JP2005258271A - Color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter having excellent adhesive property to various members such as a colored layer and manufactured with good manufacture efficiency. <P>SOLUTION: The color filter has base material, a light shielding part formed on the base material, a photocatalyst containing layer formed to cover over the base material and the light shielding part and containing a photocatalyst and organo-polysiloxane, and the colored layer formed on the photocatalyst containing layer. The photocatalyst containing layer has minute holes and particulate organic and inorganic composite material. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a color filter suitable for a color liquid crystal display, which is obtained by coloring a colored layer by an inkjet method.

  In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, since this color liquid crystal display is expensive, there is an increasing demand for cost reduction, and in particular, there is a high demand for cost reduction for a color filter having a high specific gravity.

  In such a color filter, it is usually provided with coloring patterns of three primary colors of red (R), green (G), and blue (B), and electrodes corresponding to the respective pixels of R, G, and B are turned on, By turning it off, the liquid crystal operates as a shutter, and light passes through each of the R, G, and B pixels, and color display is performed.

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

Another method is a pigment dispersion method. In this method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and this is patterned to obtain a monochromatic pattern. Further, this process is repeated three times to form R, G, and B color filter layers.
Still other methods include an electrodeposition method, a method in which a pigment is dispersed in a thermosetting resin, R, G, and B are printed three times, and then the resin is thermoset. However, in any method, it is necessary to repeat the same process three times in order to color the three colors of R, G, and B, and there is a problem that the cost is high, and the yield decreases because the process is repeated. There's a problem.

  Therefore, a photocatalyst-containing layer is formed on the base material using a coating solution for property change pattern formation containing a photocatalyst and a material whose properties change due to the action of the photocatalyst accompanying energy irradiation, and is exposed in a pattern. Thus, the inventors have studied a method for manufacturing a color filter that forms a pattern with changed characteristics and forms a colored layer (Patent Document 1). According to this method, it is possible to easily form a colored layer using the characteristics of the photocatalyst-containing layer.

  Here, since various members, such as a colored layer and an ITO layer, are provided on the photocatalyst-containing layer, by making the adhesiveness better with other members, higher quality can be achieved. A color filter can be formed. In addition, the above-described color filter changes the characteristics of the portion irradiated with energy by utilizing the action of the photocatalyst to form patterns having different characteristics, and thus causes a difference in characteristics. It takes a predetermined time to make it happen. If this time can be shortened, further efficiency can be achieved.

Japanese Patent Laid-Open No. 2001-074928

  Therefore, it is desired to provide a color filter that has better adhesion to various members such as a colored layer and is manufactured with high manufacturing efficiency.

The present invention includes a base material, a light-shielding portion formed on the base material, a photocatalyst-containing layer formed so as to cover the base material and the light-shielding portion, and containing a photocatalyst and an organopolysiloxane, and the photocatalyst-containing material A color filter having a colored layer formed on the layer,
Provided is a color filter, wherein the photocatalyst-containing layer has fine pores and a particulate organic-inorganic composite material.

  According to the present invention, since the photocatalyst-containing layer has the fine pores, a colored layer or the like formed on the photocatalyst-containing layer can enter the photocatalyst-containing layer, and the photocatalyst-containing layer and the colored layer And high adhesiveness. In addition, since the photocatalyst-containing layer contains a photocatalyst and an organopolysiloxane, the contact angle with the surface liquid can be reduced by the action of the photocatalyst accompanying energy irradiation. Therefore, when manufacturing a color filter, by irradiating energy only to the region where the colored layer is formed, the contact angle with the liquid in this region can be reduced, and this difference in wettability is utilized. Thus, a colored layer can be easily formed by an ink jet method or the like. At this time, since the photocatalyst-containing layer has fine vacancies, the action of the photocatalyst accompanying energy irradiation can generate active oxygen species and the like in the fine vacancies, and the photocatalyst has good sensitivity. It can be done.

  In the said invention, it is preferable that the largest major axis of the said particulate organic inorganic composite material contains the thing in the range of 0.03 micrometer-0.3 micrometer.

  Moreover, in the said invention, it is preferable that the said photocatalyst containing layer has a surface fine void | hole which has a depth of 30 nm or more from the line | wire which connected the convex part which the said photocatalyst containing layer surface adjoins. Thereby, the said colored layer etc. can penetrate | invade in a photocatalyst containing layer, and the adhesiveness of these layers and a photocatalyst containing layer can be improved.

  Still further, in the invention, the photocatalyst-containing layer has the fine surface pores having a pore diameter in a range of 10 nm to 30 nm at a depth of 30 nm from a line connecting adjacent convex portions on the surface of the photocatalyst-containing layer. It is preferable to have. This is because the adhesion between the photocatalyst-containing layer and the colored layer can be made better.

  Moreover, in the said invention, the said colored layer shall have a thermosetting resin and dye or a pigment at least. The colored layer may have at least an ultraviolet curable resin and a dye or pigment.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness of a photocatalyst containing layer and the colored layer formed on the photocatalyst containing layer can be made high. In addition, by utilizing the difference in wettability of the photocatalyst-containing layer, a colored layer can be easily formed by an inkjet method or the like, and the sensitivity of the photocatalyst can be improved. Color filter.

The present invention relates to a color filter suitable for a color liquid crystal display obtained by coloring a colored layer by an inkjet method and a method for producing the same, and the color filter of the present invention includes a base material and the base material. A color filter having a formed light-shielding portion, a photocatalyst-containing layer containing a photocatalyst and an organopolysiloxane, and a colored layer formed on the photocatalyst-containing layer, so as to cover the substrate and the light-shielding portion Because
The photocatalyst-containing layer has fine pores and a particulate organic-inorganic composite material.

  For example, as shown in FIG. 1, the color filter of the present invention includes a base material 1, a light shielding part 2 formed on the base material 1, a photocatalyst containing layer 3 formed on the light shielding part 2, and A color filter having a colored layer 4 formed on the photocatalyst-containing layer 3, wherein the photocatalyst-containing layer has fine pores and a particulate organic-inorganic composite material.

