it is sufficiently miscible with water within the range of the blending ratio.

The water-soluble organic solvent mixed with water can be sufficiently mixed with water, and the wettability of the reaction curable ink composition before and after changing the wettability of the wettability variable layer described later. So that the difference between
Using the standard solution shown in the wetting test specified in K6768, the contact angle (θ) was measured after 30 seconds from contacting the droplets, and the critical surface tension determined by the graph of Zisman plot was 30 mN / m. It is preferable to use a test piece having a contact angle with the surface of 10 ° or more and a contact angle with the surface of a test piece having a critical surface tension of 70 mN / m, which is obtained by the same measuring method, of 10 ° or less.

Here, the test piece having the above-mentioned characteristics regarding the critical surface tension may be made of any material. Examples of the test piece having a critical surface tension of 30 mN / m include polymethylmethacrylate having a smooth surface,
Applicable ones can be selected from the polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and those obtained by coating the above-mentioned polymer and surface modifier on a smooth glass surface by actually carrying out the above test. Further, as the test piece showing the critical surface tension of 70 mN / m, for example, a test piece to which the above test is actually performed can be selected from those coated with nylon, a hydrophilized glass surface or the like.

Specific examples of the water-soluble organic solvent satisfying such a wettability property include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol and isopropanol, ethylene glycol monomethyl ether and ethylene glycol. Monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene Glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether Le, triethylene glycol monobutyl -n- butyl ether, ethylene glycol mono -t-
Butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-
n-propyl ether, propylene glycol mono-i
So-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono Examples thereof include glycol ethers such as -n-butyl ether, formamide, acetamide, dimethylsulfoxide, sorbit, sorbitan, acetin, diacetin, triacetin, and sulfolane.

From the viewpoint of the evaporation property of the ink composition,
Water-soluble glycols are preferably used as the water-soluble organic solvent. When a water-soluble glycol is used as the water-soluble organic solvent, evaporation of the ink composition can be suppressed, and the ink can be prevented from drying and clogging in the inkjet head.

Specific examples of the water-soluble glycols include:
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, molecular weight 200
0 or less polyethylene glycol, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, Mesoerythritol, pentaerythritol and the like can be mentioned.

Among the water-soluble glycols exemplified above, ethylene glycol satisfies the above-mentioned preferable conditions for wettability, and is therefore particularly preferably used as the water-soluble organic solvent.

The water-soluble solvent containing water is 40 to 95 with respect to the total amount of the reaction curable ink composition containing the solvent.
A coating liquid of the ink composition is prepared by using it in a weight percentage. When the amount of the solvent is too small, the viscosity of the ink is high and it becomes difficult to eject the ink from the inkjet head. Further, if the amount of the solvent is too large, the ink film deposited on the wettability changed portion will rupture before the predetermined ink wettability portion (ink layer formation portion) has a sufficient amount of ink (ink accumulation amount). However, it protrudes to the surrounding unexposed portion, and further wets and spreads to the adjacent wettability changing portion (ink layer forming portion). In other words, the amount of ink that can be deposited without protruding from the wettability change site (ink layer formation site) to which the ink should be applied is insufficient, and the film thickness after drying is too thin, which is sufficient. The transmission density cannot be obtained.

The mixing ratio of water and the water-soluble solvent is preferably 5 to 50 parts by weight with respect to 100 parts by weight of water.

(Binder System) The reaction-curable ink composition according to the present invention has a reaction-curable binder system. The reaction-curable binder system essentially comprises a binder and a bifunctional or trifunctional reaction-curable monomer, and if necessary, a tetrafunctional or higher-functional reaction curable monomer, a monofunctional reaction-curable monomer, a polymerization initiator, a curing agent. , Other components such as a sensitizer and a curing accelerator are appropriately selected and blended according to the reaction format.

The reaction-curable binder system may be of any reaction type, and for example, a photo-curable binder system or a thermosetting binder system can be used.

The binder is the main component relating to the film forming property. As the binder, either a resin which itself has no polymerization reactivity or a resin which itself has polymerization reactivity may be used, or two or more binders may be used in combination.

When a resin having no polymerization reactivity is used as a binder, a bifunctional to trifunctional reaction curable monomer which is an essential component in the reaction curable ink composition, and
The other reaction curable monomer, which is a desired component, cures by forming a cross-linkage bond by a polymerization reaction.

On the other hand, as the binder which is itself polymerizable, an oligomer obtained by introducing a polymerizable functional group into the molecule of a non-polymerizable binder or a polymer having a larger molecular weight than the oligomer is used. The polymerizable functional group of the polymerizable binder is one that can polymerize in the same reaction mode as the reaction curable monomer used in combination with the polymerizable binder to form a cross-linking bond with the reaction curable monomer (typically Has the same polymerizable functional group as the reaction curable monomer)
To use.

For example, when a photopolymerization reactive monomer is used as the bifunctional or trifunctional reaction curable monomer,
Using a photopolymerizable (photocurable) binder, bifunctional or trifunctional
When a thermopolymerization reactive monomer is used as the functional reaction curable monomer, a thermopolymerization (thermosetting) binder is used.

The binder is usually added in a proportion of 1 to 50% by weight based on the total solid content of the reaction curable ink composition. Here, the solid content of the reaction curable ink composition for specifying the blending ratio includes all components except the solvent, and the liquid reaction curable monomer is also included in the solid content.

The reaction curable monomer is the main component relating to the strength and adhesiveness of the coating film. The reaction curable ink composition for a color filter of the present invention contains a bifunctional to trifunctional reaction curable monomer as an essential component.

Conventionally, a photocurable ink composition has a polyfunctional group having two or more polymerizable functional groups in order to increase the film strength of a cured layer obtained by curing the ink composition and the adhesion to a substrate. A monomer is blended, but in order to obtain sufficient film strength and adhesiveness, a polyfunctional monomer having four or more functional groups is usually used. However, when a polyfunctional monomer with a large number of functional groups is blended in a photo-curable ink and sprayed onto a substrate by an inkjet method, the ink dries at the tip of the inkjet head during the spraying operation and the viscosity gradually increases. And the dischargeability of ink deteriorates.

On the other hand, in the present invention, since a reactive curable monomer having a relatively small number of bifunctional or trifunctional functional groups is used, it is difficult for the viscosity to increase at the tip of the head during the ink jetting operation. In addition, the head is not clogged, and the ink dischargeability during work is stable. Therefore, the ink ejection amount and ejection direction are kept constant, and the ink is accurately and accurately printed on the substrate in a predetermined pattern.
And it can be made to adhere uniformly.

The proportion of the bifunctional to trifunctional reactive curable monomer is usually 20 to 70% by weight based on the total solid content of the reactive curable ink composition.

When the proportion of the bifunctional or trifunctional reaction-curable monomer is less than 20% by weight of the total solid content, the ink composition is not sufficiently diluted with the monomer and the ink viscosity is low. It may be high from the beginning or after evaporation of the solvent, which may cause clogging of the inkjet head. Further, when the mixing ratio of the bifunctional or trifunctional reaction curable monomer exceeds 70% by weight of the total solid content, the crosslink density of the coating film becomes low, and the solvent resistance, adhesion and hardness of the coating film. May be poor and sufficient characteristics may not be obtained.

In the present invention, in the reaction curable ink composition for a color filter, a monofunctional monomer of the same reaction type, and / or, if necessary, together with the above-mentioned bifunctional or trifunctional polyfunctional monomer are used. You may mix | blend a tetrafunctional or more functional monomer.

In particular, it is preferable that the reaction curable ink composition according to the present invention contains a bifunctional or trifunctional reaction curable monomer and a tetrafunctional or higher functional reaction curable monomer. When all the reaction-curable monomers contained in the reaction-curable ink composition are bifunctional or trifunctional monomers, it is difficult for the viscosity to increase due to the drying of the ink, so that the ejection property of the inkjet head is stable. On the other hand,
The cured layer obtained by curing the ink layer may have insufficient film strength or adhesion to the substrate. Therefore, by mixing an appropriate amount of a polyfunctional monomer having a functionality of 4 or more with the above-mentioned difunctional or trifunctional monomer, it is possible to impart sufficient film strength and adhesion to the pattern of the cured layer.

The tetra- or higher-functional reaction-curable monomer is usually used in an amount of 1 to 1 based on the total solid content of the reaction-curable ink composition.
It is mixed at a ratio of 30% by weight. Further, in order to balance discharge stability with a bifunctional or trifunctional monomer and improvement in strength and adhesiveness with a tetrafunctional or higher functional monomer, the tetrafunctional or higher functional monomer is added to 100 parts by weight of the bifunctional or trifunctional monomer. The compounding ratio is usually 1 to 50 parts by weight, preferably the lower limit of the compounding ratio is 2 parts by weight or more, and /
Alternatively, the upper limit of the blending ratio is 35 parts by weight or less.

Here, the compounding ratio of the tetra- or higher functional reaction-curable monomer is the aforementioned bi- or tri-functional reaction-curable monomer 1.
If the amount is less than 1 part by weight with respect to 00 parts by weight, properties such as hardness and solvent resistance after the ink is cured may not be sufficiently obtained. When the compounding ratio of the tetrafunctional or higher-functional reaction-curable monomer exceeds 50 parts by weight, the curing speed of the ink may be slow and the process speed may be slow.

