JP4629370B2 - Color filter and manufacturing method thereof - Google Patents

Description

  The present invention relates to a color filter suitable for a color liquid crystal display (LCD) obtained by coloring a pixel portion by an ink jet method and a method for manufacturing the color filter.

In LCDs, color filters are widely used for color display. For example, in an active matrix type LCD using a thin film transistor (TFT), a film having excellent light-shielding properties called a black matrix (BM) is patterned, and the three primary colors red (R) and green (G) are formed thereon. , Blue (B) coloring pattern, the liquid crystal operates as a shutter by turning on or off the electrode corresponding to each pixel of R, G, B, and light passes through each pixel of R, G, B Color display is performed. An arbitrary color is visually displayed on the retina according to an additive color mixing principle in which liquid crystal shutters corresponding to pixels of two or more colors are opened and mixed. Conventional color filters are manufactured by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. In the case of a TFT-LCD, the pigment dispersion method is the mainstream.
In the pigment dispersion method, a photosensitive resin layer in which a pigment is dispersed is first formed on a substrate, and a monochromatic pattern is obtained by patterning the photosensitive resin layer. 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, in order to color three colors of R, G, and B, it is necessary to repeat the same process three times, and there is a problem that the cost is high, and the yield decreases because the process is repeated. There's a problem.

Further, as a new color filter manufacturing method, the present applicant has developed a color filter manufacturing method for forming a pattern using a substance whose wettability is changed by the action of a photocatalyst (for example, Patent Document 1, Patent Document). 2). FIG. 7 is a schematic cross-sectional view showing an example of a conventional color filter formed using the action of a photocatalyst. A black matrix 80 is formed on a transparent substrate 71, and the wettability changing component layer covers the black matrix 80. 73, a predetermined colored layer 83 is formed on a specific wettability region 78 formed by pattern exposure with ultraviolet rays on the wettability changing component layer 73, There is a wettability region 78 of the wettability changing component layer below the colored layer 83, and the colored layer 83 is not directly formed on the transparent substrate 71.
JP 2000-227513 A JP 2004-20745 A

However, with respect to color filters, the conventional pigment dispersion method requires coating, exposure, and development steps such as spin coating, and a cleaning step for each black matrix and three-color coloring pattern formation, and at least four exposure steps. Therefore, it is difficult to improve the material use efficiency and simplify the process, which hinders the reduction of the manufacturing cost.
In addition, the conventional method for producing a pattern forming body by the action of a photocatalyst requires at least two exposure steps for the formation of a black matrix and the formation of a colored layer. Simplification is required. Furthermore, since the wettability region of the wettability changing component layer exists below the colored layer, there is a problem that the transmittance of the colored layer is slightly reduced.
An object of the present invention is to provide a high-quality color filter that shortens the manufacturing process, reduces the manufacturing cost, is easy to manufacture, enables high-definition patterning, and has excellent spectral characteristics of the colored layer, and a manufacturing method thereof. Is to provide.

The color filter of the present invention according to claim 1 has at least a transparent substrate, a colored layer in which a plurality of colors are provided in a predetermined pattern on the transparent substrate, and a black matrix located at a boundary portion of the colored layer. A transparent substrate between the black matrix and the wettability changing component layer, wherein the wettability changing component layer that is liquid repellent is laminated on the black matrix with a width substantially equal to the black matrix. A colored layer composed of a plurality of colors is formed thereon.
The color filter of the present invention according to claim 2 is characterized in that the black matrix has a light shielding film made of a metal film formed on the transparent substrate, and the wettability changing component layer provided on the light shielding film is specified. by wet etching through the hydrophilic areas, certain of the hydrophilic region of the wettability changing component layer is characterized in that the one formed by Rukoto is lifted off removed.
The color filter of the present invention described in claim 3 is characterized in that the wettability changing component layer is a layer composed of at least a binder.
The color filter of the present invention according to claim 4 is characterized in that the wettability changing component layer is a photocatalyst-containing layer comprising at least a binder and a photocatalyst.
The color filter of the present invention according to claim 5 is characterized in that the binder is a layer containing an organopolysiloxane.
The color filter of the present invention according to claim 6 is characterized in that the organopolysiloxane is a polysiloxane containing a fluoroalkyl group.
The color filter of the present invention according to claim 7 is characterized in that the organopolysiloxane is YnSiX _(4-n) (where Y is an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group. X represents an alkoxyl group or halogen, and n is an integer from 0 to 3.) One or more hydrolyzed condensates or cohydrolyzed condensates of a silicon compound represented by It is characterized by being siloxane.
In the color filter of the present invention according to claim 8, the photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ). ), Bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ), one or more substances.
The color filter of the present invention according to claim 9 is characterized in that the photocatalyst is titanium oxide (TiO ₂ ).
The color filter of the present invention according to claim 10 is characterized in that the wettability changing component layer has a thickness in the range of 0.001 μm to 1 μm.

The method for producing a color filter of the present invention according to claim 11 includes (1) a step of forming a light-shielding film made of a metal film on a transparent substrate, and (2) wettability by the action of a photocatalyst on the light-shielding film. A step of forming a wettability changing component layer containing at least a binder that changes, and (3) the photocatalyst layer side of the photocatalyst layer substrate on which the photocatalyst layer containing a photocatalyst is formed and the wettability changing component layer, After being arranged with a gap of 200 μm or less, the photocatalyst layer was exposed to ultraviolet light from the substrate side, and the wettability changing component layer exposed to the liquid had a reduced contact angle with the liquid compared to before exposure to ultraviolet light. And (4) wet-etching the light-shielding film through the hydrophilic region of the wettability changing component layer to form a black matrix, and forming the wet matrix. A step of lifting off the wettability changing component layer on the coated light shielding film to expose the transparent substrate, and forming a colored layer forming portion in a pattern on the transparent substrate; and (5) inkjet printing on the colored layer forming portion. And a step of forming a colored layer by coloring with a method.
The method for producing a color filter of the present invention according to claim 12 includes (1) a step of forming a light shielding film made of a metal film on a transparent substrate, and (2) wettability by the action of a photocatalyst on the light shielding film. A step of forming a wettability changing component layer comprising at least a binder and a photocatalyst that changes, and (3) pattern exposure of the wettability changing component layer with a photomask having a light shielding layer pattern, and exposure of the wettability changing component layer Forming a hydrophilic region in which the contact angle with the liquid is reduced compared to before exposure to ultraviolet light, and (4) wet etching the light-shielding film through the hydrophilic region of the wettability changing component layer In addition to forming a black matrix, the wettability changing component layer on the light-shielded light-shielding film is lifted off to expose the transparent substrate, and a colored layer forming portion is formed on the transparent substrate. Forming the over down form and is characterized in that it comprises the steps of coloring with an ink jet system, to form a colored layer (5) the colored layer forming portion.