Here, the particulate organic-inorganic composite material refers to a material in which an inorganic material such as the photocatalyst is partially or entirely coated with an organic material such as organopolysiloxane. In addition, the photocatalyst of the particulate organic-inorganic composite material may be partially exposed, and further, the photocatalyst particles may be coated with an organic substance such as organopolysiloxane. Also good.
The photocatalyst-containing layer contains fine pores and fine-particle organic-inorganic composite material, for example, as shown in FIG. 2, the fine-particle organic-inorganic composite material is formed so as to have fine pores in the photocatalyst-containing layer. It means being done.

  In the present invention, since the photocatalyst-containing layer has fine pores, a material such as a colored layer formed on the photocatalyst-containing layer enters the fine pores and exhibits an anchor effect. Adhesiveness with the member formed on the containing layer can be made favorable.

  In the present invention, since the organopolysiloxane is contained in the photocatalyst-containing layer, the contact angle with the liquid on the surface can be reduced by the action of the photocatalyst accompanying energy irradiation, and this wetting By utilizing the difference in properties, the colored layer can be easily formed by an inkjet method or the like. The mechanism of action of such a photocatalyst is not necessarily clear, but radicals generated by light irradiation are reacted directly with nearby compounds, or by active oxygen species generated in the presence of oxygen and water, It is thought to change the chemical structure of organic matter. In the present invention, it is considered that these radicals and active oxygen species act on the organopolysiloxane in the photocatalyst-containing layer to reduce the contact angle with the liquid on the surface.

In the present invention, since the photocatalyst-containing layer has the fine vacancies, the amount of active oxygen species and the like generated by reacting with oxygen and the like in the fine vacancies by the action of the photocatalyst excited by energy irradiation. Can be many. Accordingly, the sensitivity of the photocatalyst can be improved, and the contact angle of the organopolysiloxane with the liquid can be efficiently reduced. In addition, since the contact angle with the liquid can be reduced not only to the surface of the photocatalyst-containing layer but also to the inside of the photocatalyst-containing layer, the sensitivity of the photocatalyst is improved and the wettability with the liquid is improved. Compared with a photocatalyst-containing layer that does not have a light-emitting layer, the layer can be made much better, and the color filter can be produced efficiently.
Hereinafter, each configuration of the color filter of the present invention will be described in detail.

1. Photocatalyst containing layer First, the photocatalyst containing layer used for this invention is demonstrated. The photocatalyst-containing layer used in the present invention contains a photocatalyst and an organopolysiloxane, and is formed so as to cover a base material and a light-shielding portion to be described later. If it has a composite material, it will not specifically limit.

  Here, the size of the fine-particle organic-inorganic composite material contained in the photocatalyst-containing layer of the present invention is particularly limited as long as the wettability of the surface can be changed by the action of the photocatalyst accompanying energy irradiation. However, it is preferable to include those having a maximum major axis of 0.03 μm to 0.3 μm, particularly 0.05 μm to 0.2 μm, and those having a maximum major axis within the above range are photocatalysts. It is preferable that about 50 to 90 weight% is contained in solid content which comprises a content layer. Here, the maximum major axis means a length that maximizes the diameter in one particle.

  Further, the photocatalyst-containing layer preferably has fine pores on the surface, and in particular, a surface fine void having a depth of 30 nm or more from the line connecting the convex portions on the surface of the photocatalyst-containing layer, particularly a depth in the range of 50 to 200 nm. It is preferable to have a hole. This is because the action of the photocatalyst can be further exhibited. The depth of the surface micropores at this time is calculated by, for example, photographing the cross section of the photocatalyst containing layer with an electron microscope and measuring the surface micropores in the range of the length of the photocatalyst containing layer surface of 1.0 μm. can do. In the present invention, it is preferable that the surface fine pores have about 20 / μm to 50 / μm with respect to the length of the surface.

  Further, at this time, the photocatalyst-containing layer has the above-described surface fine voids having a pore diameter at a position of 30 nm from a line connecting the convex portions of the adjacent photocatalyst-containing layer surfaces within a range of 10 nm to 30 nm, especially 15 nm to 20 nm. It is preferable to have a hole. The pore diameter can also be obtained from a photograph taken with an electron microscope, as in the case of measuring the depth of the surface fine pores. Moreover, it is preferable that the surface fine void | hole which has the said hole diameter is formed within the range of 30% -80% in all the surface fine void | holes, especially 40% -70%. This is because the adhesion between the photocatalyst-containing layer and other layers can be further improved.

  Here, since the photocatalyst-containing layer contains organopolysiloxane, the contact angle with the liquid on the surface can be reduced by the action of the photocatalyst when irradiated with energy, and the region irradiated with energy. Can be defined as a lyophilic region, and a region not irradiated with energy as a lyophobic region.

  In the present invention, the contact angle with a liquid having a surface tension of 30 mN / m is 10 ° or more in a contact angle with a liquid with a surface tension of 30 mN / m in a portion not irradiated with energy, that is, a liquid repellent region. In particular, the contact angle with a liquid having a surface tension of 20 mN / m is preferably 10 ° or more. This is because the part that is not irradiated with energy is a part that requires liquid repellency, so when the contact angle with the liquid is small, the liquid repellency is not sufficient. For example, a colored layer described later is formed. When the colored layer forming coating liquid is applied by an inkjet method and cured, the colored layer forming coating liquid may adhere to the liquid-repellent region. This is because it becomes difficult to form a colored layer.

  The photocatalyst-containing layer has a contact angle with a liquid of 40 mN / m of less than 9 °, preferably a liquid with a surface tension of 50 mN / m, in a portion irradiated with energy, that is, a lyophilic region. The layer is preferably such that the contact angle with a liquid having a surface tension of 10 ° or less, particularly 60 mN / m, is 10 ° or less. When the contact angle with the liquid in the energy irradiated part, that is, the lyophilic region is high, for example, the colored layer forming coating liquid for forming the colored layer may be repelled in the lyophilic region. This is because, for example, when the coating liquid for forming a colored layer is applied by an inkjet method, the coating liquid for forming a colored layer is not sufficiently spread and spread, and it may be difficult to form a colored layer.

  In addition, the contact angle with the liquid here is measured using a contact angle measuring instrument (Kyowa Interface Science Co., Ltd. CA-Z type) with a liquid having various surface tensions (from the microsyringe to the liquid. 30 seconds after dropping), and the result was obtained or the result was graphed. In this measurement, as a liquid having various surface tensions, a wetting index standard solution manufactured by Pure Chemical Co., Ltd. was used.