Regarding the wettability of the above-mentioned bifunctional or trifunctional monomer, and the reaction-curable monomer such as a tetrafunctional or higher functional monomer or a monofunctional monomer which is used as necessary, as in the case of the water-soluble organic solvent, JIS K6768. The contact angle (θ) after 30 seconds from contacting the liquid droplets was measured using the standard solution shown in the wetting test specified in 1., and the critical surface tension obtained from the graph of Zisman plot was 30 mN.
/ M shows a contact angle with respect to the surface of the test piece of 10 ° or more, and the critical surface tension determined by the same measurement method is 70.
It is preferable that the contact angle of mN / m with respect to the surface of the test piece is 10 ° or less.

The reaction curable ink composition of the present invention uses water as a part of the solvent so that the wettability of the wettability variable layer can be adjusted before and after the wettability of the wettability variable layer is changed. Although it is possible to make a large difference, when the reaction curable monomer in the reaction curable ink composition satisfies the above-mentioned conditions regarding wettability, the reaction curable ink composition has a wettability variable layer described later. Before changing the wettability, with respect to the surface of the wettability variable layer,
After exhibiting even greater repulsion and increasing the hydrophilicity by changing the wettability of the wettability variable layer, the wettability variable layer is shown to have even greater affinity with the surface of the wettability variable layer. become.

Therefore, the affinity of the reaction curable ink composition is maintained between the ink layer forming region formed by partially changing the wettability of the wettability variable layer and the ink layer non-forming region existing around the region. It is preferable because the difference in sex can be very large.

The components incorporated in the photocurable binder system and the thermosetting binder system will be described in detail below.

(Blending component of photo-curable binder system) When a resin having no polymerization reactivity is used as the binder of the photo-curable binder system, for example, a copolymer composed of two or more of the following monomers is used. Can: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomers, and polymethylmethacrylate macromonomers.

More specifically, acrylic acid / benzyl acrylate copolymer, acrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / styrene copolymer, acrylic acid / methyl acrylate / polystyrene macromonomer copolymer Polymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2 -Hydroxyethyl acrylate / benzyl acrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethylmethacrylate Macromonomer copolymers, acrylic acid / benzyl methacrylate copolymer, an acrylic acid / methyl methacrylate / styrene copolymer, an acrylic acid /
Benzyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / polymethylmethacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic Acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer,
Use acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethylmethacrylate macromonomer copolymer You can

Continuing with the specific example, methacrylic acid /
Benzyl acrylate copolymer, methacrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid /
Methyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer Polymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polystyrene macromonomer copolymer,
Methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / methyl methacrylate /
Styrene copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethylmethacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / Polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer,
Methacrylic acid / 2-hydroxyethyl methacrylate /
Examples thereof include methacrylic acid copolymers such as benzyl methacrylate / polymethyl methacrylate macromonomer copolymer.

The solvent of the ink composition according to the present invention is blended with an organic solvent in order to obtain the solubility and dispersibility of the binder, but since it is mainly composed of water, it has some solubility in water as the binder. It is preferable to use one. From this point of view, the binder preferably has a hydrophilic group such as a carboxyl group. Specifically, among the above-mentioned non-polymerizable binders, a methacrylic acid / benzyl methacrylate copolymer, a methacrylic acid / benzyl methacrylate / styrene copolymer, and a benzyl methacrylate / styrene copolymer are preferably used. In order to ensure sufficient solubility and dispersibility of these copolymers in water, the monomer unit containing a carboxyl group is preferably contained in the copolymer in an amount of 5% by weight or more. .

As the photopolymerizable binder per se, use of a prepolymer compounded in a UV curable resin composition conventionally used in various fields such as inks, paints and adhesives. it can. Conventionally known prepolymers include radical polymerization type prepolymers, cationic polymerization type prepolymers, thiol / ene addition type prepolymers, and any of them may be used.

Of these, radical-polymerizable prepolymers are the most readily available on the market and include, for example, ester acrylates, ether acrylates, urethane acrylates, epoxy acrylates, amino resin acrylates, acrylic resin acrylates, Radical-polymerizable prepolymers such as unsaturated polyesters can be exemplified.

The bifunctional to trifunctional photopolymerization-reactive monomer may be a photopolymerization initiator which itself induces a polymerization reaction upon irradiation with light, or a photopolymerization initiator which is activated upon irradiation with light. The molecule has two or three functional groups that induce a polymerization reaction by the action of the components, and the two or three functional monomers are polymerized with each other, and / or are polymerized with other monomers or binders. What can be used can be used. A monomer having an ethylenically unsaturated bond can be used as such a photopolymerization-reactive monomer, and in this case, photoradical polymerization is possible.

Examples of the bifunctional photopolymerizable monomer include diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol, propylene glycol and hexanediol; diacrylates and dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Methacrylates can be exemplified.

Specific examples of the trifunctional photopolymerizable monomer include, for example, trivalent or higher polyvalent monomers such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Examples thereof include triacrylates or trimethacrylates of polyhydric alcohols.

These bifunctional to trifunctional photopolymerizable monomers may be used alone or in combination of two or more.

Examples of the monofunctional monomer for the photopolymerization reaction include vinyl monomers such as styrene and vinyl acetate, and n.
Examples thereof include monofunctional acrylic monomers such as hexyl acrylate and phenoxyethyl acrylate.

Examples of the tetra- or higher functional photopolymerization-reactive monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. it can.

Furthermore, among the di- or trifunctional photopolymerization-reactive monomers, the standard solution shown in the wetting test specified in JIS K6768 was used to bring the droplets into contact with each other,
The contact angle (θ) after a second was measured, and the contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m, which was obtained from the graph of Zisman plot, was 10 ° or more, and was obtained by the same measurement method. Examples of materials having a contact angle of 10 ° or less with respect to the surface of a test piece having a critical surface tension of 70 mN / m include, for example, ethylene glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, and 1,9. Examples thereof include nonanediol diacrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and 1,3-butylene glycol dimethacrylate.

If necessary, the photocurable binder system may include a photopolymerization initiator, a sensitizer and a curing accelerator (chain transfer agent).
A component that accelerates the photopolymerization reaction, such as or a photocrosslinking agent, is added.

The photopolymerization initiator is appropriately selected in consideration of the reaction types of the binder and the monomer (for example, photoradical polymerization and photocationic polymerization) and the type of each material.
Examples of the photo-radical polymerization initiator include 1-hydroxycyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-Monfolinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-
1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1
-Propan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, bisacylphosphine oxide, benzoin ethyl ether,
Benzoin isobutyl ether, benzoin isopropyl ether, 2-isopropylthioxanthone, 2,4
-Diethylthioxanthone, 2- (3-dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9
H-thioxanthone-9-one mesochloride, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,
3 ', 4,4'-tetra (t-butylperoxycarbonyl), p-dimethylaminobenzoic acid ethyl ester,
p-Dimethylaminobenzoic acid isoamyl ester, 1,
3,5-triacroylhexahydro-s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(Furan-2-yl) ethenyl]-
4,6-bis (trichloromethyl) -s-triazine,
Examples thereof include methylbenzoyl formate and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

As the sensitizer, for example, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 2-
Examples thereof include ethylhexyl-1,4-dimethylaminobenzoate.

Examples of the curing accelerator (chain transfer agent) include 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2,5-dimercapto-1,3,4-thiadiazole. can do.

It is also possible to use a photocrosslinking agent or a photosensitizer made of a polymer compound. The polymer photocrosslinking / sensitizer is a polymer compound having a functional group capable of functioning as a photocrosslinking agent or a photosensitizer in the main chain and / or side chain, and examples thereof include 4-azidobenzaldehyde. Of polyvinyl alcohol with polyvinyl alcohol, a condensate of 4-azidobenzaldehyde with phenol novolac resin, 4-
Examples thereof include (co) polymers of (meth) acryloylphenylcinnamoyl ester, 1,4-polybutadiene, and 1,2-polybutadiene.

(Components of Thermosetting Binder System) When a resin having no polymerization reactivity is used as the binder of the thermosetting binder system, it is the same as the non-polymerizable resin used in the photocurable binder system described above. Any thing can be used. In this case, it is also preferable that the non-polymerizable binder preferably has a hydrophilic group such as a carboxyl group.

Examples of the binder having thermopolymerization per se include, for example, homopolymers or copolymers obtained by polymerizing one or more of the following monomers having an ethylenically unsaturated bond and an epoxy group. Polymers can be used: glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, -3,4-epoxybutyl acrylate. , Methacrylic acid-3,4-epoxybutyl, methacrylic acid-
(Meth) acrylates such as 4,5-epoxypentyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl; o-vinyl Vinyl glycidyl ethers such as phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether; 2,3-di Glycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene,
3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrenediene Glycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3 ，
4-trihydroxymethylstyrene triglycidyl ether and 1,3,5-trihydroxymethylstyrene triglycidyl ether.

Further, a copolymer obtained by polymerizing one or more kinds of monomers having an ethylenically unsaturated bond and an epoxy group as described above and a monomer not having an epoxy group as described below is also heat-resistant. It can be used as a polymerizable binder: acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate,
Styrene, polystyrene macromonomers, and polymethylmethacrylate macromonomers.

Examples of the thermopolymerizable binder other than the epoxy resin include melamine resin, urea resin, alkyd resin, phenol resin, cyclopentadiene resin and the like.

As the bifunctional to trifunctional thermopolymerization reactive monomer, a monomer having a functional group capable of thermal radical polymerization such as an ethylenic unsaturated bond, or an epoxy group-containing monomer can be used.

As the difunctional to trifunctional ethylenically unsaturated bond-containing monomer, the same ones as those exemplified as the above-mentioned monomer capable of photoradical polymerization reaction can be used.