  In the present invention, without using a photosensitive resist necessary for forming a black matrix of a color filter, by using the wettability changing component layer instead of the photosensitive resist, the resist coating, developing, and stripping steps are eliminated. By eliminating the exposure, development, and washing steps of the coloring process, the color filter manufacturing process is greatly shortened, the manufacturing cost is low, the manufacturing is easy, and a high-definition pattern can be formed. A color filter having excellent spectral characteristics and a method for producing the same can be achieved.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the first embodiment of the color filter of the present invention, and FIGS. 3 and 4 are schematic cross-sectional views showing the manufacturing process thereof. FIG. 2 is a schematic cross-sectional view showing an example of a second embodiment of the color filter of the present invention, and FIGS. 5 and 6 are schematic cross-sectional views showing the manufacturing process thereof.

<Color filter>
FIG. 1 is a schematic cross-sectional view showing an example of a first embodiment of a color filter of the present invention. A transparent substrate 11 and a colored layer 23 in which a plurality of colors are provided in a predetermined pattern on the transparent substrate 11 by an inkjet method. And a black matrix 20 positioned at the boundary of the colored layer 23, and the wettability changing component layer 13 is laminated on the black matrix 20 with a width substantially equal to that of the black matrix. The wettability changing component layer 13 is a layer composed of at least a binder.
FIG. 2 is a schematic cross-sectional view showing an example of the second embodiment of the color filter of the present invention. The transparent substrate 31 and a colored layer 43 in which a plurality of colors are provided in a predetermined pattern on the transparent substrate 31 by an inkjet method. And a black matrix 40 located at the boundary of the colored layer 43, and the wettability changing component layer 33 is laminated on the black matrix 40 with a width substantially equal to that of the black matrix. The wettability changing component layer 33 is a layer composed of at least a binder and a photocatalyst.
In the present invention, there are a case where the layer containing the photocatalyst is not on the color filter substrate side (first embodiment) and a case where the layer containing the photocatalyst is on the color filter substrate side (second embodiment). First, items common to the first embodiment and the second embodiment will be described.

(Transparent substrate)
The transparent substrates 11 and 31 are not particularly limited as long as they are conventionally used for color filters. For example, transparent flexible materials such as quartz glass, Pyrex glass (registered trademark), synthetic quartz plates and the like, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates are used. Can do. 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 substrate can also be used. Further, the transparent substrate may be subjected to surface treatment for preventing alkali elution, imparting a gas barrier property or other purposes as required.

(Black matrix)
In the color filter of the present invention, black matrices 20 and 40 are formed on transparent substrates 11 and 31. The black matrices 20 and 40 are not particularly limited as long as they are metal thin films conventionally used for color filters. For example, a metal thin film such as chromium, chromium / chromium oxide (transparent substrate side) two-layer film, or chromium oxide / chromium / chromium oxide three-layer film can be used. These metal thin films are usually formed to a thickness of about 100 to 200 nm by a sputtering method, a vacuum deposition method or the like.
In the present invention, the black matrices 20 and 40 are formed by passing a light shielding film made of a metal film formed on the transparent substrates 11 and 31 through a specific hydrophilic region of the wettability changing component layer provided on the light shielding film. It is formed by etching.

(Wetting change component layer)
In the present invention, the wettability changing component layers 13 and 33 provided on the black matrices 20 and 40 are layers whose wettability changes due to the action of the photocatalyst, have a large contact angle with the liquid before the ultraviolet exposure, and the ultraviolet rays. It is a wettability changing layer in which the contact angle with the liquid changes small after exposure.
As will be described later in the method for producing a color filter of the present invention, the wettability changing component layers 13 and 33 have a contact angle with a liquid such as water on the surface of the wettability changing component layer due to the action of a photocatalyst accompanying ultraviolet exposure. This is because the wettability is changed so as to decrease, and the light-shielding film can be etched into a pattern in the present invention using this hydrophilic region exposed to ultraviolet rays. Here, the hydrophilic region is a region having a small contact angle with a liquid containing water, and the water repellent region is a region having a large contact angle with a liquid containing water.
In the present invention, the wettability changing component layers 13 and 33 on the black matrices 20 and 40 remain as unexposed portions and exhibit water repellency.

  The wettability changing component layers 13 and 33 have a contact angle with a liquid having a surface tension of 40 mN / m of 10 ° or more, preferably a surface tension of 30 mN / m, in a portion not exposed to ultraviolet light, that is, in a liquid repellent region. It is preferable that the contact angle with the liquid is 10 ° or more, particularly the wettability with the contact angle with the liquid having a surface tension of 20 mN / m is 10 ° or more. This is because the part that is not exposed to ultraviolet light is a part that requires liquid repellency in the present invention, and therefore, when the contact angle with the liquid is smaller than the above range, the liquid repellency is not sufficient, This is because it is difficult to form a fine pattern, which is not preferable.

  Further, the wettability changing component layers 13 and 33 have a contact angle with a liquid that is reduced by an action of a photocatalyst when exposed to ultraviolet rays, and a contact angle with a liquid having a surface tension of 40 mN / m is 9 ° or less, preferably the surface. A layer that is a hydrophilic region such that the contact angle with a liquid having a tension of 50 mN / m is 10 ° or less, and particularly the contact angle with a liquid having a surface tension of 60 mN / m is preferably 10 ° or less. When the contact angle with the liquid in the part exposed to ultraviolet light, that is, the hydrophilic region is higher than the above range, the etching solution penetrates through the specific hydrophilic region of the wettability changing component layer provided on the light shielding film, This is because it takes time to etch the light shielding film in the lower layer or uneven etching occurs, making uniform etching difficult.