  The photocatalyst-containing layer used in the present invention contains fluorine in the photocatalyst-containing layer, and when the fluorine content on the surface of the photocatalyst-containing layer is irradiated with energy to the photocatalyst-containing layer, The photocatalyst-containing layer may be formed so as to be lower than that before energy irradiation, and is decomposed by the action of the photocatalyst by energy irradiation, thereby improving the wettability on the photocatalyst-containing layer. It may be formed so as to contain a decomposition substance capable of

  Hereinafter, the photocatalyst, organopolysiloxane, and other components constituting such a photocatalyst-containing layer will be described.

a. Photocatalyst First, the photocatalyst used in the present invention will be described. Examples of the photocatalyst used in the present invention include titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), which are known as photo semiconductors. Bismuth oxide (Bi ₂ O ₃ ) and iron oxide (Fe ₂ O ₃ ) can be mentioned, and one or a mixture of two or more selected from these can be used.

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

  Examples of such anatase type titanium dioxide include hydrochloric acid peptizer type anatase type titania sol (STS-02 manufactured by Ishihara Sangyo Co., Ltd. (average particle size 7 nm), ST-K01 manufactured by Ishihara Sangyo Co., Ltd.), nitric acid solution An anatase type titania sol (TA-15 manufactured by Nissan Chemical Co., Ltd. (average particle size 12 nm)) and the like can be mentioned.

  The smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs. The average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less.

  The content of the photocatalyst in the photocatalyst containing layer used in the present invention can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. The thickness of the photocatalyst containing layer is preferably in the range of 0.05 to 10 μm.

b. Organopolysiloxane Next, the organopolysiloxane used in the present invention will be described. The organopolysiloxane used in the present invention is not particularly limited as long as it can reduce the contact angle with the liquid on the surface of the photocatalyst containing layer by the action of the photocatalyst accompanying energy irradiation, and is not particularly limited. It is preferable that the main skeleton has a high binding energy such that it is not decomposed by photoexcitation of the photocatalyst, and has an organic substituent that is decomposed by the action of the photocatalyst. Specifically, (1) an organopolysiloxane that exerts a high strength by hydrolyzing and polycondensing chloro or alkoxysilane by sol-gel reaction or the like, and (2) a reactive silicone excellent in water repellency and oil repellency. Cross-linked organopolysiloxanes can be mentioned.

In the case of (1) above, the general formula:
Y _n SiX _(4-n)
(Where Y is an alkyl group, fluoroalkyl group, vinyl group, amino group, phenyl group, chloroalkyl group, isocyanate group, or epoxy group, or an organic group containing these, and X is an alkoxyl group, acetyl group, or Represents halogen, n is an integer from 0 to 3)
It is preferable that it is the organopolysiloxane which is a 1 type, or 2 or more types of hydrolysis condensate or cohydrolysis condensate of the silicon compound shown by these. Here, the alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Moreover, it is preferable that the carbon number of the whole organic group shown by Y exists in the range of 1-20, especially in the range of 5-10.

  Thus, when the photocatalyst-containing layer is formed, the surface can be made liquid-repellent by Y constituting the organopolysiloxane, and the Y is decomposed by the action of the photocatalyst accompanying energy irradiation. This is because it can be made lyophilic.

In particular, when an organopolysiloxane in which Y constituting the organopolysiloxane is a fluoroalkyl group is used, the photocatalyst-containing layer before energy irradiation can be made particularly high in liquid repellency. When high liquid repellency is required, it is preferable to use an organopolysiloxane having these fluoroalkyl groups. Specific examples of such organopolysiloxanes include one or more of the following hydroalkyl silanes, co-hydrolysis condensates, and are generally known as fluorine-based silane coupling agents. Can be used.
_{CF 3 (CF 2) 3 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 CH} 2 CH 2 Si (OCH 3) 3;
_{CF 3 (CF 2) 9 CH} 2 CH 2 Si (OCH 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 (CF 2) 3 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3;
_{CF 3 (CF 2) 3 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 5 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 7 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{CF 3 (CF 2) 9 CH} 2 CH 2 SiCH 3 (OCH 3) 2;
_{(CF 3) 2 CF (CF} 2) 4 CH 2 CH 2 SiCH 3 (OCH 3) 2;
_{(CF 3) 2 CF (CF} 2) 6 CH 2 CH 2 Si CH 3 (OCH 3) 2;
_{(CF 3) 2 CF (CF} 2) 8 CH 2 CH 2 Si CH 3 (OCH 3) 2;
_{CF 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 CH 3) 3;
_{CF 3 (CF 2) 5 CH} 2 CH 2 Si (OCH 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;
_{CF 3 (CF 2) 7 SO} 2 N (C 2 H 5) C 2 H 4 CH 2 Si (OCH 3) 3.

  Examples of the reactive silicone (2) include compounds having a skeleton represented by the following general formula.

However, n is an integer of 2 or more, R ^1, R ² are each a substituted or unsubstituted alkyl having 1 to 10 carbon atoms, alkenyl, aryl or cyanoalkyl group, the total molar ratio of 40% or less Vinyl, phenyl and phenyl halide. Further, those in which R ¹ and R ² are methyl groups are preferable because the surface energy becomes the smallest, and the methyl groups are preferably 60% or more by molar ratio. In addition, the chain end or side chain has at least one reactive group such as a hydroxyl group in the molecular chain.

  The organopolysiloxane is preferably contained in the photocatalyst-containing layer in an amount of 5 to 90% by weight, especially about 30 to 60% by weight.

c. Other Substances In the photocatalyst-containing layer used in the present invention, a stable organosilicon compound that does not undergo a crosslinking reaction, such as dimethylpolysiloxane, may be mixed with a binder together with the organopolysiloxane. Furthermore, examples of the binder include polysiloxanes having a high binding energy that does not cause the main skeleton to be decomposed by photoexcitation of the photocatalyst, or that do not have an organic substituent, or have an organic substituent. You may contain what hydrolyzed and polycondensed methoxysilane, tetraethoxysilane, etc.