Examples of the bifunctional to trifunctional epoxy group-containing monomer include, for example, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl. Ether, 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene,
2,6-diglycidyloxystyrene, 5-vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethyl Styrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5
-Dihydroxymethylstyrene diglycidyl ether,
2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, 1,3,5-trihydroxymethylstyrene triglycidyl ether and the like can be exemplified, and one of these can be used. Can be used alone or in combination of two or more.

As the thermopolymerization-reactive monofunctional monomer,
A monofunctional epoxy group-containing monomer can be used,
More specifically, methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, butyl phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether,
Examples include polypropylene glycol glycidyl ether and butoxy polyethylene glycol monoglycidyl ether.

As the tetrafunctional or higher functional thermopolymerization-reactive monomer, a tetrafunctional or higher functional epoxy group-containing resin can be used. Specifically, novolac resins such as phenol novolac epoxy and cresol novolac epoxy and tetra Examples thereof include glycidyl amine resins such as glycidyl diaminodiphenyl methane and tetraglycidyl metaxylene diamine, and glycidyl ether resins such as tetraphenyl glycidyl ether ethane and triphenyl glycidyl ether methane.

Further, among the bifunctional or trifunctional thermopolymerization-reactive monomers, the standard solution shown in the wetting test specified in JIS K6768 was used to bring the droplets into contact with each other, and
The contact angle (θ) after a second was measured, and the contact angle with respect to the surface of the test piece having a critical surface tension of 30 mN / m, which was obtained from the graph of Zisman plot, was 10 ° or more, and was obtained by the same measurement method. Examples of materials having a contact angle of 10 ° or less with respect to the surface of a test piece having a critical surface tension of 70 mN / m include, for example, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Ether, trimethylolpropane polyglycidyl ether, 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene,
3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrenediene Glycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3 ，
4-trihydroxymethyl styrene triglycidyl ether, 1,3,5-trihydroxymethyl styrene triglycidyl ether, etc. can be illustrated.

If necessary, the thermosetting binder system may contain components such as a thermal polymerization initiator and a curing agent that accelerate the thermal polymerization reaction.

When the reaction-curable monomer or binder of the thermosetting binder system has a thermal radical polymerizable property, a thermal radical polymerization initiator is usually used.

Examples of the thermal radical polymerization initiator include:
Azo compounds, organic or inorganic peroxides can be used. Specifically, as the azo compound, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-
Dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), dimethyl-2
2'-azobisisobutyrate can be exemplified. Examples of organic peroxides include lauryl peroxide, benzoyl peroxide, and tert-butyl peroctoate. Examples of the inorganic peroxide include potassium persulfate and ammonium persulfate.

When an epoxy group-containing compound is used as the thermopolymerization-reactive monomer, a curing agent is usually combined. As the curing agent, for example, polycarboxylic acid anhydride or polycarboxylic acid is used.

Specific examples of the polycarboxylic acid anhydride include:
Phthalic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, hexahydrophthalic anhydride,
Aliphatic or alicyclic dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride, hymic acid anhydride, and nazic anhydride; 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Aliphatic polycarboxylic acid dianhydrides such as; aromatic polycarboxylic acid anhydrides such as pyromellitic anhydride, trimellitic anhydride, and benzophenone tetracarboxylic anhydride; ethylene glycol bis trimellitate, glycerin tris trimellitate, etc. Of the ester group-containing acid anhydrides, and particularly preferably, aromatic polyvalent carboxylic acid anhydrides. Further, a commercially available epoxy resin curing agent composed of carboxylic acid anhydride can also be suitably used.

Specific examples of the polycarboxylic acid include:
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, butanetetracarboxylic acid, maleic acid and itaconic acid; hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid , Aliphatic polycarboxylic acids such as cyclopentane tetracarboxylic acid, and phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1, 4,
Aromatic polycarboxylic acids such as 5,8-naphthalene tetracarboxylic acid and benzophenone tetracarboxylic acid can be mentioned, and aromatic polycarboxylic acids are preferable.

These polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids may be used either individually or in combination of two or more. The compounding amount of the curing agent used in the present invention is such that the epoxy group-containing component (monomer and binder) is 10
It is usually in the range of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 0 parts by weight. If the compounding amount of the curing agent is less than 1 part by weight, curing will be insufficient and a strong coating film cannot be formed. On the other hand, if the amount of the curing agent added exceeds 100 parts by weight, the adhesion of the coating film to the substrate will be poor and a uniform and smooth coating film cannot be formed.

(Colorant) On the substrate of the color filter,
When a colored pattern such as a pixel portion or a black matrix is formed using the reaction curable ink composition of the present invention, a colorant is added to the reaction curable ink composition. An arbitrary colorant can be selected from the organic colorant and the inorganic colorant and used according to the desired color such as R, G, B of the pixel portion. As the organic colorant, for example, a dye, an organic pigment, a natural pigment or the like can be used. Further, as the inorganic colorant, for example, an inorganic pigment, an extender pigment or the like can be used. Among these, organic pigments are preferably used because they have high color developability and high heat resistance. Examples of organic pigments include color index (CI; The Soci
Compounds classified as Pigment (published by ety of Dyers and Colorists), specifically,
The color index (CI) numbers as shown below can be given.

CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, C.I.
I. Pigment Yellow 15, CI Pigment Yellow 1
6, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61,
CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI
Pigment Yellow 95, CI Pigment Yellow 9
7, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 10
6, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 11
4, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 12
6, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 13
9, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 15
4, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 17
5; CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI
Pigment Orange 34, CI Pigment Orange 3
6, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61,
CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 3
6, CI Pigment Violet 38; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 8, 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI
Pigment Red 40, CI Pigment Red 41, C.
I. Pigment Red 42, CI Pigment Red 48:
1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49:
2, CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1,
CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1,
CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97, C.
I. Pigment Red 101, CI Pigment Red 10
2, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114,
CI Pigment Red 122, CI Pigment Red 1
23, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI
Pigment Red 166, CI Pigment Red 16
8, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177,
CI Pigment Red 178, CI Pigment Red 1
79, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI
Pigment Red 193, CI Pigment Red 19
4, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216,
CI Pigment Red 220, CI Pigment Red 2
24, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI
Pigment Red 255, CI Pigment Red 26
4, CI Pigment Red 265; CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, C.I.
I. Pigment Blue 60; CI Pigment Green 7,
CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7.

Specific examples of the inorganic pigments or extender pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), and cadmium red. , Ultramarine, dark blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. In the present invention, the colorants may be used alone or in combination of two or more.

When a pattern of a light-shielding layer is formed on the substrate of a color filter using the reaction-curable ink composition of the present invention, a black colorant having a high light-shielding property is blended in the reaction-curable ink composition. To do. Since it is difficult for light to reach the inside of the ink layer containing a colorant having a high light-shielding property, it is difficult to cure when a photocurable ink composition is used as the reaction curable ink composition. Therefore, when forming a colored layer having a high light-shielding property, it is preferable to use a thermosetting ink composition. However, even when using a photocurable ink composition containing a colorant having a high light-shielding property, photocuring can be performed by adjusting the curing method such as increasing the thickness of the ink layer or the light irradiation time. It is possible. As the black colorant having a high light-shielding property, for example, an inorganic colorant such as carbon black or ferrosoferric oxide, or an organic colorant such as cyanine black can be used.

When the reaction-curable ink composition of the present invention is used to form a colorless, transparent or color-unnecessary cured layer in a predetermined pattern, a colorant is particularly used. No need.

When the pixel portion is formed, the coloring agent is usually added in an amount of 1 to the total solid content of the reaction curable ink composition.
It is mixed in a proportion of 60% by weight, preferably 15 to 40% by weight. When the amount of the colorant is too small, the transmission density when the reaction curable ink composition is applied to a predetermined film thickness (usually 0.1 to 2.0 μm) may be insufficient. Further, when the amount of the colorant is too large, the properties as a coating film such as the adhesion to the substrate when the reaction curable ink composition is applied onto the substrate and cured, and the coating film hardness may be insufficient. is there.

(Dispersant) A dispersant is optionally incorporated in the reaction curable ink composition in order to favorably disperse the colorant. As the dispersant, for example, a cationic type,
Anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants can be used. Among the surfactants,
Polymer surfactants (polymer dispersants) as shown below
Is preferred.

That is, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene alkyl such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Polymer surfactants such as phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes are preferably used.

(Other Components) The reaction curable ink composition for a color filter of the present invention may optionally contain one or more other additives.
The following can be illustrated as such an additive.

A) Dispersion aid: For example, a blue pigment derivative such as a copper phthalocyanine derivative or a yellow pigment derivative.

B) Filler: For example, glass, alumina or the like.

C) Adhesion promoter: For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and the like.

D) Antioxidants: for example, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6
-Di-t-butylphenol and the like.

E) UV absorber: For example, 2- (3-t
-Butyl-5-methyl-2-hydroxyphenyl) -5
-Chlorobenzotriazole, alkoxybenzophenone and the like.

F) Anti-agglomeration agent: for example, sodium polyacrylate or various surfactants.

(Preparation of Reactive Curable Ink Composition for Color Filter) The binder, the bifunctional or trifunctional monomer and, if necessary, other components are mixed in any order, or the components are optionally mixed. In the order of, put in a water-soluble solvent, sufficiently stir with a dissolver, etc.,
By uniformly dissolving and dispersing, the reaction-curable water-based ink composition for color filters of the present invention can be prepared.

(Production of Color Filter) In the present invention, an ink layer is formed by selectively adhering the reaction curable ink composition for a color filter according to the present invention to a predetermined region on the surface of a substrate to form an ink layer. By reacting and curing the layer to form a cured layer having a predetermined pattern, details of the color filter, for example, a colored layer such as a pixel portion or a light shielding portion (black matrix layer) can be formed.