  In addition, the contact angle with the liquid containing water said here measures the contact angle with the liquid which has various surface tensions using a contact angle measuring device (Kyowa Interface Science Co., Ltd. product CA-Z type). 30 seconds after dropping a droplet from the syringe), and the result was obtained or a graph was obtained. Further, in this measurement, the liquid having various surface tensions is a value using a pure chemical standard wetting index solution.

  Further, when the wettability changing component layers 13 and 33 as described above in the present invention are used, fluorine is contained in the wettability changing component layer, and the fluorine content on the surface of the wettability changing component layer is set to be wet. The wettability changing component layer may be formed such that when the property changing component layer is exposed to ultraviolet light, the photocatalyst acts to lower the property changing component layer as compared to before the ultraviolet exposure.

  With the wettability changing component layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by exposure to ultraviolet rays. 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 hydrophilic region compared to the portion with a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than the surrounding surface forms a hydrophilic region pattern in the water repellent region.

Therefore, when such a wettability changing component layer is used, a hydrophilic region pattern can be easily formed in the water repellent region by exposing the wettability changing component layer to ultraviolet rays. An etching solution is infiltrated into the wettability changing component layer through the property region, and the lower light shielding film is etched into a pattern to form a black matrix. As the light shielding film is etched, the hydrophilic wettability change component layer on the etched light shielding film is removed by lift-off because the underlying light shielding film is corroded and dissolved by the etching solution. The film is etched into a pattern to expose the surface of the transparent substrate. The exposed surface of the transparent substrate becomes a colored layer forming part.
As described above, in the present invention, pattern exposure by the photolithography method or the like of the light shielding film itself is unnecessary, and the light shielding film is formed after etching the light shielding film through the wettability changing component layer that has been rendered hydrophilic by pattern exposure. Further, there is an advantage that the water repellent wettability changing component layer of the unexposed portion is laminated on the black matrix with a width substantially equal to that of the black matrix, the overlay accuracy is substantially equal, and the black matrix can be patterned by so-called self-alignment.

As described above, the fluorine content contained in the wettability changing component layer containing fluorine is not exposed to ultraviolet light in the hydrophilic region having a low fluorine content formed by ultraviolet exposure. When the fluorine content of the part is 100, it is preferably 10 or less, preferably 5 or less, particularly preferably 1 or less. This rate of decrease is based on weight.
By setting it within such a range, it is possible to make a great difference in wettability between the ultraviolet exposed portion and the unexposed portion.

  The measurement of the fluorine content in the wettability changing component layer can be performed by various commonly used methods. For example, X-ray photoelectron spectroscopy (ESCA) (X-ray Photoelectron Spectroscopy, ESCA ( Electron Spectroscopy 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.

  As the material used for such wettability changing component layers 13 and 33, the wettability of the above-described wettability changing component layer, that is, a material whose wettability is changed by the action of the photocatalyst by ultraviolet exposure, and by the action of the photocatalyst. The main chain is not particularly limited as long as it has a main chain that is difficult to be degraded and decomposed. For example, (1) chloro- or alkoxysilane is hydrolyzed and polycondensed by sol-gel reaction or the like to exhibit high strength. Examples include organopolysiloxanes, and (2) organopolysiloxanes crosslinked with reactive silicones having excellent water and oil repellency.

In the case of (1) above, the general formula:
YnSiX (4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxy group, an acetyl group or a 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 number of carbon atoms of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.

  In particular, an organopolysiloxane containing a fluoroalkyl group can be preferably used, and specific examples thereof include one or two or more hydrolytic condensates and cohydrolytic condensates of the following fluoroalkylsilanes. In general, those 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 SiCH ₃ (OCH ₃ ) ₂ ;
_{(CF 3) 2 CF (CF} 2) 8 CH 2 CH 2 SiCH 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

  By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the water repellency of the non-exposed part of the wettability changing component layer is greatly improved, and for example, the function of preventing the adhesion of the ink for the colored layer is exhibited. To do.

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

However, n is an integer greater than or equal to 2, R1, R2 is a C1-C10 substituted or unsubstituted alkyl, alkenyl, aryl, or cyanoalkyl group, respectively, 40% or less of the whole is vinyl, Phenyl and halogenated phenyl. R1 and R2 having a methyl group are preferable because the surface energy becomes the smallest, and the methyl group is 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.
Moreover, you may mix the stable organosilicone compound which does not carry out a crosslinking reaction like dimethylpolysiloxane with said organopolysiloxane.

  In the present invention, various materials such as organopolysiloxane can be used in the wettability changing component layer as described above. However, as described above, it is possible to include fluorine in the wettability changing component layer. It is effective for pattern formation. Therefore, it can be said that it is preferable that fluorine be contained in a material that is not easily deteriorated or decomposed by the action of the photocatalyst, specifically, that the organopolysiloxane material contains fluorine to form a wettability changing component layer.

  As described above, as a method for containing fluorine in the organopolysiloxane material, a method in which a fluorine compound is bonded with a relatively weak bond energy to a main agent that usually has a high bond energy, or a fluorine bonded with a relatively weak bond energy. Examples thereof include a method of mixing a compound into the wettability changing component layer. By introducing fluorine by such a method, when exposed to ultraviolet light, the fluorine binding site having a relatively low binding energy is first decomposed, so that fluorine can be removed from the wettability changing component layer. It is.

  Examples of the first method, that is, a method of bonding a fluorine compound to a binder having a high binding energy with a relatively weak binding energy include a method of introducing a fluoroalkyl group as a substituent into the organopolysiloxane. be able to.