  Furthermore, in order to assist the function of changing the wettability of the organopolysiloxane, a decomposition substance that is decomposed by energy irradiation may be included. Examples of such decomposition substances include surfactants that have the function of decomposing by the action of a photocatalyst and reducing the contact angle with the liquid on the surface of the photocatalyst-containing layer by being decomposed. Specifically, hydrocarbons such as NIKKOL BL, BC, BO, BB series manufactured by Nikko Chemicals Co., Ltd., ZONYL FSN, FSO manufactured by DuPont, Surflon S-141, 145 manufactured by Asahi Glass Co., Ltd., Dainippon Megafac F-141, 144 manufactured by Ink Chemical Industry Co., Ltd., Footgent F-200, F251 manufactured by Neos Co., Ltd., Unidyne DS-401, 402 manufactured by Daikin Industries, Ltd., Fluorard FC-170 manufactured by 3M Co., Ltd. Fluorine-based or silicone-based nonionic surfactants such as 176, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  Besides surfactants, 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, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene, oligomers, polymers, and the like.

d. In addition, in the present invention, when the photocatalyst containing layer contains fluorine, and the fluorine content on the surface of the photocatalyst containing layer is irradiated with energy to the photocatalyst containing layer, the photocatalyst containing layer is irradiated with energy by the action of the photocatalyst. It is preferable that the photocatalyst-containing layer is formed so as to be lower than before. Thereby, the pattern which consists of a part with little content of fluorine can be easily formed by irradiating energy with a pattern so that it may mention later. Here, fluorine has an extremely low surface energy. Therefore, the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a small fluorine content is larger than the critical surface tension of the surface of the portion having a large fluorine content. This means that the portion with a low fluorine content is a lyophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a lower fluorine content than the surrounding surface forms a pattern of a lyophilic region in the liquid repellent region.

  Therefore, when such a photocatalyst-containing layer is used, the pattern of the lyophilic region can be easily formed in the liquid-repellent region by irradiating the pattern with energy. This is because a high-definition colored layer can be formed when the colored layer forming coating solution is applied.

  As described above, the fluorine content contained in the photocatalyst containing layer containing fluorine is not irradiated with energy in the lyophilic region having a low fluorine content formed by energy irradiation. When the fluorine content of the part is 100, it is 10 or less, preferably 5 or less, particularly preferably 1 or less.

  By setting it within such a range, it is possible to make a large difference in lyophilicity between the energy-irradiated portion and the unirradiated portion. Therefore, for example, by attaching a coating liquid for forming a colored layer to such a photocatalyst-containing layer, it becomes possible to accurately form a colored layer only in a lyophilic region having a reduced fluorine content. This is because a good color filter can be obtained. This rate of decrease is based on weight.

  For the measurement of the fluorine content in the photocatalyst-containing layer, various commonly used methods can be used. For example, X-ray photoelectron spectroscopy (ES-ray photoelectron spectroscopy, ESCA) for Chemical Analysis)), and any method that can quantitatively measure the amount of fluorine on the surface, such as X-ray fluorescence analysis and mass spectrometry, is not particularly limited.

  In the present invention, as described above, titanium dioxide is preferably used as the photocatalyst. When titanium dioxide is used in this way, the fluorine content contained in the photocatalyst-containing layer is X-ray photoelectron. When analyzed and quantified by spectroscopy, when the titanium (Ti) element is defined as 100, the fluorine (F) element is in a ratio of 500 or more, preferably 800 or more, particularly preferably 1200 or more. It is preferable that the element is contained on the surface of the photocatalyst containing layer.

  Fluorine (F) is included in the photocatalyst-containing layer to such an extent that the critical surface tension on the photocatalyst-containing layer can be sufficiently lowered, so that the liquid repellency on the surface can be secured, thereby irradiating the pattern with energy. This is because the difference in wettability with the lyophilic region on the surface of the pattern portion where the fluorine content is reduced can be increased, and the accuracy of the color filter finally obtained can be improved.

  Further, in such a color filter, the fluorine content in the lyophilic region formed by pattern irradiation with energy is 50 or less when the titanium (Ti) element is 100, preferably It is preferably contained in a ratio of 20 or less, particularly preferably 10 or less.

  If the fluorine content in the photocatalyst-containing layer can be reduced to this extent, sufficient lyophilicity can be obtained for forming a color filter, and the liquid repellency of the portion where the energy is not irradiated can be obtained. Due to the difference in wettability, the color filter can be formed with high accuracy, and a color filter with high utility value can be obtained.

e. Method for Forming Photocatalyst-Containing Layer As a method for forming the photocatalyst-containing layer as described above, a coating solution is prepared by dispersing the photocatalyst and organopolysiloxane in a solvent together with other additives as necessary. It can form by apply | coating a liquid on a base material. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The application can be performed by a known application method such as spin coating, spray coating, dip coating, roll coating, or bead coating. When an ultraviolet curable component is contained as a binder, the photocatalyst-containing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.

f. Method for forming wettability change pattern on photocatalyst-containing layer Next, the wettability change pattern in which the contact angle with the liquid is lowered into a pattern that forms a colored layer to be described later by irradiating the photocatalyst-containing layer with energy. A method for forming the film will be described. In the present invention, as described above, the contact angle between the organopolysiloxane in the photocatalyst-containing layer and the liquid is lowered by the action of the photocatalyst accompanying energy irradiation. Therefore, for example, as shown in FIG. 3, when the photocatalyst-containing layer 3 is irradiated with energy 6 using a photomask 5 or the like (FIG. 3A), the wettability on the photocatalyst-containing layer 3 becomes good. A wettability change pattern 7 is formed (FIG. 3B). When a wettability change pattern is formed on the photocatalyst-containing layer, when a coloring layer forming coating liquid for forming a colored layer described later is applied by an ink jet method or the like, an ink is not applied to a region not irradiated with energy. The coating liquid for forming the colored layer can be attached with high precision only on the wettability change pattern 7 in which the contact angle with the liquid is reduced and the contact angle with the liquid is reduced, and a high-definition colored layer can be formed. It is.

  Here, the energy applied to the photocatalyst containing layer is not particularly limited as long as it is a method of irradiating energy capable of reducing the contact angle with the liquid of the photocatalyst containing layer. Absent. The energy irradiation (exposure) in the present invention is a concept including irradiation of any energy beam capable of reducing the contact angle with the liquid on the surface of the photocatalyst containing layer, and is limited to irradiation with visible light. is not.