As a method for selectively adhering the ink composition to a predetermined region on the surface of the substrate, a first method of spraying by an ink jet method or a second method of utilizing a wettability variable layer can be exemplified. .

In the following, a method of spraying by an ink jet method (first method) and a method of utilizing a wettability variable layer (second method) are applied to a pixel using the photocurable ink composition according to the present invention. A case of forming a portion will be described in detail as an example. The method described below can be applied in the case of a reaction type other than photocurability, for example, when a thermosetting ink composition is used, by modifying the reaction type. Further, the method described below can be applied by making necessary corrections even when forming details other than the pixel portion, for example, a light shielding layer.

(First Method for Producing Color Filter) An ink for forming a pixel portion is prepared by mixing the photocurable ink composition of the present invention with a desired colorant such as R, G or B to form a color filter. A pixel portion can be formed by selectively adhering to a predetermined region on the transparent substrate by an inkjet method and irradiating light to cure the same. An example of a color filter manufacturing method including such steps will be described below.

First, as shown in FIG. 1A, a transparent substrate 1 of a color filter is prepared. The transparent substrate is not particularly limited as long as it has been conventionally used for a color filter. For example, quartz glass, Pyrex (registered trademark) glass, synthetic quartz plate or the like having no flexibility and transparency. A rigid material, or a flexible transparent material having flexibility such as a transparent resin film or an optical resin plate can be used. Among them, 7059 glass manufactured by Corning Co., Ltd. is a material having a small coefficient of thermal expansion, is excellent in dimensional stability and workability in high temperature heat treatment, and is a non-alkali glass containing no alkali component in the glass. It is suitable as a color filter for color liquid crystal display devices according to the method. In the present invention, a transparent substrate is usually used, but a reflective substrate or a white-colored substrate can also be used. Further, the substrate may be subjected to surface treatment for the purpose of preventing alkali elution, imparting gas barrier property or the like, if necessary.

Next, as shown in FIG. 1B, the light-shielding portion 2 is formed in a region serving as a boundary between the pixel portions on one surface side of the transparent substrate 1. The light-shielding portion 2 can be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 Å by a sputtering method, a vacuum deposition method or the like, and patterning this thin film. As this patterning method, a normal patterning method such as sputtering can be used.

Further, the light-shielding portion 2 may be a layer in which light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments and organic pigments are contained in a resin binder. As the resin binder used, one or a mixture of two or more resins such as polyimide resin, acrylic resin, epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, and cellulose, a photosensitive resin,
Furthermore, an O / W emulsion type resin composition, for example,
It is possible to use an emulsion of reactive silicone. The thickness of such a resin light-shielding portion can be set within the range of 0.5 to 10 μm. As a method of patterning such a resin light-shielding portion, a generally used method such as a photolithography method or a printing method can be used.

Next, as shown in FIG. 1C, an ink-repellent convex portion having a width narrower than that of the light-shielding portion is formed at the center of the pattern of the light-shielding portion in the width direction. The composition of the ink-repellent convex portion is not particularly limited as long as it is a resin composition having ink repellency. Further, it need not be particularly transparent and may be colored. For example, it is possible to use a material that is used for the light-shielding portion and that does not contain a black material. Specifically, polyacrylamide, polyvinyl alcohol, gelatin,
Examples thereof include a composition in which one or more kinds of aqueous resins such as casein and cellulose are mixed, and an O / W emulsion type resin composition, for example, an emulsion of reactive silicone. In the present invention, a photocurable resin is preferably used for forming the ink-repellent convex portion, for reasons such as handleability and easy curing. Also,
Since the stronger the ink repellency is, the more preferable the ink repellent convex portion is, the surface thereof may be treated with an ink repellent treatment agent such as a silicone compound or a fluorine-containing compound.

The patterning of the ink-repellent convex portion can be carried out by printing using a coating liquid of the ink-repellent resin composition or photolithography using a photocurable coating liquid. The height of the ink-repellent convex portion is preferably set to a certain level because it is provided to prevent the inks from being mixed when coloring by the inkjet method as described above, but it is preferably a color filter. In consideration of the overall flatness in this case, the thickness is preferably close to the thickness of the pixel portion. Specifically, it is usually 0.1 to 2.0 μm, though it varies depending on the amount of ink deposited.
It is preferably within the range.

Next, a photocurable ink composition for a color filter, which is prepared by blending one or more coloring agents, is prepared for each color pixel portion forming ink. Then, as shown in FIG. 1D, the light shielding layer 2 is formed on the surface of the transparent substrate 1.
Pixel part formation region 4 of each color defined by the pattern
A pixel portion forming ink of a corresponding color is sprayed on R, 4G, and 4B by an inkjet method to form an ink layer. In this ink spraying step, the ink for forming a pixel portion according to the first aspect of the invention is unlikely to cause an increase in viscosity at the tip of the head 5, and can maintain good ejection properties. Therefore, the ink of the corresponding color can be accurately and uniformly attached in the predetermined pixel portion formation region, and the pixel portion without color unevenness or color loss can be formed with an accurate pattern. Further, the ink for forming the pixel portion of each color can be simultaneously sprayed onto the substrate by using a plurality of heads, so that the work efficiency can be improved as compared with the case where the pixel portion is formed for each color.

Next, as shown in FIG. 1E, the ink layers 6R, 6G, and 6B of the respective colors are irradiated with light 7 to be cured.
The ink layer may be irradiated with appropriate light in consideration of the curable component of the photocurable ink composition, and either visible light or invisible light may be used. Usually, light generally used for photocuring such as ultraviolet rays or ionizing radiation may be used. After curing the ink layer, if necessary,
Baking is performed to form a pixel portion. The thickness of the pixel portion is usually about 0.1 to 2.0 μm in consideration of optical characteristics and the like.

Next, as shown in FIG. 1F, a protective layer 9 is formed on the side of the transparent substrate on which the pixel portions 8R, 8G, 8B are formed. The protective layer is provided to flatten the color filter and prevent components contained in the pixel portion and the like from eluting into the liquid crystal layer of the liquid crystal display device. The thickness of the protective layer can be set in consideration of the light transmittance of the material used, the surface condition of the color filter, etc., and can be set, for example, in the range of 0.1 to 2.0 μm. The protective layer can be formed using, for example, a known transparent photosensitive resin, a two-component curable transparent resin, or the like having a light transmittance required for the transparent protective layer.

In this way, the color filter 101A is manufactured by the first method using the photocurable ink composition for color filters. In this example, the pixel portion is formed using the ink for forming a pixel portion, which is the reaction curable ink composition for a color filter according to the present invention.
According to the inkjet method using the photocurable ink composition for a color filter, a cured layer other than the pixel portion, for example, the light shielding layer 2 or the ink repellent convex portion 3 can be formed in a desired pattern.

When it is desired to form the light-shielding layer 2, a light-curable ink composition for a color filter, which is prepared by blending a light-shielding colorant such as a black pigment, is prepared. The ink for formation is selectively adhered to a predetermined area on the surface of the transparent substrate 1 by an inkjet method to form an ink layer in a predetermined pattern, and the ink layer is irradiated with light to be cured, and if necessary. The light shielding layer can be formed by baking. Although the light-shielding layer forming ink has poor light transmittance, it can be photocured by adjusting the type of light and irradiation conditions.

When it is desired to form the ink-repellent convex portion 3, an ink-repellent convex portion-forming ink which is a photocurable ink composition for a color filter and which contains an ink-repellent binder is used. This ink-repellent convex-forming ink is prepared and adhered to the center of the upper surface of the light-shielding layer 2 in a pattern narrower than the light-shielding layer 2 along the longitudinal direction of the light-shielding layer 2 by an inkjet method. Then, the ink layer is formed, the ink layer is irradiated with light to be cured, and the ink layer is baked if necessary, whereby the ink-repellent convex portion 3 can be formed. The ink-repellent convex-forming ink does not need a light-shielding property and thus has a good light-transmitting property, and thus can be easily photocured.

(Second Method for Producing Color Filter) A wettability variable layer whose wettability can be changed in a direction of increasing hydrophilicity is formed on the substrate of the color filter, and the surface of the wettability variable layer is formed. Of the photocurable ink for a color filter of the present invention described above is formed in the ink layer forming region by selectively changing the wettability within a predetermined region of By selectively adhering an ink for forming a pixel portion, which is obtained by mixing a desired colorant such as R, G or B, to the composition to form an ink layer, and irradiating the ink layer with light to cure the ink layer. ,
A pixel portion can be formed.

In the second method, as a water-soluble organic solvent used by mixing with water, JIS K6768 is used.
Using the standard solution shown in the wetting test specified in 1 above, the contact angle (θ) was measured after 30 seconds from contacting the droplets, and the critical surface tension determined by the graph of Zisman plot was 30.
The contact angle with respect to the surface of the test piece of mN / m is 10 ° or more, and the critical surface tension obtained by the same measuring method is 7
It is preferable to use a test piece having a contact angle of 10 ° or less with the surface of a test piece of 0 mN / m.

Further, bifunctional to trifunctional, tetrafunctional or higher,
Also, each of the monofunctional reaction-curable monomers can be used in accordance with JIS K6.
Using the standard solution shown in the wetting test specified in 768, the contact angle (θ) after contacting the droplet for 30 seconds was measured, and the critical surface tension determined from the graph of Zisman plot was 30 mN / m. The contact angle to the surface of the test piece is 10
And a contact angle with respect to the surface of a test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 1 or more.
It is preferably 0 ° or less.