For example, as described in (1) above, as a method for obtaining an organopolysiloxane, an organopolysiloxane exhibiting high strength can be obtained by hydrolyzing and polycondensing chloro or alkoxysilane or the like by a sol-gel reaction or the like. . Here, in this method, as described above, the above general formula:
YnSiX (4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group, an acetyl group or a halogen. N is an integer from 0 to 3. )
An organopolysiloxane is obtained by hydrolyzing or co-hydrolyzing and condensing one or two or more of the silicon compounds represented by formula (1). In this general formula, silicon having a fluoroalkyl group as the substituent Y is obtained. By synthesizing using a compound, an organopolysiloxane having a fluoroalkyl group as a substituent can be obtained. When an organopolysiloxane having such a fluoroalkyl group as a substituent is used as a binder, the carbon bond portion of the fluoroalkyl group is decomposed by the action of the photocatalyst in the photocatalyst-containing layer that comes into contact when exposed to ultraviolet light. Therefore, the fluorine content in the portion where the wettability changing component layer surface is irradiated with energy can be reduced.

  The silicon compound having a fluoroalkyl group used at this time is not particularly limited as long as it has a fluoroalkyl group, but has at least one fluoroalkyl group, and the carbon number of the fluoroalkyl group A silicon compound in which is 4 to 30, preferably 6 to 20, particularly preferably 6 to 16, is preferably used. Specific examples of such a silicon compound are as described above, and among these, the above silicon compound having a fluoroalkyl group having 6 to 8 carbon atoms, that is, a fluoroalkylsilane is preferable.

  In the present invention, such a silicon compound having a fluoroalkyl group may be used in combination with the above-mentioned silicon compound having no fluoroalkyl group, and these cohydrolyzed condensates may be used as the organopolysiloxane. In addition, one or two or more silicon compounds having such a fluoroalkyl group may be used, and these hydrolyzed condensates and cohydrolyzed condensates may be used as the organopolysiloxane.

  In the organopolysiloxane having a fluoroalkyl group thus obtained, among the silicon compounds constituting the organopolysiloxane, the silicon compound having the fluoroalkyl group is 0.01 mol% or more, preferably 0.1%. It is preferable that it is contained in mol% or more.

  Since the fluoroalkyl group is contained to such a degree, the water repellency on the wettability changing component layer can be increased, and the difference in wettability with the portion exposed to ultraviolet rays to form a hydrophilic region can be increased. It is.

  In the method shown in (2) above, an organopolysiloxane is obtained by crosslinking a reactive silicone having excellent water repellency. In this case as well, R1 and R2 in the above general formula are similarly used. By making either or both of them a fluorine-containing substituent such as a fluoroalkyl group, it is possible to include fluorine in the wettability changing component layer. Since the portion of the fluoroalkyl group having a low binding energy is decomposed, the fluorine content on the surface of the wettability changing component layer can be reduced by ultraviolet exposure.

  On the other hand, as a method for introducing a fluorine compound bonded with energy lower than the binding energy of the binder, for example, when introducing a low molecular weight fluorine compound, for example, a fluorine-based surfactant is mixed. Examples of the method of introducing a high molecular weight fluorine compound include a method of mixing a fluorine resin having high compatibility with the binder resin.

  The wettability changing component layer in the present invention may further contain a surfactant. 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 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  In addition to the above surfactants, the wettability changing component layer also includes 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, polyisoprene and other oligomers and polymers Etc. can be contained.

  Such a wettability changing component layer can be formed by dispersing the above-described components in a solvent together with other additives as necessary to prepare a coating solution, and coating the coating solution on a substrate. it can. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating or bead coating. In the case where an ultraviolet curable component is contained, the wettability changing component layer can be formed by irradiating ultraviolet rays to perform a curing treatment.

  In the present invention, the thickness of the wettability changing component layers 13 and 33 is preferably in the range of 0.001 μm to 1 μm from the relationship of the wettability change rate by the photocatalyst. Furthermore, although the etching conditions are slightly different depending on the characteristics of the light shielding film and the etching solution, the thickness of the wettability changing component layer is set to facilitate the penetration of the etching solution into the light shielding film below the hydrophilic region exposed to ultraviolet rays. A thickness of 0.2 μm or less is more preferable. On the other hand, a thickness of 0.01 μm or more is more preferable in order to easily prevent penetration of the etching solution in the water-repellent wettability changing component layer in the unexposed area. A range of 0.2 μm is more preferable.

  By using the wettability changing component layer of the above-described component in the present invention, the photocatalytic action causes the wettability of the UV-exposed portion using the action of oxidation, decomposition, etc. of organic groups and additives that are part of the above-described component. The hydrophilicity can be changed by changing the property, and a great difference can be made in the wettability with the unexposed part of the ultraviolet ray. Therefore, it is possible to form the black matrix by allowing the etching solution to penetrate to the light shielding film through the hydrophilic region.

  The wettability changing component layer used in the present invention is not particularly limited as long as the wettability changing layer is changed by the action of the photocatalyst as described above. preferable. If the photocatalyst is not included in the wettability changing component layer in this way, there is no need to worry about the effect of the photocatalyst over time when used as a color filter, and it can be used without problems for a long time. That's why.

(Colored layer)
Next, the colored layers 23 and 43 in the present invention will be described. As shown in FIGS. 1 and 2, ink was ejected onto the surface of the transparent substrate exposed by etching the light-shielding film using an ink jet apparatus, and colored layers 23 and 43 were formed by coloring in red, green, and blue, respectively. Is.

  In this case, the exposed transparent layer forming portion of the transparent layer formed by etching the light shielding film is a hydrophilic region, while the wettability changing component layers 13 and 33 laminated on the black matrices 20 and 40 are repellent. Because of being aqueous, the ink ejected from the ink jet device spreads uniformly in the portion for forming the colored layer on the transparent substrate. Since the wettability changing component layer that has not been exposed to ultraviolet light has water repellency, the ink is repelled and removed in this region.