  Usually, the wavelength of light used for such energy irradiation is set in a range of 400 nm or less, preferably in a range of 150 nm to 380 nm or less. This is because, as described above, the preferred photocatalyst used in the photocatalyst-containing layer is titanium dioxide, and light having the above-described wavelength is preferable as the energy for activating the photocatalytic action by the titanium dioxide.

  Examples of light sources that can be used for such energy irradiation include mercury lamps, metal halide lamps, xenon lamps, excimer lamps, and various other light sources. In addition to the method of performing pattern irradiation using a light mask using a light source as described above, it is also possible to use a method of drawing and irradiating in a pattern using a laser such as excimer or YAG.

In addition, the irradiation amount of energy at the time of energy irradiation is an irradiation amount necessary to reduce the contact angle with the liquid on the surface of the photocatalyst containing layer by the action of the photocatalyst in the photocatalyst containing layer.
At this time, it is preferable in that the energy can be irradiated while heating the photocatalyst-containing layer, whereby the sensitivity can be further increased and the contact angle with the liquid on the surface of the photocatalyst-containing layer can be efficiently reduced. Specifically, it is preferable to heat within a range of 30 ° C to 80 ° C.

  In the energy irradiation direction in the present invention, when the substrate to be described later is transparent, pattern energy irradiation or laser drawing irradiation through a photomask may be performed from any direction on the substrate side and the photocatalyst containing layer side. . In the present invention, since the light shielding part described later is formed on the base material, when the entire surface is irradiated with energy from the base material side, the photocatalyst-containing layer on the region where the light shielding part is formed is used. The contact angle with the liquid does not decrease, and the wettability of only the opening portion of the light shielding portion can be improved. Therefore, there is an advantage that the wettability change pattern can be efficiently formed without requiring a step of alignment of a photomask or the like.

  On the other hand, when the substrate is opaque, it is necessary to irradiate energy from the photocatalyst containing layer side.

2. Next, the colored layer used in the present invention will be described. The colored layer used in the present invention is formed on the above-described photocatalyst-containing layer. In the present invention, as described above, the wettability change pattern in which the contact angle with the liquid of the photocatalyst-containing layer is lowered is used. Can be formed.

Such a colored layer is usually formed of three colors of red (R), green (G), and blue (B). The colored pattern shape in the colored layer can be a known arrangement such as a stripe type, a mosaic type, a triangle type, or a four-pixel arrangement type, and the colored area can be arbitrarily set.
In the present invention, it is not particularly limited as a method for coloring this colored layer, for example, a coating method in which a known coating is applied by a known method such as spray coating, dip coating, roll coating, bead coating, Although a vacuum thin film form etc. can be mentioned, in this invention, it is preferable to be colored with an inkjet system. This is because a colored layer can be formed with high definition on the wettability change pattern.

  Here, the ink of an ink jet system for forming such a colored layer is largely classified into water-based and oil-based, but any ink can be used in the present invention, but from the viewpoint of surface tension. Water-based aqueous inks are preferred.

  In the water-based ink used in the present invention, water alone or a mixed solvent of water and a water-soluble organic solvent can be used as a solvent. On the other hand, oil-based ink is preferably used based on a solvent having a high boiling point in order to prevent clogging of the head. Known colorants and dyes are widely used as colorants used in such ink jet inks. Further, in order to improve dispersibility and fixability, resins that are soluble or insoluble in a solvent can be contained. Other surfactants such as nonionic surfactants, cationic surfactants and amphoteric surfactants; antiseptics; antifungal agents; pH adjusters; antifoaming agents; UV absorbers; viscosity modifiers: surface tension modifiers, etc. May be added as necessary.

  In addition, ordinary inkjet inks cannot contain a large amount of binder resin due to their low appropriate viscosity, but the colorant itself can be provided with fixing ability by granulating the colorant particles in the ink by wrapping them with resin. Such an ink can also be used in the present invention. Furthermore, so-called hot melt inks and UV curable inks can also be used.

  In the present invention, it is particularly preferable to use a curable ink, and in particular, a UV curable ink containing at least an ultraviolet curable resin and a dye or pigment, or a thermosetting resin containing a thermosetting resin and a dye or pigment. It is preferable to use ink.

  By using a UV curable ink, the ink can be colored by an ink jet method to form a colored layer, and then irradiated with UV to quickly cure the ink and immediately send it to the next step. Therefore, a color filter can be manufactured efficiently.

Such a UV curable ink is mainly composed of a prepolymer, a monomer, a photoinitiator and a colorant. As the prepolymer, any of prepolymers such as polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, polyol acrylate, and silicon acrylate can be used without any particular limitation.
Monomers include vinyl monomers such as styrene and vinyl acetate; monofunctional acrylic monomers such as n-hexyl acrylate and phenoxyethyl acrylate; diethylene glycol diacrylate, 1,6-hexanediol diacrylate, hydroxypiperic acid ester neopentyl glycol diacrylate Polyfunctional acrylic monomers such as trimethylolpropane triacrylate and dipentaerystol hexaacrylate can be used. The prepolymer and the monomer may be used alone or in combination of two or more.

  Photopolymerization initiators are isobutyl benzoin ether, isopropyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, 1-phenyl-1,2-propadion-2-oxime, 2,2-dimethoxy-2-phenylacetophenone, benzyl, hydroxy Cyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzophenone, chlorothioxanthone, 2-chlorothioxanthone, isopropylthioxanthone, 2-methylthioxanthone, chlorine-substituted benzophenone, halogen-substituted alkyl -From the allyl ketone etc., what can obtain a desired hardening characteristic can be selected and used. In addition, photoinitiators such as aliphatic amines and aromatic amines; and photosensitizers such as thioxanthone may be added as necessary.

  The thermosetting ink is characterized by containing at least a binder and a bifunctional or trifunctional epoxy group-containing monomer. The thermosetting ink used in the present invention may contain a colorant, a dispersant, a curing accelerator, or other additives as necessary. Here, in order to give the said thermosetting ink composition appropriate fluidity | liquidity for applying to an inkjet system, and discharge property, you may melt | dissolve or disperse | distribute each said component in a solvent (diluent). . The thermosetting ink used in the present invention is a combination of the above thermosetting ink composition and a bifunctional or trifunctional epoxy group-containing monomer and a tetrafunctional or higher functional epoxy group-containing resin. May be.