An example of a method of manufacturing a color filter including such steps will be described below. First, FIG. 2 (A)
As shown in, the transparent substrate 1 of the color filter is prepared. As the transparent substrate 1, the same one as used in the above-mentioned first method can be used.

Next, as shown in FIG. 2B, the light-shielding portion 2 is formed in the region serving as the boundary between the pixel portions on the one surface side of the transparent substrate 1. The pixel portion forming regions 4R, 4G, and 4B of each color are defined by the pattern of the light shielding layer. The light shield 2 also
The same as in the first method can be provided.

Next, as shown in FIG. 2C, at least a partial region of the surface of the transparent substrate 1, particularly in this example, a region including the pixel portion forming region, contains a photocatalyst as a wettability variable layer. The layer 10 is formed into a solid pattern (solid pattern).

The photocurable ink composition of the present invention in which water is used as the solvent when the wettability of the pixel portion forming region of the wettability variable layer such as the photocatalyst containing layer 10 is selectively changed to increase the hydrophilicity. Is easily attached to the pixel portion formation region and spreads uniformly, while it is strongly repelled and eliminated in the peripheral region of the pixel portion formation region, so that it adheres selectively and uniformly to the pixel portion formation region. As a result, it is possible to form a pixel portion having an accurate pattern without color unevenness or color loss.

For the wettability variable layer, the standard solution shown in the wetting test specified in JIS K6768 was used, and the contact angle (θ) was measured 30 seconds after the droplets were contacted with each other. The obtained critical surface tension shows 20 to 50 mN / m before changing the wettability,
And after changing the wettability, 40-80 mN
/ M is preferable.

When the wettability variable layer capable of changing the critical surface tension in this way is used, the photocurable ink composition of the present invention using water as a solvent changes wettability to increase hydrophilicity. In the pattern formation region such as the pixel portion formation region, a very small contact angle is shown, while in the periphery of the pattern formation region, a very large contact angle is shown, and the difference in wettability can be made very large.

Examples of the wettability variable layer whose wettability can be changed in the direction of increasing hydrophilicity include a)
In addition to the wettability variable layer 10 shown in the drawing containing a photocatalyst and increasing the hydrophilicity of the wettability variable layer itself by the action of the photocatalyst, b) the lower side of the wettability variable layer (transparent substrate side)
A photocatalyst-containing layer, the hydrophilicity of the wettability variable layer is increased by the action of a photocatalyst present in the photocatalyst-containing layer, and c) a degradable wettability variable layer comprising a photocatalyst and a binder that is decomposed by the action of the photocatalyst. Where the exposed portion of the degradable wettability variable layer is decomposed and removed to expose a hydrophilic underlayer, for example, a transparent substrate, or d) degradability composed of a binder that is decomposed by the action of a photocatalyst. A photocatalyst-containing layer is provided below the wettability variable layer, and the exposed portion of the degradable wettability variable layer is decomposed and removed by the action of the photocatalyst existing in the photocatalyst-containing layer, and a hydrophilic base, for example, a photocatalyst-containing layer is included. The thing in which a layer etc. are exposed can be illustrated.

The “wetability variable layer capable of changing the wettability in the direction of increasing hydrophilicity” in the present invention is
In the laminated body in which the wettability variable layer is provided on the substrate, the wettability of the wettability variable layer forming surface may be changed in the direction of increasing hydrophilicity, and as in the above examples a) and b), This includes not only those in which the wettability variable layer itself has an increased hydrophilicity, but also those in which the wettability variable layer is decomposed and the hydrophilic underlayer is exposed as in the above examples c) and d).

The types a) and b) will be described in detail below.

A) Photocatalyst-containing layer whose hydrophilicity increases itself Like the illustrated photocatalyst-containing layer 10, the photocatalyst-containing layer which itself functions as a wettability variable layer contains a photocatalyst and a binder as necessary. It is formed by dispersing it in a solvent together with other additives to prepare a coating liquid, applying the coating liquid, and then proceeding with hydrolysis and polycondensation reaction to firmly fix the photocatalyst in the binder.

As the photocatalyst, for example, titanium oxide (TiO ₂ ), zinc oxide (ZnO), which is known as an optical semiconductor,
Tin oxide (SnO ₂ ), strontium titanate (Sr
TiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ), may be mentioned. One selected from them or a mixture of two or more thereof may be used. Can be used.

The mechanism of action of the photocatalyst in the photocatalyst-containing layer is not always clear, but the carrier generated by irradiation of light directly reacts with a nearby compound or the activity generated in the presence of oxygen or water. Depending on the oxygen species,
It is considered that the chemical structure of an organic substance is changed, and the hydrophilicity is increased by, for example, oxidizing or decomposing an organic group or an additive which is a part of the binder.

In the present invention, titanium oxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium oxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium oxide is preferable. Anatase type titanium oxide has an excitation wavelength of 380 nm or less.

Examples of such anatase type titanium oxide include hydrochloric acid peptizing type anatase type titania sol (STS-02 (average particle size 7 nm) manufactured by Ishihara Sangyo Co., Ltd.)
Examples include ST-K01 manufactured by Ishihara Sangyo Co., Ltd. and a nitrate-deflocculating anatase-type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)).

The smaller the particle size of the photocatalyst is, the more effectively the photocatalytic reaction takes place. The photocatalyst having an average particle size of 50 nm or less is preferable, and the photocatalyst of 20 nm or less is particularly preferably used. In addition, the smaller the particle size of the photocatalyst, the smaller the surface roughness of the formed photocatalyst-containing layer, which is preferable. When the particle size of the photocatalyst exceeds 100 nm, the centerline average surface roughness of the photocatalyst-containing layer becomes large, and It is not preferable because the ink repellency of the non-exposed area of the containing layer is lowered and the ink-philicity of the exposed area is insufficiently expressed.

The binder used in the photocatalyst-containing layer of this type is preferably one having a high binding energy such that the main skeleton is not decomposed by the photoexcitation of the above-mentioned photocatalyst. For example, (1) chloro or alkoxysilane by sol-gel reaction or the like. Examples thereof include an organopolysiloxane that exhibits high strength by hydrolysis and polycondensation of the above, and (2) an organopolysiloxane obtained by crosslinking a reactive silicone having excellent water repellency and oil repellency.

In the case of the above (1), the general formula: Y _n SiX _(4-n) (wherein Y represents hydrogen or a hydrocarbon group which may have a substituent. Y's may be the same or different from each other, and n is an integer of 0 to 3), or one or more hydrolyzed condensates of the silicon compound represented by It is preferably an organopolysiloxane which is a cohydrolysis condensate.

The silicon compound represented by the above general formula preferably has at least one hydrocarbon group which may have a substituent as Y.

In the above general formula, the unsubstituted hydrocarbon group or the hydrocarbon group portion of the substituted hydrocarbon group is, for example, a straight chain or branched aliphatic hydrocarbon group such as methyl, ethyl or other alkyl. An alicyclic hydrocarbon group such as cyclohexyl; an unsaturated hydrocarbon group such as vinyl; an aromatic hydrocarbon group such as phenyl; and the like, and the number of carbon atoms of these hydrocarbon groups or hydrocarbon group portions is 1 to 20. It is preferably within the range.

Further, in the above general formula, the hydrocarbon group which may have a substituent includes a fluorine-containing hydrocarbon group such as fluoroalkyl; glycidoxyalkyl and β-.
Epoxy-containing hydrocarbon groups such as (3,4-epoxycyclohexyl) alkyl; acryloyloxy or methacryloyloxy-containing hydrocarbon groups such as (meth) acryloyloxyalkyl; amino-containing hydrocarbon groups such as aminoalkyl; mercaptoalkyl Examples thereof include mercapto-containing hydrocarbon groups; fluoroalkyl-containing hydrocarbon groups such as N-fluoroalkylsulfonamidoalkyl-containing N-fluoroalkylsulfonamide group-containing hydrocarbon groups, and the like.

The alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group or a butoxy group.

Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltribromosilane. Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n
-Propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltrit-butoxysilane; n-
Hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltrit-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane,
n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-
Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n
-Octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltrit-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl Triisopropoxysilane, phenyltri-t-butoxysilane; tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane , Dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane Phenyl methyldichlorosilane,
Phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromo Silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t
-Butoxysilane; trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltrit-butoxysilane; γ- Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-Glycidoxypropyltriisopropoxysilane, γ
-Glycidoxypropyltri-t-butoxysilane; γ-
Methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltriisopropoxysilane, γ-methacryloyloxypropyltri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane. , Γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; And their partial hydrolysates; and their mixtures.

Further, as the organopolysiloxane compound, one having a fluoroalkyl group is particularly preferable.
When the wettability changing layer is formed using an organopolysiloxane compound having a fluoroalkyl group, the water repellency and ink repellency of the non-exposed area are increased by the action of the fluoroalkyl group, and the exposed area and the water repellency are made highly hydrophilic. It is possible to make a large difference in the wettability with respect to the ink between the non-exposed area and the non-exposed area.

Specifically, the above general formula Y _n SiX is used.
A hydrolyzed condensate containing a silicon compound represented by _(4-n) as a condensation unit, or a co-hydrolysis condensate, wherein all or at least a part of the condensation units are the following fluoroalkylsilanes. It is possible to use one or more fluoroalkyl group-containing silicon compounds. The following fluoroalkylsilanes are generally known as fluorine-based silane coupling agents.

CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (O
CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (O
CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (O
CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (O
_{CH 3) 3; (CF 3} ) 2 CF (CF 2) 4 CH 2 CH
₂ Si (OCH ₃ ) ₃ ; (CF ₃ ) ₂ CF (CF ₂ ) ₆
CH ₂ CH ₂ Si (OCH ₃ ) ₃ ; (CF ₃ ) ₂ CF
_{(CF 2) 8 CH 2 CH} 2 Si (OCH 3) 3; CF 3
_{(C 6 H 4) C 2} H 4 Si (OCH 3) 3; CF 3 (C
F ₂ ) ₃ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃ ; C
_{F 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 Si (OC
_{H 3) 3; CF 3 (} CF 2) 7 (C 6 H 4) C 2 H 4 S
i (OCH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ S
iCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₅ CH ₂ C
H ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₇ C
H ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (C
F ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ; (C
_{F 3) 2 CF (CF 2} ) 4 CH 2 CH 2 SiCH 3 (O
_{CH 3) 2; (CF 3} ) 2 CF (CF 2) 6 CH 2 CH
₂ Si CH ₃ (OCH ₃ ) ₂ ; (CF ₃ ) ₂ CF (C
_{F 2) 8 CH 2 CH 2} Si CH 3 (OCH 3) 2; C
_{F 3 (C 6 H 4)} C 2 H 4 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 SiCH
₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C
₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ; CF ₃ (CF ₂ ) _{7
(C 6 H 4) C 2} H 4 SiCH 3 (OCH 3) 2; CF
₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₂ C
H ₃ ) ₃ ; CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OC
H ₂ CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si
(OCH ₂ CH ₃ ) ₃ ; CF ₃ (CF ₂ ) ₉ CH ₂ CH
₂ Si (OCH ₂ CH ₃ ) ₃ ; and CF ₃ (CF ₂ ).
₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ CH ₂ Si (OC
H _{3) 3.}

By using the polysiloxane containing a fluoroalkyl group as a binder as described above, the ink repellency before the wettability of the photocatalyst containing layer is changed becomes large, and therefore the wettability before and after the wettability is changed. A large difference can be taken.

As the reactive silicone of the above (2), compounds having a skeleton represented by the following general formula can be mentioned.

[0166]

[Chemical 1]

However, n is an integer of 2 or more, and R ¹ ,
R ² is a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and 40% or less by mole of the total is vinyl, phenyl or halogenated phenyl. Further, it is preferable that R ¹ and R ² have a methyl group because the surface energy becomes the smallest, and it is preferable that the methyl group has a molar ratio of 60% or more. Further, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.

In addition to the above-mentioned organopolysiloxane, a stable organosilicon compound which does not undergo a crosslinking reaction, such as dimethylpolysiloxane, may be mixed with the binder.

The photocatalyst-containing layer may contain a surfactant in addition to the above-mentioned photocatalyst and binder. Specifically, NIKKOL BL manufactured by Nikko Chemicals Co., Ltd.,
Hydrocarbons such as BC, BO, BB series, ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Megafac F-141, 144 manufactured by Dainippon Ink and Chemicals, Inc. , Neos Co., Ltd. Futgent F-200, F251, Daikin Industries Co., Ltd. Unidyne DS-401, 402, 3M Co., Ltd. Fluorard FC-170, 176 fluorine-based or silicone-based nonionic surfactant Examples of the agent include cationic surfactants, anionic surfactants, and amphoteric surfactants.

In the photocatalyst-containing layer, in addition to the above-mentioned surfactant, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin. , Polycarbonate, polyvinyl chloride, polyamide, polyimide, styrene-butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, oligomers such as polyisoprene, A polymer or the like can be included.

The content of the photocatalyst in the photocatalyst containing layer is 5 to
It can be set in the range of 60% by weight, preferably 20-40% by weight. The thickness of the photocatalyst containing layer is 0.
The range of 05 to 10 μm is preferable.

As a solvent for dissolving and dispersing each of the above components, alcoholic organic solvents such as ethanol and isopropanol are preferable. The coating can be carried out by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. When the binder contains an ultraviolet-curable component, the photocatalyst-containing layer can be formed by performing a curing treatment by irradiating with ultraviolet rays.

B) A photocatalyst-containing layer is provided under the wettability variable layer to increase the hydrophilicity of the wettability variable layer. To form this type of wettability variable layer, first, the binder and the photocatalyst are dissolved. After coating the dispersed coating solution on the transparent substrate of the color filter, the hydrolysis or polycondensation reaction proceeds to form a photocatalyst containing layer or a photocatalyst containing layer of a single photocatalyst. Next, a thin film wettability variable layer made of a hydrophobic organic material is formed on the photocatalyst containing layer. As the photocatalyst, binder, solvent or the like, the same one as used in the above type a) may be used.

In order to form a thin film of an organic material, a vapor deposition method such as solution coating, surface graft treatment, surfactant treatment, PVD or CVD can be used. As the organic substance, it is possible to use a low molecular weight compound, a high molecular weight compound, a surfactant or the like, which changes the wettability by a photocatalyst. Specific examples include a silane compound in which an organic group is converted into a hydroxyl group by the action of a photocatalyst, a silane coupling agent, chlorosilane, alkoxysilane, or a hydrolytic condensate or a cohydrolytic condensate of two or more of these. be able to. On the photocatalyst containing layer, a wettability variable layer made of the above-mentioned organopolysiloxane may be formed,
In that case, it is preferable to use an organopolysiloxane containing a fluoroalkyl group.

The wettability variable layer exemplified above is a photocatalyst containing layer in which the wettability variable layer itself contains a photocatalyst, or a photocatalyst containing layer provided on the transparent substrate side of the wettability variable layer. By irradiating the photocatalyst-containing layer with a light beam, the photocatalyst is activated, and the wettability is changed by the action of the activated photocatalyst in the direction of increasing hydrophilicity. That is, each of the wettability variable layers shown in the examples changes the wettability in the direction in which the hydrophilicity is increased by the irradiation of light rays.

However, the wettability variable layer in the present invention is not particularly limited as long as the wettability of the surface can be changed by an external stimulus such as a physical stimulus or a chemical stimulus. is not. For example, the surface roughness may be changed by acid or alkali, and the wettability may be changed. Further, the wettability variable layer may be irradiated with energy such as ultraviolet rays, visible light, or heat. It may be a layer or the like in which the substance changes to change the wettability.

The photocatalyst-containing layer used in the exemplified method is irradiated with light rays on the pixel portion forming region to increase hydrophilicity, and the photocurable ink composition of the present invention is selectively attached thereto. By providing a wettability variable layer whose hydrophilicity is reduced by some kind of stimulus on the transparent substrate of the color filter and giving a stimulus that changes the wettability in a negative pattern of the pixel portion forming region, the light of the present invention can be obtained. It is possible to selectively deposit the curable ink composition only in desired areas.

Next, as shown in FIG. 2D, an ink-repellent convex portion 3 having a width narrower than that of the light-shielding portion is formed at the center of the pattern of the light-shielding portion in the widthwise direction through the photocatalyst containing layer 10. To form. As the ink-repellent convex portion, the same one as in the first method can be provided.

Next, as shown in FIG. 2 (E), the photocatalyst containing layer 10 is exposed by irradiating it with a light beam 7 through a photomask 11 to make the pixel portion forming regions 4R, 4G, 4B hydrophilic. Increase. When exposure is performed using the photomask 11, the width of the exposed portion 12 is set to be wider than the width of the pixel portion forming area 4 while ensuring an unexposed portion at the boundary between adjacent pixel portion forming areas. Is preferred. By doing so, the corners of the pixel portion forming region 4 are sufficiently exposed and the hydrophilicity is increased, so that inconvenience such as color loss in the pixel portion does not occur. The photocatalyst containing layer 10 may be exposed in a predetermined pattern by another method such as photolithography by scanning with a laser beam without using a photomask. In addition, the back surface side of the transparent substrate (the photocatalyst containing layer 10
When the light is exposed from the side opposite to that on which the photomask is provided, the photomask is unnecessary because the light-shielding layer 2 functions as a photomask.

The light with which the photocatalyst-containing layer 10 is irradiated may be visible light or invisible light as long as it can activate the photocatalyst, but usually light containing ultraviolet light is used. As a light source containing such ultraviolet light,
For example, a mercury lamp, a metal halide lamp, a xenon lamp, etc. can be mentioned. The wavelength of light used for this exposure can be set within a range of 400 nm or less, preferably within a range of 380 nm or less, and the irradiation amount of light at the time of exposure is such that the exposed portion has increased hydrophilicity due to the action of a photocatalyst. The irradiation dose required for this can be set.

Next, a photocurable ink composition for a color filter of the present invention, which is prepared by blending one or more coloring agents, is prepared for each color pixel portion forming ink. Then, the pixel portion forming inks of corresponding colors are selectively adhered to the pixel portion forming regions 4R, 4G, and 4B whose hydrophilicity has been increased in the step of FIG. )
Ink layers 6R, 6G, and 6B as shown in are formed.

The pixel portion forming ink can be attached to the pixel portion forming region by any method such as printing.
As shown in (F), it is preferable to spray onto the pixel portion formation region by an inkjet method. The pixel portion forming ink according to the present invention is unlikely to cause an increase in viscosity at the tip portion of the head 5, and can maintain good ejection properties.
Therefore, the photocurable ink composition of the present invention can be accurately and uniformly adhered by spraying it onto a predetermined pattern forming region having an increased hydrophilicity by changing the wettability, thereby accurately and uniformly adhering. With such a pattern, a pixel portion without color unevenness or color loss can be formed. Moreover, since the ink for forming the pixel portion of each color can be simultaneously sprayed onto the substrate by using the plurality of heads 5, the work efficiency can be improved as compared with the case where the pixel portion is formed for each color.