  Usually, the colored layer is formed of three colors of red (R), green (G), and blue (B). The coloring pattern and the coloring area in the pixel portion can be arbitrarily set. Ink-jet inks that form such a colored layer are largely classified into water-based and oil-based inks. In the present invention, any ink can be used, but water-based inks are used because of surface tension. A water-based ink is 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 inks that are based on a solvent with a high boiling point are preferably used in order to prevent clogging of the head. Known pigments 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.

  Also, normal ink-jet inks cannot contain a large amount of binder resin due to their low appropriate viscosity, but the colorant itself can have fixing ability by being granulated in the form of being wrapped with resin. it can. Such an ink can also be used in this embodiment. 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 UV curable 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. Further, as described above, since the ink in the colored layer forming portion spreads uniformly, when the ink is solidified in this way, a colored layer free from color loss and color unevenness can be formed.

  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 allyl ketone etc., what can obtain desired hardening wettability and recording wettability 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.

(Protective layer)
Although not shown in FIG. 1 or FIG. 2, a protective layer may be further formed so as to cover the colored portion in the present invention. This protective layer is provided to flatten the color filter and prevent elution of the components contained in the colored portion or in the photocatalyst containing layer on the black matrix layer in the second embodiment into the liquid crystal layer. Is.

  The thickness of the protective layer can be set in consideration of the light transmittance of the material used, the surface state of the color filter, and the like, 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, two-component curable transparent resin, or the like having a light transmittance required as a transparent protective layer.

(Layer containing photocatalyst)
(First embodiment)
In the first embodiment, the photocatalyst is not provided on the color filter substrate side, and is used separately as a photocatalyst layer substrate.
The photocatalyst layer substrate has a substrate such as a transparent glass substrate and a photocatalyst layer containing a photocatalyst formed on the substrate. Such a photocatalyst layer substrate has at least a photocatalyst layer and a substrate, and is usually formed by forming a thin-film photocatalyst layer formed by a predetermined method on the substrate. In addition, as the photocatalyst layer substrate, one having a light-shielding portion formed in a pattern like a photomask can be used.

  The photocatalyst layer used in the present embodiment is not particularly limited as long as the photocatalyst in the photocatalyst layer is configured to change the wettability of the target wettability changing layer, and includes a photocatalyst and a binder. What is comprised may be sufficient and what was formed into a film by the photocatalyst single-piece | unit may be sufficient. The wettability of the surface may be particularly hydrophilic or water repellent.

The photocatalyst layer used in this embodiment may be a photocatalyst layer 15 formed on the entire surface of a photomask 14 as shown in FIG. 3C, for example. In this case, the photocatalyst layer The step of patterning is not required.
For example, it may be formed in a pattern by a photocatalyst containing layer on a transparent glass substrate or the like. When the photocatalyst layer is formed in a pattern, a photomask or the like is used when the photocatalyst layer is placed at a predetermined distance from the wettability changing layer and exposed to ultraviolet light, as will be described later in the ultraviolet exposure process. There is no need to use it, and by irradiating the entire surface, a pattern with changed wettability can be formed on the wettability changing layer. The method for patterning the photocatalyst layer is not particularly limited, but can be performed by, for example, a photolithography method.

  Thus, the action mechanism of the photocatalyst represented by titanium dioxide as described later in the photocatalyst layer is not necessarily clear, but the carrier generated by light irradiation reacts directly with a nearby compound, or It is considered that the active oxygen species generated in the presence of oxygen and water change the chemical structure of organic matter. In this embodiment, it is considered that this carrier acts on the compound in the wettability changing layer disposed in the vicinity of the photocatalyst layer.

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

  In this embodiment, 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 anatase type and rutile type, and both can be used in this embodiment, but anatase type titanium dioxide is preferable. 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 having a particle size of 20 nm or less.

The photocatalyst layer in this embodiment may be formed by the photocatalyst alone as described above, or may be formed by mixing with a binder.
In the case of a photocatalyst layer comprising only a photocatalyst, the efficiency with respect to the change in wettability on the wettability changing layer is improved, which is advantageous in terms of cost such as shortening of the processing time. On the other hand, a photocatalyst layer composed of a photocatalyst and a binder has an advantage that the photocatalyst layer can be easily formed.

  Examples of a method for forming a photocatalyst layer composed only of a photocatalyst include a method using a vacuum film forming method such as a sputtering method, a CVD method, or a vacuum deposition method. By forming the photocatalyst layer by a vacuum film forming method, it is possible to obtain a photocatalyst layer that is a uniform film and contains only the photocatalyst, and this can uniformly change the wettability on the wettability changing layer. Since it is possible and consists only of a photocatalyst, it is possible to efficiently change the wettability on the wettability changing layer as compared with the case of using a binder.

  In addition, as a method for forming a photocatalyst layer composed of only a photocatalyst, for example, when the photocatalyst is titanium dioxide, amorphous titania is formed on a substrate, and then a phase change is made to crystalline titania by firing. As the amorphous titania used here, for example, hydrolysis, dehydration condensation, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, titanium inorganic salts such as titanium tetrachloride and titanium sulfate, An organic titanium compound such as tetramethoxytitanium can be obtained by hydrolysis and dehydration condensation in the presence of an acid. Next, it can be modified to anatase titania by baking at 400 ° C. to 500 ° C. and modified to rutile type titania by baking at 600 ° C. to 700 ° C.

  Moreover, when using a binder, what has the high bond energy that the main frame | skeleton of a binder is not decomposed | disassembled by photoexcitation of said photocatalyst is preferable, for example, organopolysiloxane etc. can be mentioned.

  When organopolysiloxane is used as a binder in this way, the photocatalyst layer is prepared by dispersing the photocatalyst and the binder organopolysiloxane in a solvent together with other additives as necessary, It can be formed by applying this coating solution on a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating 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 layer can be formed by performing a curing treatment by irradiating ultraviolet rays.

Moreover, an amorphous silica precursor can be used as a binder. This amorphous silica precursor is represented by the general formula SiX ₄ , wherein X is a silicon compound such as halogen, methoxy group, ethoxy group, or acetyl group, a hydrolyzate thereof, silanol, or an average molecular weight of 3000 or less. Polysiloxane is preferred.

  Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, and tetramethoxysilane. In this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in a non-aqueous solvent, hydrolyzed with moisture in the air on the substrate to form silanol, and then at room temperature. A photocatalyst layer can be formed by dehydration condensation polymerization. If dehydration condensation polymerization of silanol is carried out at 100 ° C. or higher, the degree of polymerization of silanol increases and the strength of the film surface can be improved. Moreover, these binders can be used individually or in mixture of 2 or more types.

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

  In addition to the photocatalyst and the binder, the photocatalyst layer can contain a surfactant. 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 can be used, and cationic surfactants, anionic surfactants, and amphoteric surfactants can also be used.

  In addition to the above surfactants, the photocatalyst layer includes polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, poly Contains oligomers and polymers such as vinyl chloride, polyamide, polyimide, styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, polyisoprene Can be made.

(Second Embodiment)
In the second embodiment, the photocatalyst is included in the wettability changing component layer 33 on the side of the color filter substrate together with the binder, and the binder is the material exemplified in the wettability changing component layer, that is, the photocatalyst by ultraviolet exposure. There is no particular limitation as long as it is a material whose wettability is changed by the action of and having a main chain that is not easily deteriorated or decomposed by the action of the photocatalyst. For example, (1) Examples include organopolysiloxanes that exhibit high strength by hydrolysis and polycondensation of alkoxysilanes, etc., and (2) organopolysiloxanes that are crosslinked with reactive silicones that are excellent in water and oil repellency. it can. Hereinafter, specific examples are also the same as the wettability changing component layer.

As the photocatalyst used in this embodiment, the same material as that of the first embodiment can be applied. That is, known as optical semiconductors, for example, titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O _3). ), And iron oxide (Fe ₂ O ₃ ), and one or a mixture of two or more selected from these can be used. In particular, titanium dioxide has a high band gap energy and chemical properties. It is preferably used because it is stable, non-toxic and easily available. Titanium dioxide includes anatase type and rutile type, and both can be used in this embodiment, but anatase type titanium dioxide is preferable.
Further, the smaller the particle size of the photocatalyst, the more effective the photocatalytic reaction occurs, and the average particle size is preferably 50 nm or less, and it is particularly preferable to use a photocatalyst of 20 nm or less.

<Manufacturing method of color filter>
The method for producing a color filter of the present invention can be divided into two methods depending on where the layer having the photocatalyst is provided. That is, the photocatalyst can be divided into two methods: a method of providing the photocatalyst on the substrate side such as a photomask on which the black matrix original plate is formed, and a method of providing the photocatalyst on the color filter forming substrate side.
In the first embodiment, as shown in FIG. 3 and the subsequent FIG. 4, the wettability changing component layer is subjected to proximity exposure with a photocatalyst layer substrate such as a photomask having a photocatalyst layer, so that only the exposed portion is exposed. It is a method of forming a hydrophilic region by making it hydrophilic.
In the second embodiment, as shown in FIG. 5 and subsequent FIG. 6, a wettability changing component layer containing a photocatalyst is provided on the color filter forming substrate side and exposed by a photomask, thereby exposing the exposed portion. This is a method of hydrophilizing only.
Hereinafter, each method will be described.

(First embodiment)
As shown in FIG. 3A, a light shielding film 12 is formed on one main surface of the transparent substrate 11 by a method such as sputtering or vacuum deposition. In the present invention, the light shielding film 12 is a metal film, but includes a light-shielding thin film such as a metal oxide, metal nitride, or metal oxynitride of the metal.
Next, the wettability changing component layer 13 is applied to the film forming surface side of the transparent substrate on which the light shielding film 12 is formed (FIG. 3B).

Next, a base such as a transparent glass substrate and a photocatalyst layer base on which a photocatalyst layer containing a photocatalyst formed on the base is formed are prepared. Such a photocatalyst layer substrate has at least a photocatalyst layer and a substrate, and is usually formed by forming a thin-film photocatalyst layer formed by a predetermined method on the substrate. FIG. 3C illustrates a photocatalyst layer substrate 16 in which a photocatalyst layer 15 is provided on a photomask 14 on which a black matrix original plate (positive plate) is formed.
Subsequently, as shown in FIG. 3C, the photocatalyst layer 15 side of the photocatalyst layer substrate 16 and the wettability changing component layer 13 are prepared with active oxygen species and the like generated by the photocatalytic reaction in the gap. In order to generate and act on the photocatalyst, a gap is formed so as to be 200 μm or less, more preferably 5 to 20 μm, and then proximity exposure is performed with ultraviolet rays 17 from the photocatalyst layer substrate 16 side.

  The exposed area of the wettability changing component layer 13 by UV exposure forms a specific hydrophilic area 18 having a contact angle with the liquid that is lower than that before UV exposure (FIG. 3D).

  Next, the light-shielding film 12 is wet-etched with the wet-etching liquid 19 for the light-shielding film through the specific hydrophilic region 18 of the wettability changing component layer 13 (FIG. 3E). Etching solution 19 is etched into the wettability changing component layer in which hydrophilic region 18 is formed by a method such as spray etching or dip etching, so that etching solution 19 penetrates only into hydrophilic region 18 that is an ultraviolet-exposed portion, and its lower layer. The wettability changing component layer on the wet-shielded light-shielding film is lifted off and peeled off, and the black matrix 20 is formed and the transparent substrate 11 is exposed, and the transparent substrate 11 is colored. The layer forming part 21 is formed in a pattern (FIG. 4F).

  Next, the colored layer forming portion 21 is colored by the ink jet 22 method (FIG. 4G), and the colored layer 23 is formed to form a color filter (FIG. 4H).

(Second Embodiment)
As shown in FIG. 5A, a light shielding film 32 is formed on one main surface of the transparent substrate 31 by a method such as sputtering or vacuum deposition. In the present invention, the light shielding film 32 is a metal film, but includes a light-shielding thin film such as a metal oxide, metal nitride, or metal oxynitride of the metal.
Next, a wettability changing component layer 33 composed of at least a binder and a photocatalyst whose wettability is changed by the action of the photocatalyst is applied and formed on the light shielding film 32 (FIG. 5B).