  As the binder, either a resin having no polymerization reactivity per se or a resin having a polymerization reactivity per se may be used, or two or more binders may be used in combination.

  For example, when a resin having no polymerization reactivity is used as a binder, a bifunctional or trifunctional epoxy group-containing monomer in the thermosetting ink composition, other thermosetting components, and the like are polymerized and cured by heating. . Examples of such non-polymerizable binders include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and poly Copolymers composed of two or more methyl methacrylate macromonomers can be used.

  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, 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 / polymethyl methacrylate macromono -Copolymer, Acrylic acid / Benzyl methacrylate copolymer, Acrylic acid / Methyl methacrylate / Styrene copolymer, Acrylic acid / Benzyl methacrylate / Styrene copolymer, Acrylic acid / Methyl methacrylate / Polystyrene macromonomer copolymer, Acrylic Acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / Benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethylmeta It can be used acrylic acid copolymers such as Li rate macromonomer copolymer.

  Furthermore, 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, methacrylic acid / 2-hydroxyethyl acrylate / benzyl Acrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl acrylate / benzyl acrylate / polymethyl methacrylate Tomacromonomer 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 / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxy Ethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzine Methacrylate / polymethyl methacrylate macromonomer copolymers methacrylic acid copolymers such as and the like.

  Among the above non-polymerizable binders, in particular, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, benzyl methacrylate / styrene copolymer, benzyl methacrylate macromonomer / styrene copolymer, benzyl A methacrylate / styrene macromonomer copolymer is preferred.

  On the other hand, as the binder having polymerizability by itself, it is possible to use an oligomer obtained by introducing a thermally polymerizable functional group such as an epoxy group into a non-polymerizable binder molecule or a polymer having a higher molecular weight than an oligomer. it can. The molecules of the polymerizable binder are polymerized between the binders, and also polymerized with a bifunctional or trifunctional polyfunctional monomer and other polymerizable monomers to be thermally cured.

  Examples of the heat-polymerizable binder include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and 3,4-acrylic acid. Epoxybutyl, methacrylic acid-3,4-epoxybutyl, methacrylic acid-4,5-epoxypentyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6 , 7-epoxyheptyl (meth) acrylates; o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether, p-vinylphenyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p- Vinyl benzylglyce Vinyl glycidyl ethers such as dil ether; 2,3-diglycidyloxystyrene, 3,4-diglycidyloxystyrene, 2,4-diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-di Glycidyloxystyrene, 5-vinyl pyrogallol triglycidyl ether, 4-vinyl pyrogallol triglycidyl ether, vinyl phloroglicinol triglycidyl ether, 2,3-dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4-dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6-dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydride Homopolymers obtained by polymerizing one or more monomers containing an ethylenically unsaturated bond and an epoxy group, such as loxymethylstyrene triglycidyl ether and 1,3,5-trihydroxymethylstyrene triglycidyl ether Alternatively, a copolymer can be used.

  Further, a copolymer obtained by polymerizing one or more monomers containing an ethylenically unsaturated bond and an epoxy group as described above and a monomer not containing an epoxy group as described below is also thermally polymerizable. It can be used as a binder. Examples of monomers that do not contain an epoxy group include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer, and polymethyl methacrylate. Macromonomer etc. are mentioned.

  Moreover, a binder is normally mix | blended in the ratio of 1 to 50 weight% with respect to the solid content whole quantity of a thermosetting ink composition. Here, the solid content of the thermosetting ink composition for specifying the blending ratio includes all components except the solvent, and the liquid polymerizable monomer is also included in the solid content.

3. Next, the light shielding part used in the present invention will be described. The light-shielding part used in the present invention is formed on a base material to be described later, and is not particularly limited as long as it shields the irradiated energy when a color filter is formed. Such a method for forming the light shielding portion is appropriately selected and used depending on the shielding property against the required energy.

  For example, it may be formed by forming a metal thin film of chromium or the like having a thickness of about 1000 to 2000 mm by a sputtering method, a vacuum deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.

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

  Furthermore, in the present invention, the light shielding portion may be formed by a thermal transfer method. The thermal transfer method for forming a light-shielding part is usually a thermal transfer sheet having a light-to-heat conversion layer and a light-shielding part transfer layer provided on one side of a transparent film base material, and energy is applied to the area where the light-shielding part is formed. By irradiating, the light shielding part transfer layer is transferred onto the substrate to form the light shielding part. The thickness of the light-shielding portion formed by such a thermal transfer method can usually be about 0.5 μm to 10.0 μm, particularly about 0.8 μm to 5.0 μm.

  The light shielding part transferred by the thermal transfer method is usually composed of a light shielding material and a binder, and inorganic particles such as carbon black and titanium black can be used as the light shielding material. The particle diameter of such a light-shielding material is preferably 0.01 μm to 1.0 μm, and more preferably 0.03 μm to 0.3 μm.

  Further, the binder is preferably a resin composition having thermoplasticity and thermosetting properties, has a thermosetting functional group, and has a softening point in the range of 50 ° C to 150 ° C, particularly 60 ° C. It is preferable to be comprised by the resin material which exists in the range of -120 degreeC, a hardening | curing agent, etc. Specific examples of such a material include a combination of an epoxy compound or epoxy resin having two or more epoxy groups in one molecule and a latent curing agent thereof. As a latent curing agent for epoxy resins, it does not have reactivity with epoxy groups up to a certain temperature, but when it reaches the activation temperature by heating, it changes to a molecular structure with reactivity with epoxy groups. A curing agent can be used. Specific examples include neutral salts and complexes of acidic or basic compounds having reactivity with epoxy resins, block compounds, high melting point bodies, and microcapsules. In addition to the above materials, the light-shielding part may contain a release agent, an adhesion assistant, an antioxidant, a dispersant, and the like.

