JP2001109091A - Pattern forming body, pattern forming method and functional element, color filter and microlens each using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pattern forming body using a photocatalyst and to produce a functional element. SOLUTION: The pattern forming body has a photocatalyst-containing layer on a substrate and the photocatalyst-containing layer is a layer containing a material whose oil repellency is varied to lipophilic property by the action of the photocatalyst when it is patternwise exposed, or the pattern forming body has a layer containing a material whose oil repellency is varied to lipophilic property by the action of a photocatalyst when it is patternwise exposed on a photocatalyst-containing layer. A functional material, a colorable material and a microlens forming material are each patterned in accordance with a pattern formed by providing lipophilic property by exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pattern-forming body which can be used for various applications, preferably a pattern-forming body and a pattern-forming method based on a change in wettability, and its printing, a color filter, a lens and the like. It is about application.

[0002]

2. Description of the Related Art A pattern formed body having, on a surface of a base material, an area having a different wettability to a liquid than a surrounding area, for example,
Used in many technical fields. For example, patterns, images,
On a pattern forming body used for printing characters and the like, a pattern that receives or repels ink when transferring printing ink is formed. Also, such patterns include:
Some are a patterned layer and a transferred layer formed on the pattern forming body according to a change in wettability.

As a method for forming a high-definition pattern,
Expose the pattern to the photoresist layer applied on the substrate, develop the exposed photoresist, then perform further etching, or use a substance with functional photoresist to expose the photoresist, There is known a method using photolithography such as directly forming a pattern to be formed.

The formation of a high-definition pattern by photolithography includes forming a color pattern of a color filter used for a liquid crystal display device, forming a micro lens,
Used in the manufacture of fine electrical circuit boards, chrome masks used for pattern exposure, etc.Depending on these methods, photoresist is used, and after exposure, development with a liquid developer or etching is performed. Therefore, there is a problem that it is necessary to treat a waste liquid, and when a functional substance is used as a photoresist, it is deteriorated by an alkali solution used for development. There was also a problem. A high-definition pattern such as a color filter is also formed by printing or the like, but the pattern formed by printing has problems such as positional accuracy, and it is difficult to form a high-definition pattern. .

In order to solve such a problem, the present inventors have already provided a pattern forming body and a pattern forming method for forming a pattern using a substance whose wettability changes by the action of a photocatalyst. As proposed in Japanese Patent Application No. 9-214845, the present invention provides a pattern formed body and a pattern forming method having more excellent characteristics in such a pattern formed body and a forming method using a photocatalyst. .

In a liquid crystal display (LCD), a color filter is used in both an active matrix system and a simple matrix system in order to perform color display. For example, in an active matrix type liquid crystal display using a thin film transistor (TFT), a color filter has three primary color patterns of red (R), green (G), and blue (B). The electrode corresponding to the pixel of
By turning off N, the liquid crystal operates as a shutter,
Light is transmitted through each of the R, G, and B pixels to perform color display. The color mixing is performed according to the principle of additive color mixing by opening liquid crystal shutters corresponding to pixels of two or more colors.

A conventional color filter is prepared by applying a dyeing base material on a transparent substrate, exposing and developing the resulting pattern through a photomask, and dyeing the formed pattern into a colored layer. A pigment dispersion method in which a coloring pigment is dispersed in a conductive resist layer in advance and then exposed and developed through a photomask to form a coloring layer; a printing method of printing a coloring layer of each color with a printing ink on a transparent substrate; a transparent substrate An operation of forming a transparent electrode pattern on the transparent electrode pattern in an electrode solution of a predetermined color and performing electrodeposition by performing R, G, and B three times to form a colored pattern of each color by an electrodeposition method or the like. Being manufactured.

However, in the conventional dyeing method and pigment dispersing method, material loss in the step of coating the transparent substrate by spin coating or the like is inevitable, and a developing step and a washing step are required for each color pattern formation. In some cases, it is difficult to improve the material use efficiency and simplify the process, which hinders the reduction of the manufacturing cost. Further, in the printing method, it is difficult to form a high-definition pattern, and there is a problem that the pattern shape that can be formed in the electrodeposition method is limited.

[0009] Among lenses conventionally used, in particular, a microlens or a microlens array formed by regularly arranging microlenses is used in fine optics and other fields. There is an increasing demand for a component constituting the lens and as a lens component for a charge-coupled solid-state imaging device (CCD) used for a video camera or the like.