  Next, the wettability changing component layer 33 is pattern-exposed with ultraviolet rays 37 using a photomask 34 on which a black matrix original plate (positive plate) is formed (FIG. 5C), and the exposed portion of the wettability changing component layer 33 is exposed. A specific hydrophilic region 38 having a reduced contact angle with the liquid as compared with that before the ultraviolet exposure is formed (FIG. 5D).

  The exposed area of the wettability changing component layer 33 by UV exposure forms a specific hydrophilic area 38 having a contact angle with the liquid that is lower than that before UV exposure (FIG. 5D).

  Next, the light-shielding film 32 is wet-etched with a wet-etching liquid 39 for the light-shielding film through the specific hydrophilic region 38 of the wettability changing component layer (FIG. 5E). Since the specific hydrophilic region 38 of the wettability changing component layer is thin and hydrophilic, the etching solution gradually penetrates into the lower layer, etching the lower light shielding film, and changing the wettability on the wet etched light shielding film. The component layer is lifted off and peeled off, and the black matrix 40 is formed and the transparent substrate 31 is exposed, and the colored layer forming portion 41 is formed in a pattern on the transparent substrate 31 (FIG. 6F).

  Next, the colored layer forming portion 41 is colored by applying red, green, and blue pattern paints by the ink jet 42 method (FIG. 6G). Since the wettability changing component layer 33 on the black matrix 40 exhibits high water repellency, it does not diffuse and is applied only to the black matrix opening, which is the colored layer forming portion 41, thereby forming the colored layer 43 to form a color filter. (FIG. 6 (h)).

  FIG. 8 is an explanatory diagram showing an example of a surface reaction in which part of the wettability changing component layer changes to a hydrophilic region. FIG. 8 (a) shows a state where active oxygen species generated by UV exposure attack the side chain on the surface of the wettability changing component layer and break the bond of the side chain. FIG. 8 (b) This shows a state in which a hydroxyl group is bonded to the cleaved site and changes to hydrophilicity. In the hydrophilization treatment that causes the surface reaction in FIG. 8, for example, taking the first embodiment as an example, the wettability changing component layer and the mask having the photocatalyst layer are separated by a predetermined distance (for example, 5 to 20 μm). Is preferably arranged. By disposing the wettability changing component layer and the mask having the photocatalyst layer at a predetermined interval, active oxygen species and the like generated by the photocatalytic reaction can be easily generated in the gap. Examples of the active oxygen species include active oxygen or active hydroxyl groups generated based on the photoelectrochemical reaction in the photocatalyst particles, and these active oxygen species and the like are side chains (for example, alkyl side chains) shown in FIG. ) And the side chain bond is cleaved. The active oxygen species and the like are exchanged and bonded to the portion where the side chain is cleaved to change to the hydrophilic group shown in FIG.

Examples of the present invention will be described in detail below.
Example 1
On a glass substrate (1737 material, manufactured by Corning) as a cleaned substrate, a two-layer film of chromium oxide and metal chromium was formed by sputtering in the order of chromium oxide and metal chromium to form a light shielding film. Next, a water-repellent fluorine-based silicone resin (manufactured by Toshiba Silicone Co., Ltd., TSL8233 and TSL8114) is spin-coated at 1000 rpm for 5 seconds on this light-shielding film and dried at 150 ° C. for 10 minutes, and the wettability changing component layer (thickness 0.1 μm) Formed.

  Next, on this wettability changing component layer, a photomask having a photocatalyst layer was brought close to an interval of 5 μm and subjected to proximity exposure with ultraviolet rays having a wavelength of 200 to 370 nm from the photomask side. The exposed portion of the wettability changing component layer changed from hydrophobic to hydrophilic. The photosk was spin-coated with a silane compound (manufactured by Toshiba Silicone, TSL8114) at 750 rpm for 5 seconds on a quartz glass substrate on which a light-shielding pattern made of chromium (black matrix original plate, positive plate) was formed, and at 150 ° C. A photocatalyst layer containing anatase-type titanium oxide particles as a photocatalyst is spin-coated at 350 rpm for 5 seconds and dried at 150 ° C. for 10 minutes, and a photomask with a photocatalyst-containing layer (patterned substrate) It was created. This photocatalyst layer contained 50% by weight of titanium oxide particles in a binder resin (silicone resin).

Next, using an etching solution of cerium ammonium nitrate-based chromium and performing spray etching, the etching solution penetrates only into the hydrophilic region, and the light shielding film is etched to form a black matrix and etched. The wettability changing component layer on the light shielding film was lifted off and peeled and removed, and the transparent substrate serving as the colored layer forming portion was exposed.
Next, using inkjet, apply the red, green, and blue pigment dispersion to the colored layer forming part where the nozzle is exposed, and apply a black matrix at the boundary between the red, green, and blue colored layers and the colored layer. A color filter having was obtained.
The color filter according to this example showed excellent spectral characteristics.

(Example 2)
30 g of isopropyl alcohol, 0.4 g of MF-160E (manufactured by Tochem Products Co., Ltd.) whose main component is fluoroalkylsilane as a binder, 3 g of trimethoxymethylsilane (TSL8113 manufactured by Toshiba Silicone Co., Ltd.), and photocatalyst 20 g of ST-K01 (Ishihara Sangyo Co., Ltd.) which is a titanium oxide aqueous dispersion was mixed and stirred at 100 ° C. for 20 minutes. This was diluted 3 times with isopropyl alcohol to obtain a composition for a photocatalyst-containing layer.

  Next, on a glass substrate (1737 material, manufactured by Corning) as a cleaned substrate, a two-layer film of chromium oxide and metal chromium was formed by sputtering in the order of chromium oxide and metal chromium to form a light-shielding film. Next, the composition is applied onto the light-shielding film by a spin coater and dried at 150 ° C. for 10 minutes to form a transparent wettability changing component layer (thickness 0.1 μm) composed of a binder and a photocatalyst. did.