  In the present invention, a primer layer may be formed between the photocatalyst containing layer and the light shielding part. Although the action and function of this primer layer are not necessarily clear, by forming the primer layer, it becomes a factor that inhibits the above-mentioned wettability change of the photocatalyst-containing layer from the light-shielding part and the opening existing between the light-shielding parts. This is considered to exhibit a function of preventing diffusion of impurities, particularly residues generated when the light shielding portion is patterned, and impurities. Therefore, by forming the primer layer, the contact angle with the liquid of the photocatalyst containing layer can be improved with high sensitivity, and as a result, a high resolution pattern can be obtained.

  In the present invention, the primer layer prevents the impurities present in the openings formed between the light shielding portions as well as the light shielding portions from affecting the action of the photocatalyst. Therefore, the primer layer includes the openings. It is preferable that it is formed over the entire light shielding portion.

  The primer layer in the present invention is not particularly limited as long as the primer layer is formed so that the light-shielding portion and the photocatalyst-containing layer are not in contact with each other.

The material constituting the primer layer is not particularly limited, but an inorganic material that is not easily decomposed by the action of the photocatalyst is preferable. Specific examples include amorphous silica. When such amorphous silica is used, the precursor of the amorphous silica is represented by the general formula SiX ₄ and X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, Silanol which is a hydrolyzate thereof or polysiloxane having an average molecular weight of 3000 or less is preferable.

  The thickness of the primer layer is preferably in the range of 0.001 μm to 1 μm, particularly preferably in the range of 0.001 μm to 0.1 μm.

4). Next, the substrate used in the present invention will be described. As a base material used for this invention, if the said light-shielding part and a photocatalyst content layer can be formed, it will not specifically limit and what was conventionally used for the color filter etc. can be used. Specifically, transparent flexible materials such as quartz glass, Pyrex (registered trademark) glass, and synthetic quartz plates, or flexible flexible materials such as transparent resin films and optical resin plates, etc. Can be mentioned. Among them, Corning 7059 glass is a material having a small coefficient of thermal expansion, excellent dimensional stability and workability in high-temperature heat treatment, and is an alkali-free glass containing no alkali component in the active matrix. Suitable for color filters for color liquid crystal display devices. 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 preventing alkali elution, imparting a gas barrier property or other purposes as required.

5). Color filter The color filter of the present invention comprises the above-described base material, a light shielding part formed on the base material, a photocatalyst containing layer formed so as to cover the base material and the light shielding part, and the photocatalyst containing layer. If it has the formed colored layer, it will not specifically limit, For example, a protective layer, an ITO layer, etc. may be formed in addition.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

[Example 1]
1. Formation of light shielding layer First, a soda glass substrate having a thickness of 1.1 mm was coated with a light shielding material having the following composition, and then prebaked at 100 ° C. for 15 minutes to dry the light shielding material to form a film. At this time, the light shielding material was applied by spin coating. The spin coating conditions were 1500 rpm / min.
・ Carbon black (black pigment) 28.5%
-Partially cyclized polyisoprene (negative photopolymer) 15.0%
・ Aromatic bisazide (photosensitive agent) 1.5%
・ Other additives 0.3%
・ Polyethylene glycol monomethyl ether acetate (solvent) 54.7%
Next, the light-shielding material thin film formed as described above was irradiated with ultraviolet rays through a photomask, exposed at an exposure amount of 300 mJ / cm ² , and then developed and rinsed. For development, a 0.1% NaCO ₃ aqueous solution was used as a developer. Thereafter, the light shielding layer obtained above was dried and then post-baked at 200 ° C. for 10 minutes to obtain a substrate having a light shielding layer with a film thickness of 1.2 μm, a line width of 30 μm, and an interval of 100 μm.

2. Formation of Photocatalyst Containing Layer 0.5 g of MF-160E (manufactured by Tochem Products Co., Ltd.) and trimethoxymethylsilane (manufactured by Toshiba Silicone Co., Ltd., TSL8113), whose main components are 30 g of isopropyl alcohol and fluoroalkylsilane 5 g and 21 g of ST-K01 (Ishihara Sangyo Co., Ltd.), which is a titanium oxide aqueous dispersion as a photocatalyst, were mixed and stirred at 100 ° C. for 20 minutes. This was diluted 3.5 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.
A transparent photocatalyst-containing layer (thickness: 0.3 μm) is prepared by applying the composition to a transparent substrate made of soda glass on which the light-shielding layer is formed in advance using a spin coater and performing a drying treatment at 150 ° C. for 10 minutes. Formed.
As a result of cutting this substrate and observing a photograph (Hitachi S5000) of the cutting part by a scanning electron microscope, the photocatalyst-containing layer mainly has a maximum diameter of 0.05 to 0.2 μm. Organopolysiloxane and titanium oxide The depth from the line connecting the adjacent convex portions on the surface is 50 to 100 nm, and 30 nm from the line connecting the adjacent convex portions on the surface. It was found that fine pores having a pore diameter of 10 to 30 nm at the position were formed. Here, 25 fine pores having a depth of 30 nm or more from a line connecting adjacent convex portions on the surface were formed in a range of 1 μm in length on the surface of the photocatalyst containing layer. Further, 50% of fine pores having a depth of 30 nm or more from a line connecting adjacent convex portions on the surface had a pore diameter within the above range.

3. Confirmation of formation of ink-philic region by exposure This photocatalyst-containing layer is exposed to light through a mask with a mercury lamp (wavelength 365 nm) at an illuminance of 70 mW / cm ² for 50 seconds to form an exposed portion, and an unexposed portion and an exposed portion The contact angle with the liquid was measured. In the non-exposed area, a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) is used for the contact angle with a liquid having a surface tension of 30 mN / m (manufactured by Junsei Chemical Co., Ltd., ethylene glycol monoethyl ether). As a result of measurement (30 seconds after dropping a droplet from the microsyringe), it was 30 degrees. In the exposed area, the contact angle with a liquid having a surface tension of 50 mN / m (manufactured by Junsei Co., Ltd., wetting index standard solution No. 50) was measured in the same manner, and as a result, it was 7 degrees. As described above, it was confirmed that the exposed portion becomes an ink-philic region as compared with the non-exposed portion, and it is possible to form a pattern due to the difference in wettability between the exposed portion and the non-exposed portion.