As a method of manufacturing such a microlens, for example, as described in JP-A-3-21901 and JP-A-5-164904, a transparent thermally deformable resin pattern is obtained by etching through a mask. After that, a method of forming a microlens by deforming a thermally deformable resin pattern by heating is known. However, in this method, it is difficult to form a fine lens because the progress of the etching is isotropic, and the adjustment of the focal length of the lens is restricted, and the process is complicated.
As another method of manufacturing a microlens, for example, as described in JP-A-2-165932, a microlens array is formed by discharging a composition for a lens on a transparent substrate as small droplets and then curing the composition. Methods are known.

However, in this method, since the lens shape is restricted by the contact angle between the transparent substrate and the lens composition, it is difficult to adjust the focal length. In addition, in order to obtain a specific contact angle, a lens composition having a specific surface tension must be selected, and the range of material selection is narrow. Further, the shape of the contact surface was limited to a circle, and it was impossible to have a contact surface of a polygonal pattern. In addition, conventionally, there has been a problem that the adhesive force is deteriorated because the lens composition and the substrate must be repelled to increase the curvature of the lens.

Further, as described in Japanese Patent Application Laid-Open No. 5-206429, a single colored microlens array layer performs the function of a microlens array and a colored filter array formed by laminating a plurality of color filters. Has been proposed. As a method for manufacturing such a colored microlens array, for example, Japanese Patent Laid-Open No. 5-620624
As described in Japanese Patent Publication No. 9 (1994), a color filter array is formed by photolithography, a microlens mold is formed on each color filter, and this mold is transferred to the color filter array by isotropic etching. There is a method in which the filter array is formed into a micro lens. Further, as described in Japanese Patent Application No. 8-201793, a method of forming a lens-shaped concave portion on a glass substrate by photoresist and glass etching, and filling a portion corresponding to each color with a colored lens forming material. There is. However, in the former example, the process is very complicated, and in the latter example, a lens is formed in the concave portion of the glass substrate, and it is very difficult to control the etching process. However, there is a problem that the lens effect cannot be obtained unless the value is made large.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new pattern forming body and a new pattern forming method. It is an object of the present invention to provide a pattern forming body that can provide a novel printing plate precursor that can solve the problem. It is an object to provide a pattern forming body and a pattern forming method capable of providing a functional element.

Further, a color filter used in a liquid crystal display device or the like requires a developing step and a washing step for forming a colored pattern of each color as seen in the conventional dyeing method, pigment dispersing method and the like. To provide a color filter which is high-definition and has no defects such as white spots, and a method for manufacturing a color filter which is excellent in material use efficiency and which does not include a developing step and a washing step and which has a simple process. Is the subject.

A method of manufacturing a lens with a simple process, particularly a method of manufacturing a microlens and a microlens array with high positional accuracy and easily changing the focal length of the microlens. It is an object of the present invention to provide a lens, a micro lens, and a micro lens array manufactured by the method.

[0016]

SUMMARY OF THE INVENTION The present invention relates to a pattern forming body for optically forming a pattern, comprising a photocatalyst-containing layer on a substrate, wherein the photocatalyst-containing layer acts on the photocatalyst by exposing the pattern. The object of the present invention is to solve the above-mentioned problem by providing a pattern forming form containing a substance which changes from oleophobic to lipophilic. Further, a pattern forming body for optically forming a pattern, having a photocatalyst containing layer on the substrate, on the photocatalyst containing layer, having a layer that is decomposed and removed by the action of the photocatalyst by exposure of the pattern, As a result, the pattern formed body changes from oil repellency to lipophilicity. A pattern forming body for optically forming a pattern, having a photocatalyst containing layer on the substrate, on the photocatalyst containing layer,
It is a pattern formed body having a layer containing a substance that changes from oleophobic to lipophilic by pattern exposure. A pattern forming body that optically forms a pattern, having a composition layer composed of a photocatalyst, a substance that is decomposed by the action of the photocatalyst upon exposure of the pattern, and a binder, and is oil-repellent to lipophilic by light irradiation. The pattern formed body changes to

In the above-mentioned pattern formed body, the photocatalyst-containing layer contains a compound having a siloxane bond. The photocatalyst-containing layer is the above-described pattern-formed body containing silicone. It is the above-described pattern forming body in which a fluoroalkyl group is bonded to a silicon atom of silicone. The above pattern-forming body, wherein the silicone is obtained from a composition containing an organoalkoxysilane. The above pattern-formed body, wherein the silicone is obtained from a composition containing a reactive silicone compound. Further, the pattern formed body is a functional element in which a functional layer is disposed on a portion corresponding to a pattern of the pattern formed body obtained by pattern exposure, a color filter, or a micro formed lens. is there.