This transparent wettability changing component layer was exposed to a black matrix pattern with an illuminance of 70 mW / cm ^{2 with} UV light having a wavelength of 254 nm through a photomask to form a hydrophilic region in the exposed portion. The contact angle of the exposed part and the non-exposed part 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. Thus, it was confirmed that the exposed portion is a hydrophilic region.

Next, using an etching solution of cerium ammonium nitrate-based chromium and performing spray etching, the etching solution penetrates only into the hydrophilic region, and the light shielding film is etched to form a black matrix and etched. The wettability changing component layer on the light shielding film was lifted off and peeled and removed, and the transparent substrate serving as the colored layer forming portion was exposed.
Next, using ink jet, the red, green and blue pigment dispersions are applied to the colored layer forming part where the nozzle is exposed, and the boundary between the red, green and blue colored layers and the colored layer on the transparent substrate. A color filter having a black matrix in the part was obtained.
The color filter according to this example showed excellent spectral characteristics.

It is a cross-sectional schematic diagram which shows an example of 1st Embodiment of the color filter of this invention. It is a cross-sectional schematic diagram which shows an example of 2nd Embodiment of the color filter of this invention. It is a cross-sectional schematic diagram which shows the manufacturing process of the color filter of the 1st Embodiment of this invention. It is a cross-sectional schematic diagram which shows the manufacturing process of the color filter of the 1st Embodiment of this invention following FIG. It is a cross-sectional schematic diagram which shows the manufacturing process of the color filter of the 2nd Embodiment of this invention. It is a cross-sectional schematic diagram which shows the manufacturing process of the color filter of the 2nd Embodiment of this invention following FIG. It is a cross-sectional schematic diagram which shows an example of the conventional color filter formed using the effect | action of a photocatalyst. It is explanatory drawing which shows an example of the surface reaction in which a part of wettability change component layer changes to a hydrophilic region.

Explanation of symbols

11, 31 Transparent substrate 12, 32 Light-shielding film 13, 33 Wetting property changing component layer 14, 34 Photomask 15 Photocatalyst layer 16 Photocatalyst layer substrate 17, 37 Ultraviolet ray 18, 38 Hydrophilic region 19, 39 Etching solution 20, 40 Black matrix 21, 41 Colored layer forming part 22, 42 Inkjet 23, 43 Colored layer 71 Transparent substrate 73 Wetting property changing component layer 78 Hydrophilic region 80 Black matrix 83 Colored layer

Claims (12)

  A color filter having at least a transparent substrate, a colored layer provided with a plurality of colors in a predetermined pattern on the transparent substrate, and a black matrix located at a boundary portion of the colored layer, wherein the liquid repellent material is provided on the black matrix. The wettability changing component layer is laminated with a width substantially equal to that of the black matrix, and a colored layer having a plurality of colors is formed on the transparent substrate between the black matrix and the wettability changing component layer. A color filter characterized by that. The black matrix is wet etched through a specific hydrophilic region of the wettability changing component layer provided on the light shielding film, the light shielding film made of a metal film formed on the transparent substrate, The color filter according to claim 1, wherein the specific hydrophilic region of the wettability changing component layer is formed by being lifted off and removed.   The color filter according to claim 1, wherein the wettability changing component layer is a layer made of at least a binder.   The color filter according to claim 1, wherein the wettability changing component layer is a photocatalyst-containing layer comprising at least a binder and a photocatalyst.   The color filter according to claim 3 or 4, wherein the binder is a layer containing an organopolysiloxane.   The color filter according to claim 5, wherein the organopolysiloxane is a polysiloxane containing a fluoroalkyl group. The organopolysiloxane is YnSiX _(4-n) (wherein Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group or an epoxy group, X represents an alkoxyl group or a halogen, and n represents Or an organopolysiloxane which is one or more hydrolyzed condensates or co-hydrolyzed condensates of a silicon compound represented by the following formula: Item 7. The color filter according to Item 6. The photocatalyst is composed of titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and oxidation. The color filter according to claim 4, wherein the color filter is one or more substances selected from iron (Fe ₂ O ₃ ). The color filter according to claim 8, wherein the photocatalyst is titanium oxide (TiO ₂ ).   The color filter according to claim 1, wherein a thickness of the wettability changing component layer is in a range of 0.001 μm to 1 μm. (1) forming a light-shielding film made of a metal film on a transparent substrate;
(2) forming a wettability changing component layer containing at least a binder that changes wettability by the action of a photocatalyst on the light shielding film;
(3) A photocatalyst layer containing a photocatalyst is formed on a substrate. After the photocatalyst layer side of the photocatalyst layer side and the wettability changing component layer are arranged with a gap of 200 μm or less, the photocatalyst layer UV exposure from the substrate side, forming a hydrophilic region in the exposed portion of the wettability changing component layer in a pattern in a hydrophilic area with a reduced contact angle with the liquid compared to before UV exposure;
(4) The light shielding film is wet etched through the hydrophilic region of the wettability changing component layer to form a black matrix, and the wettability changing component layer on the wet etched light shielding film is lifted off to be transparent. Exposing the substrate and forming a colored layer forming portion in a pattern on the transparent substrate;
(5) coloring the colored layer forming portion by an ink jet method to form a colored layer;
A method for producing a color filter, comprising: (1) forming a light-shielding film made of a metal film on a transparent substrate;
(2) forming a wettability changing component layer comprising at least a binder and a photocatalyst on the light-shielding film, the wettability being changed by the action of the photocatalyst;
(3) The wettability changing component layer is subjected to pattern exposure with a photomask having a light shielding layer pattern, and the exposed portion of the wettability changing component layer has a lower contact angle with the liquid than before exposure to ultraviolet light. Forming a region;
(4) The light shielding film is wet etched through the hydrophilic region of the wettability changing component layer to form a black matrix, and the wettability changing component layer on the wet etched light shielding film is lifted off to be transparent. Exposing the substrate and forming a colored layer forming portion in a pattern on the transparent substrate;
(5) coloring the colored layer forming portion by an ink jet method to form a colored layer;
A method for producing a color filter, comprising:

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