Next, as shown in FIG. 3G, the ink layers 6R, 6G, and 6B of the respective colors are irradiated with light 7 to be cured.
The ink layer may be irradiated with appropriate light in consideration of the curable component of the photocurable ink composition as in the first method. After curing the ink layer, baking is performed as necessary to form a pixel portion. The thickness of the pixel portion is usually about 0.1 to 2.0 μm in consideration of optical characteristics and the like.

Next, as shown in FIG. 3H, a protective layer 9 is formed on the side of the transparent substrate on which the pixel portions 8R, 8G, 8B are formed. The protective layer is provided to flatten the color filter and prevent components contained in the pixel portion and the like from eluting into the liquid crystal layer of the liquid crystal display device. The thickness of the protective layer can be set in consideration of the light transmittance of the material used, the surface condition of the color filter, etc., and can be set in the range of 0.1 to 2.0 μm, for example. The protective layer may be the same as in the first method.

In this way, the color filter 1 was prepared using the photocurable ink composition for a color filter of the present invention.
02 is manufactured. In this example, the pixel portion is formed using the ink for forming a pixel portion, which is the photocurable ink composition for a color filter of the present invention, and the photocurable ink composition for a color filter of the present invention is formed on the substrate surface. By selectively adhering only to the ink-philic region by utilizing the difference in wettability of the ink, the cured layer other than the pixel portion, for example, the light-shielding layer 2 or the ink-repellent convex portion 3 is formed into a desired pattern. It can also be formed.

When it is desired to form the light-shielding layer 2, first, a light-curing ink composition for a color filter of the present invention, which is prepared by blending a light-shielding colorant such as a black pigment, is prepared. To do. Next, the wettability changing layer 10 is formed on the transparent substrate 1, the wettability of the region where the light shielding layer is to be formed is changed to increase the hydrophilicity, and the light shielding layer forming ink prepared in advance is used. The ink layer is selectively adhered to the light-shielding layer forming region having an increased hydrophilicity (ink affinity) by a method such as an inkjet to form a predetermined pattern, and the ink layer is irradiated with light to be cured, The light-shielding layer can be formed by baking if necessary. Although the light-shielding layer forming ink has poor light transmittance, it can be photocured by adjusting the type of light and irradiation conditions.

When it is desired to form the ink-repellent convex portion 3, first, the photo-curable ink composition for a color filter of the present invention, which comprises an ink-repellent binder, is prepared. Prepare a part forming ink. Next, the light shielding layer 1 and the wettability changing layer 10 are sequentially formed on the transparent substrate 1. Next, in the center of the upper surface of the light-shielding layer 2, an ink-repellent convex-portion forming region having a different wettability is formed in a pattern shape narrower than the light-shielding layer 2 along the longitudinal direction of the light-shielding layer 2. To do. Next, the ink layer is selectively adhered to the ink-repellent convex portion forming region where the hydrophilicity (ink affinity) is increased by a method such as an inkjet method to form an ink layer in a predetermined pattern, and the ink layer is irradiated with light. Then, the ink-repellent convex portion 3 can be formed by curing and then baking if necessary. The ink-repellent convex-forming ink does not need a light-shielding property and thus has a good light-transmitting property, and thus can be easily photocured.

[0188]

EXAMPLES (Example 1) (1) Preparation of coating liquid for photocatalyst-containing layer The following components were mixed and stirred at 100 ° C. for 20 minutes to prepare a coating liquid for photocatalyst-containing layer. <Composition of coating liquid for photocatalyst-containing layer> -Isopropyl alcohol: 3 g-Fluoroalkylsilane (MF manufactured by Tochem Products)
-160E: N- [3- (trimethoxysilyl) propyl] -N-ethyl-perfluorooctanesulfonamide 50% by weight isopropyl ether solution): 0.07
g ・ Titanium oxide sol (STK-01 made by Ishihara Sangyo): 3 g ・ Silica sol (Grasca HPC700 made by Japan Synthetic Rubber)
2): 0.6 g-Alkylalkoxysilane (HPC4 made by Japan Synthetic Rubber)
02C): 0.2 g (2) Formation of photocatalyst-containing layer The above-mentioned coating for photocatalyst-containing layer was formed on a transparent substrate made of soda glass having a black matrix composed of a chromium thin film pattern having an opening of 76 μm × 259 μm and a line width of 23 μm. The solution was applied with a spin coater, dried at 150 ° C. for 10 minutes, and then hydrolyzed and polycondensed to proceed, whereby the photocatalyst was firmly fixed in the organopolysiloxane and contained a transparent photocatalyst with a thickness of 0.5 μm. Layers were formed.

This photocatalyst-containing layer was irradiated with light through a mask with a mercury lamp (wavelength: 365 nm) at an illuminance of 70 mW / cm ² for 3 minutes, and the contact angle of water between the non-irradiated part and the irradiated part was measured. The contact angle was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) 30 seconds after dropping a water droplet from a microsyringe on the non-irradiated site or the irradiated site. As a result, the contact angle of water at the non-irradiated site is 70 °, whereas the contact angle of water at the irradiated site is 10 ° or less, and the irradiated site becomes highly hydrophilic, and the non-irradiated site does not. It was confirmed that pattern formation was possible by utilizing the difference in wettability with the site.

Further, using the standard solution shown in the wetting test specified in JIS K6768, the contact angle (θ) was measured after 30 seconds from contacting the droplet with the non-irradiated site on the surface of the photocatalyst containing layer, When a Zisman plot (horizontal axis: surface tension of standard solution, vertical axis: cos θ) is created and the graph is extrapolated, the surface tension at the point where cos θ = 0, that is, the critical surface tension of the non-irradiated site is It was 30 mN / m.
When the critical surface tension at the irradiated site was measured by the same method, it was 70 mN / m.

(3) An exposure pattern pitch of the photocatalyst-containing layer is 76 μm × 259 μm, and a mask having a light-shielding pattern having a width (10 μm) narrower than the line width (23 μm) of the black matrix is used as a photocatalyst for the transparent substrate. After arranging on the containing layer and aligning so as to overlap with the black matrix, the photocatalyst containing layer is exposed for 50 seconds with an illuminance of 70 mW / cm ² by a mercury lamp (wavelength 365 nm) through this mask to expose the irradiation site. Made highly hydrophilic. Each irradiation site is divided by a non-irradiation part having a width of 10 μm existing on the black matrix, and has a pixel part formation region of a size of 76 μm × 259 μm surrounded by the black matrix and a region overlapping the surrounding black matrix. Was.

(4) Preparation of Color Ink for Pixel Part Of the following components, first, a pigment, a polymer dispersant and a solvent were mixed, and a three-roll and a bead mill were used to obtain a pigment dispersion. While sufficiently agitating the pigment dispersion liquid with a dissolver or the like, other materials were added little by little to prepare a colored ink for a red pixel portion. <Composition of coloring ink for red pixel portion> Pigment (CI Pigment Red 254): 5 parts by weight Polymer dispersant (SOLECUS 270 manufactured by AVECIA)
00): 1 part by weight-Binder (benzyl methacrylate-methacrylic acid copolymer): 5 parts by weight-Monomer (ethylene glycol diacrylate): 1
7 parts by weight Initiator (2-hydroxy-2-methyl-1-phenyl-propane) -1-one: 2 parts by weight Solvent (water): 78 parts by weight Further, ethylene glycol diacrylate which is a bifunctional monomer is , In a similar test, the critical surface tension is 30
The contact angle with respect to the surface of the test piece of mN / m was 29.9 °, and the contact angle with respect to the surface of the test piece with the critical surface tension of 70 was 10 ° or less.

Furthermore, C.I. I. Pigment Red 254, and C.I. I. Pigment Green 36
A green-red pixel portion colored ink was prepared in the same manner as the red-pixel portion colored ink except that the same amount was used. Furthermore, C.I. I. Pigment Red 254, and C.I. I. Pigment Blue 15: 6 was used in the same amount, and a blue pixel portion colored ink was prepared in the same manner as the red pixel portion colored ink.

(5) Manufacture of Color Filter The above ink for ink for red pixel portion was filled in an ink jet head, and a drop diameter of 30 μm was applied from the head to the center of each pixel portion forming region for red formed on the substrate. Dropped. Similarly, the colored ink for the green pixel portion is dropped from the head to the center of each pixel portion forming region for green with a drop diameter of 30
It was dripped at μm. In addition, the color ink for the blue pixel part,
A drop diameter of 30 μm was dropped from the head to the center of each pixel portion formation region for blue. The dropped color ink for pixel portions of each color was repelled at the non-irradiated portion on the black matrix, and uniformly diffused and selectively adhered to the pixel portion forming region of each color.

After that, the colored ink layers of respective colors were applied at 80 ° C. for 3 days.
After drying for 70 minutes, use a mercury lamp (wavelength 365 nm) to 70
Light rays were irradiated for 30 seconds at an illuminance of mW / cm ² , and heat treatment was further performed at 200 ° C. for 60 minutes to form a pixel portion.

Then, a two-component mixed type thermosetting agent (SS7265 manufactured by Nippon Synthetic Rubber Co., Ltd.) was applied on the pixel portion by a spin coater, and a curing treatment was performed at 200 ° C. for 30 minutes to form a protective layer. , A color filter was obtained.

(Evaluation of Physical Properties) The viscosity of each of the red, green and blue colored inks immediately after preparation was measured. In addition, spin coating a well washed glass substrate with each coloring ink, drying it sufficiently, irradiating it with UV at an irradiation dose of 500 mJ, and then performing post-baking at 200 ° C. for 1 hour on a hot plate. A cured coating having a thickness of 1 μm was obtained. Adhesion of the obtained cured film, and
The pencil hardness was evaluated. The procedure of each evaluation method is shown below.
The evaluation results are shown in Table 1.