The present invention also provides a method for optically forming a pattern, comprising forming a photocatalyst-containing layer containing a substance, which changes from oil-repellent to lipophilic by the action of a photocatalyst, on a substrate; A patterned body in which a layer containing a substance that changes from oleophobic to lipophilic by the action of a photocatalyst is formed on the photocatalyst-containing layer formed on the photocatalyst-containing layer, and the pattern is formed on the photocatalyst-containing layer by exposing the pattern to Pattern-forming body having a layer that is decomposed and removed by the action of a photocatalyst, or pattern formation in which a composition layer comprising a photocatalyst, a substance that is decomposed by the action of a photocatalyst by exposure of a pattern, and a binder is formed on a substrate This is a pattern forming method in which a body is exposed to a pattern and the surface is changed from oleophobic to lipophilic by the action of a photocatalyst. The pattern exposure of the photocatalyst-containing layer is the above-described pattern forming method performed by irradiation with optical drawing. The pattern exposure for the photocatalyst-containing layer is the above-described pattern forming method performed by exposure through a photomask. The pattern exposure for the photocatalyst-containing layer is the above-described pattern forming method performed while heating the pattern formed body.

Further, the functional layer is provided on a portion corresponding to the pattern of the pattern formed body obtained by any one of the pattern forming bodies obtained by any one of the above-described pattern exposures on the base material. Device. A functional layer formed on a portion corresponding to the pattern of the pattern formed body obtained by any one of the pattern exposures on the pattern formed body, formed by transferring the functional layer onto another substrate. One of the above-mentioned elements.

An element fabrication having any one of the above-described pattern-formed bodies on a substrate and forming a functional layer on a portion corresponding to the pattern of the pattern-formed body obtained by any of the above-described pattern exposure methods Is the way. On the pattern formed body, the functional layer is transferred onto another base material by transferring the functional layer onto a portion corresponding to the pattern of the pattern formed body obtained by pattern exposure according to any of the above. This is the above-described element manufacturing method in which a conductive layer is formed. A step of laminating the functional layer composition on the entire surface of the pattern-formed body, forming a functional layer in a pattern only on specific portions of the layer where the oil repellency of the exposed portion has changed from oleophobic to lipophilic due to the repulsion of the unexposed portion This is the above-described element manufacturing method including the step of performing the following. A step of laminating the functional layer composition on the entire surface of the pattern formed body,
The above-described device manufacturing method includes a step of forming a functional layer in a pattern by removing the functional layer in an unexposed portion. A step of laminating the functional layer composition on the entire surface of the pattern-formed body, forming a functional layer in a pattern only on specific portions of the layer where the oil repellency of the exposed portion has changed from oleophobic to lipophilic due to the repulsion of the unexposed portion This is the above-described element manufacturing method including the step of performing the following. The above method for producing an element, comprising the steps of laminating a functional layer composition over the entire surface of a pattern formed body, and forming a functional layer in a pattern by removing an unexposed portion of the functional layer.

The formation of the functional layer on the pattern formed body is the above-described method for producing an element by applying a functional layer composition or discharging from a nozzle. The formation of the functional layer on the pattern-formed body is the above-described element manufacturing method by transfer from a functional layer composition-coated film by heat or pressure. The formation of the functional layer on the pattern forming body is the above-described element manufacturing method by film formation using vacuum film formation means or electroless plating.

Further, at least one of a transparent substrate and a colored layer of a plurality of colors formed in a predetermined pattern on the transparent substrate is formed through a specific portion of the layer that changes from oleophobic to lipophilic. This is a color filter formed on a substrate. A transparent substrate, and a light-shielding layer at a boundary between colored layers formed of a plurality of colors formed in a predetermined pattern on the transparent substrate, wherein at least one of the colored layer and the light-shielded layer is provided.
A color filter, wherein the layer is formed on the transparent substrate via a specific portion of the layer that changes from oleophobic to lipophilic. A transparent substrate provided with a light-shielding layer in a predetermined pattern, and a layer that changes from oil-repellent to lipophilic on the transparent substrate so as to cover the light-shielding layer, and specifies a layer that changes from oil-repellent to lipophilic. A laminated body with a colored layer formed in a predetermined pattern on a site is provided by laminating a desired number of colors, or a light-shielding layer formed in a predetermined pattern is provided, and the oil-repellent property changes to lipophilic. The layer to be formed is a color filter which is a photocatalyst containing layer composed of a photocatalyst and a binder. The binder is a color filter containing a composition containing chlorosilane or alkoxysilane, or an organopolysiloxane obtained from a composition containing reactive silicone.