4). Next, using a photomask on the photocatalyst-containing layer, exposure (same exposure conditions as 3) with a line width of 110 μm and an interval of 20 μm (of which the side width of 5 μm is formed on the light-shielding layer) ) To make the exposed portion for the pixel portion ink-philic. Next, thermal curing of each color of RGB including 5 parts by weight of a pigment, 20 parts by weight of a solvent, 70 parts by weight of an acrylic acid / benzyl acrylate copolymer, and 5 parts by weight of a bifunctional epoxy-containing monomer is performed using each RGB inkjet device. The type polyepoxyacrylate ink was attached to the exposed portion of the pixel portion which was made ink-philic and colored, and was cured by heat treatment at 150 ° C. for 30 minutes. Here, for each of the red, green, and blue inks, the solvent is polyethylene glycol monomethyl ethyl acetate, the pigment is CI Pigment Red 177 for red ink, CI Pigment Green 36 for green ink, and CI Pigment Green 36 for blue ink Pigment Blue 15+ CI Pigment Violet 23 was used.
As a result, an RGB stripe color filter having a line width of 100 μm and a light shielding portion of 30 μm was obtained.
In order to evaluate the adhesion of the colored portion of the color filter, a peel test was conducted with a tape peel strength tester (TPM-200: manufactured by CNC) under the conditions of a tape width of 20 mm, a peel speed of 300 mm / min, and a peel strength of 200 g. As a result, no peeling was observed and good adhesion with the photocatalyst containing layer was shown.

[Example 2]
A photocatalyst containing layer was formed under the same conditions as in Example 1 except that the dilution ratio of isopropyl alcohol in forming the photocatalyst containing layer composition was tripled. As a result of cutting this substrate and observing a photograph (Hitachi S5000) of the cut portion by a scanning electron microscope, the photocatalyst-containing layer mainly has an organopolysiloxane and titanium oxide having a maximum diameter of 0.05 to 0.3 μm. From a line connecting adjacent convex portions on the surface and having a depth of 50 to 150 nm from a line connecting adjacent convex portions on the surface. It was found that fine pores having a pore diameter of 15 to 30 nm at a position of 30 nm were formed. Here, 20 fine pores having a depth of 30 nm or more from a line connecting adjacent convex portions on the surface were formed in a range of 1 μm in length on the surface of the photocatalyst containing layer. In addition, 60% of fine pores having a depth of 30 nm or more from a line connecting adjacent convex portions on the surface had a pore diameter within the above range.
Moreover, as a result of forming a colored layer on the photocatalyst-containing layer in the same manner as in Example 1 and performing a peel test on the colored layer, no peel was observed, and good adhesion of the colored layer was obtained. The photosensitivity of the layer was also equivalent to Example 1.

[Comparative Example 1]
A photocatalyst containing layer was formed under the same conditions as in Example 1 except that the dilution ratio of isopropyl alcohol in forming the photocatalyst containing layer composition was 1.5 times.
As a result of cutting this substrate and observing a photograph (Hitachi S5000) of the cut portion with a scanning electron microscope, the photocatalyst-containing layer has a thickness of 0.5 μm, whereas it is mainly 0.4 to 0.9 μm. Although it is composed of a fine-grained organic-inorganic mixture composed of a mixture of an organopolysiloxane and titanium oxide having a maximum diameter of 5 mm, fine pores are formed but the boundary portion is unclear.
Further, the contact angle with a liquid having a surface tension of 50 mN / m (made by Pure Chemical Co., Ltd., Wetting Index Standard Solution No. 50) was measured in the same manner, and as a result, it was 15 degrees.
After forming a colored layer on the photocatalyst-containing layer in the same manner as in Example 1, as a result of performing a peel test on the colored layer in the same manner, the colored layer was partially peeled from the photocatalyst-containing layer, and a good colored layer was obtained. Adhesion was not obtained.

[Comparative Example 2]
After forming the photocatalyst-containing layer in the same manner as in Example 1, rolling was performed 10 times with a rubber roller at a pressure of 100 kg / cm ³ . Similarly, as a result of observing a photograph (Hitachi S5000) of the cutting part with a scanning electron microscope, the photocatalyst-containing layer did not change with a film thickness of 3 μm, but the particulate organic-inorganic mixture was compressed and its boundary Became unclear.
The photocatalyst-containing layer was irradiated with energy in the same manner as in Example 1, and the contact angle with a liquid having a surface tension of 50 mN / m (made by Junsei Chemical Co., Ltd., wetting index standard solution No. 50) was similarly set. As a result of measurement, it was 20 degrees. In addition, after forming a colored layer on the photocatalyst-containing layer in the same manner as in Example 1, a colored layer peeling test was performed in the same manner as in Example 1. As a result, the colored layer was partially detached from the photocatalyst-containing layer. Good adhesion of the colored layer was not obtained.

It is a schematic sectional drawing which shows an example of the color filter of this invention. It is explanatory drawing which showed the photocatalyst content layer used for this invention. It is explanatory drawing which showed the process of reducing the contact angle with the liquid of the photocatalyst content layer used for this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Base material 2 ... Light-shielding part 3 ... Photocatalyst containing layer 4 ... Colored layer

Claims (6)

A base material, a light-shielding part formed on the base material, a photocatalyst-containing layer containing a photocatalyst and an organopolysiloxane formed so as to cover the base material and the light-shielding part, and formed on the photocatalyst-containing layer A color filter having a colored layer,
The color filter, wherein the photocatalyst-containing layer has fine pores and a particulate organic-inorganic composite material.   2. The color filter according to claim 1, wherein the particulate organic-inorganic composite material includes one having a maximum major axis in the range of 0.03 μm to 0.3 μm.   3. The color according to claim 1, wherein the photocatalyst-containing layer has surface fine pores having a depth of 30 nm or more from a line connecting adjacent convex portions on the surface of the photocatalyst-containing layer. filter.   The photocatalyst-containing layer has the surface fine pores having a pore diameter in a range of 10 nm to 30 nm at a depth of 30 nm from a line connecting adjacent convex portions on the surface of the photocatalyst containing layer. The color filter according to 3.   The color filter according to claim 1, wherein the colored layer includes at least a thermosetting resin and a dye or a pigment. The color filter according to claim 1, wherein the colored layer includes at least an ultraviolet curable resin and a dye or a pigment.

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