<Viscosity> Viscosity was measured by a vibrating tube flow method using VILASTIC SCIENTIFIC VI.
Using LASTIC V-E SYSTEM, frequency 2
Hz, use tube CURRENT TUBE Tub
It was measured under the condition of e # 1.

<Adhesion Procedure> Films Obtained Using Each Colored Ink JIS K5400 (1990)
The result of the cross-cut tape peeling test specified in 8.5 was 6 or more, and it was judged as good.

<Procedure for Pencil Hardness> Regarding the film obtained by using each coloring ink, JIS K5400 (1990)
Of the pencil scratching tests specified in Section 8.4.1, the 8.4.1 test method was performed, and when the pencil hardness was 2H or more, it was judged as good.

[0201]

[Table 1]

[0202]

As described above, in the present invention, in the reaction curable ink composition for color filters,
Since a reactive curable monomer having a relatively small number of bifunctional or trifunctional functional groups is used, the viscosity at the tip of the head is unlikely to increase during the spraying operation of the inkjet method, and the head does not become clogged. Ink dischargeability is stable. Therefore, the ejection amount and the ejection direction of the ink are kept constant, and the ink can be accurately and uniformly adhered onto the substrate in a predetermined pattern.

Further, in the present invention, since the water-soluble solvent containing water as the main component is used, the wettability of a part of the surface of the wettability variable layer is changed so that the wettability becomes larger and the predetermined pattern is formed. A large difference can be obtained between the wettability of the photocurable ink composition with respect to the ink layer forming region and the wettability of the photocurable ink composition with respect to the surrounding region.
Therefore, the reaction curable ink composition for a color filter of the present invention can be accurately and uniformly adhered to the ink layer forming region. Therefore, the reaction curable ink composition of the present invention is excellent not only in the ink for forming the pixel portion but also in the inkjet system.

Further, in the present invention, by using a water-soluble solvent mainly composed of water as a solvent for the photocurable ink composition, the amount of the organic solvent used can be reduced and the organic solvent used in the ink manufacturing process or the color filter manufacturing process can be reduced. Since it is possible to avoid volatilization of the solvent, it is preferable from the viewpoint of work hygiene and environmental hygiene.

[Brief description of drawings]

FIG. 1 is an explanatory view of a first method of manufacturing a color filter.

FIG. 2 is an explanatory diagram of a second method (first half) of manufacturing a color filter.

FIG. 3 is an explanatory diagram of a second method (second half) of manufacturing a color filter.

[Explanation of symbols]

1 ... Transparent substrate 2 ... Shading section 3 ... Ink-repellent convex 4 ... Pixel portion forming region 5 ... Inkjet head 6 ... Ink layer 7 ... Ray 8 ... Pixel part 9 ... Protective film 10 ... Photocatalyst-containing layer 11 ... Photomask 12 ... Exposure unit

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/004 505 G03F 7/027 502 7/027 502 B41J 3/04 101Y (72) Inventor Nishiyama Masa Tokyo 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. (72) Manabu Yamamoto 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dai-Nippon Printing Co., Ltd. F-term (reference) 2C056 FB01 2H025 AA02 AA11 AB13 AC01 AD01 BC13 BC42 BC51 BC82 CC17 2H048 BA11 BA47 BA64 BB01 BB42 2H091 FA02Y GA01 LA15 4J039 AD03 AD09 AD10 AD20 AD21 AE05 BA12 BC08 BC09 BE12 CA03 CA06 EA03 EA05 EA44 GA24 EA43 GA24 EA43

Claims (20)

[Claims] 1. A color filter, comprising at least a binder and a bifunctional to trifunctional reaction-curable monomer dissolved or dispersed in a water-soluble solvent comprising water and a water-soluble organic solvent. Reaction curable water-based ink composition. 2. The reaction curable water-based ink composition for a color filter according to claim 1, further comprising a colorant. 3. The reaction for a color filter according to claim 1, wherein the bifunctional to trifunctional reaction-curable monomer is a photopolymerization-reactive or thermal-polymerization-reactive monomer. Curable water-based ink composition. 4. The bifunctional to trifunctional photopolymerization-reactive monomer has an acryloyloxy group and / or a methacryloyloxy group as a functional group, and is characterized in that: Reactive curable water-based ink composition for color filters. 5. The difunctional to trifunctional photopolymerization reactive monomer is ethylene glycol diacrylate, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, or 1; At least one selected from 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and 1,3-butylene glycol dimethacrylate. The reaction curable water-based ink composition for a color filter according to item 4. 6. The reaction curable water-based ink for a color filter according to claim 3, wherein the bifunctional to trifunctional thermopolymerization reactive monomer has an epoxy group as a functional group. Composition. 7. The bifunctional to trifunctional thermopolymerization reactive monomer is polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane polyglycidyl. Ether, 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene,
3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 5-vinylpyrogallol triglycidyl ether, 4-vinylpyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrenediene Glycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3 ，
The reaction for a color filter according to claim 6, which is at least one selected from 4-trihydroxymethylstyrene triglycidyl ether and 1,3,5-trihydroxymethylstyrene triglycidyl ether. Curable water-based ink composition. 8. A reaction-curable monomer having a functionality of 4 or more and capable of polymerizing with the reaction-curable monomer having a functionality of 2 to 3 is added to the reaction-curable monomer 100 having a functionality of 2 to 3.
The reaction curable water-based ink composition for color filters according to any one of claims 1 to 7, which is contained in a ratio of 1 to 50 parts by weight with respect to parts by weight. 9. The water-soluble organic solvent is JIS K6.
Using the standard solution shown in the wetting test specified in 768, the contact angle (θ) after contacting the droplet for 30 seconds was measured, and the critical surface tension determined from the graph of Zisman plot was 30 mN / m. The contact angle to the surface of the test piece is 10
And a contact angle with respect to the surface of a test piece having a critical surface tension of 70 mN / m determined by the same measurement method is 1 or more.
2. It shows that the angle is 0 ° or less.
9. A reaction curable water-based ink composition for a color filter according to any one of 8 to 8. 10. The bifunctional to trifunctional reaction-curable monomer is a standard solution shown in a wetting test specified in JIS K6768, and a contact angle (θ) after 30 seconds from contacting a droplet is used. A test in which the contact angle with respect to the surface of a test piece having a critical surface tension of 30 mN / m determined by the graph of Zisman plot is 10 ° or more, and the critical surface tension determined by the same measurement method is 70 mN / m. The reaction curable water-based ink composition for a color filter according to claim 9, wherein the contact angle with respect to the surface of the piece is 10 ° or less. 11. The reaction curable monomer having 4 or more functional groups is a standard solution shown in a wetting test specified in JIS K6768, and the contact angle (θ) is measured after 30 seconds from contacting the droplets. A test piece with a critical surface tension of 30 mN / m, obtained by the graph of Zisman plot, shows a contact angle of 10 ° or more with respect to the surface of the test piece, and a critical surface tension of 70 mN / m obtained by the same measurement method. The photocurable water-based ink composition for a color filter according to claim 9 or 10, wherein the contact angle with respect to the surface of the ink is 10 ° or less. 12. The reaction curable water-based ink composition for a color filter according to claim 1, wherein the water-soluble organic solvent is a water-soluble glycol. 13. (1) An ink layer is formed by selectively adhering the reaction curable ink composition for a color filter according to any one of claims 1 to 12 to a predetermined region on a substrate by an inkjet method. And a step (2) of reacting and curing the ink layer to form a cured layer having a predetermined pattern, the method for producing a color filter. 14. A step of (1) forming a wettability variable layer capable of changing wettability on a substrate in a direction of increasing hydrophilicity, and (2) a predetermined region on the surface of the wettability variable layer. 13. A step of selectively changing the wettability of the inside to form an ink layer forming region having a hydrophilicity larger than that of the surroundings, and (3) the ink layer forming region, wherein
A step of selectively adhering the reaction curable water-based ink composition for a color filter according to any one to form an ink layer, and (4) reacting and curing the ink layer to form a cured layer having a predetermined pattern. The method for producing a color filter, comprising: 15. The method according to claim 14, wherein the reaction curable water-based ink composition for a color filter according to any one of claims 9 to 12 is used. 16. The manufacturing method according to claim 14, wherein the reaction curable water-based ink composition for a color filter is selectively attached to the ink layer forming region by an inkjet method. . 17. The wettability variable layer according to JIS K6.
Using the standard solution shown in the wetting test specified in 768, the contact angle (θ) after contacting the droplet for 30 seconds was measured, and the critical surface tension obtained from the graph of the Zisman plot showed the wettability. 20-50mN before changing
/ M, and 4 after changing the wettability
15. Showing 0 to 80 mN / m.
17. The method according to any one of 16 to 16. 18. The wettability variable layer changes wettability in a direction of increasing hydrophilicity by being irradiated with a light beam, according to claim 14. Manufacturing method. 19. The wettability variable layer is a photocatalyst containing layer in which the wettability variable layer itself contains a photocatalyst, or a photocatalyst containing layer provided on the substrate side of the wettability variable layer. It is characterized in that the photocatalyst is activated by irradiating the photocatalyst-containing layer with a light beam, and by the action of the activated photocatalyst, the wettability is changed in the direction in which the hydrophilicity increases. The manufacturing method according to claim 18. 20. A pixel portion as the cured layer is formed by using the reaction curable water-based ink composition for a color filter according to claim 2.
20. The manufacturing method according to any one of 3 to 19.