A photocatalyst layer composed of a binder and a photocatalyst substance is formed on a transparent substrate, and the photocatalyst layer is exposed to light in a predetermined pattern to form a portion that changes from oil repellency to lipophilicity. Alternatively, this is a method for manufacturing a color filter in which a colored layer is formed by attaching any of the colored layer paints. Forming a photocatalyst-containing layer comprising at least a binder and a photocatalyst on a transparent substrate, irradiating the photocatalyst-containing layer with light, and forming the light-irradiated portion from a portion that changes from oil-repellent to lipophilic by the action of the photocatalyst; This is a method for manufacturing a filter. Formed on a transparent substrate,
The photocatalyst-containing layer composed of a binder and a photocatalyst is irradiated with light in a predetermined pattern to the photocatalyst-containing layer to form a light-irradiated part changed from oleophobic to lipophilic by the action of the photocatalyst. A method for producing a color filter in which a light-shielding layer is formed by adhering a light-shielding layer paint to the color filter, or an operation of adhering the color-layer coating is performed at least once or more. The light irradiation on the photocatalyst-containing layer is a method for producing the color filter by either pattern exposure through a mask or light drawing irradiation. At least one of the light-shielding layer paint and the colored layer paint is attached by the above-described method for producing a color filter, which is performed by any of a coating method, a nozzle discharging method, and a vacuum thin film forming method. In the vacuum thin film forming method, the method for producing a color filter described above, further comprising a step of removing a thin film made of a light-shielding layer paint or a colored layer paint adhered to a portion other than a portion changed from oleophobic to lipophilic after the thin film is formed. It is.

In the method of manufacturing a lens, a photocatalyst-containing layer containing a photocatalyst and a binder formed on the surface of a substrate is irradiated with light, so that the surface of the substrate changes from oleophobic to lipophilic by photocatalysis. After a pattern is formed by the difference in wettability by forming a part to be formed, a liquid containing a material for forming a lens is attached, and then the liquid is cured according to the pattern to form a lens. It is a manufacturing method. Further, in the above-mentioned method for producing a lens, the photocatalyst-containing layer contains at least an optical semiconductor substance as a photocatalyst and a binder component. The method of manufacturing a lens, wherein a liquid containing a material for forming the lens is attached to a portion of the substrate that has changed from oleophobic to lipophilic by light irradiation.

[0025] In the above-mentioned method for manufacturing a lens, a liquid containing a material for forming the lens is applied to the base material or adhered by nozzle discharge. The method of manufacturing a lens described above, wherein a colored microlens array is obtained by applying a liquid containing a material for forming the colored lens to the base material by a required number of colors by discharging from a nozzle for each color. . This is a method for manufacturing a lens, wherein a colored microlens array of a plurality of colors is obtained by repeating the process for one substrate for each color of the lens. The method of manufacturing a lens, wherein a focal length of the lens is adjusted by changing an amount of a liquid containing a material for forming the lens on the substrate.

Forming a pattern by changing from oleophobic to lipophilic by irradiating light to form a light-shielding layer pattern corresponding to the lens pattern on the back surface of the transparent substrate on which the lens is not formed; Adhering a liquid containing a material for forming a light-shielding layer to the lipophilic portion of the light-shielding layer pattern of the base material, and curing the liquid containing a material for forming the light-shielding layer to form a light-shielding layer And forming a light-shielding layer. This is a method for manufacturing the above-described lens having the light-shielding layer to which a liquid containing a material for forming the light-shielding layer is applied by application or ejection from a nozzle.

In a lens formed on a transparent substrate, a lens pattern is formed on a portion of the transparent substrate on which the lens is not formed, the portion having changed from oil-repellent to lipophilic by the action of the photocatalyst by light irradiation on the photocatalyst. In the above lens, a light-shielding layer pattern corresponding to the above is formed. The above lens is a microlens or a microlens array in which the lenses are arranged in an array. In the above lens, the lens is a colored lens of at least one color.

An imaging apparatus using the above-described microlens or microlens array. A display device using the microlens or the microlens array.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a pattern forming body and a pattern forming method for forming a pattern by using a photocatalyst capable of causing a chemical change in a nearby substance by irradiation of light. Further, the pattern of the present invention is a region in which the characteristics are different from the surroundings formed on the pattern forming body in accordance with the change from oleophobic to lipophilic, and a transcript in which they are transferred to another base material. There is also a case.

The mechanism of action by the photocatalyst represented by the titanium oxide of the present invention is not necessarily clear, but the carrier generated by the light irradiation may react directly with a nearby compound or in the presence of oxygen and water. It is thought that the generated reactive oxygen species change the chemical structure of organic matter. Using the action of such a photocatalyst, oily stains are decomposed by light irradiation, and the oily stains are made hydrophilic so that they can be washed with water, or a hydrophilic film is formed on the surface of glass or the like to provide anti-fog properties. A so-called antibacterial tile or the like has been proposed in which a photocatalyst-containing layer is applied or formed on the surface of a tile to reduce the number of airborne bacteria.

In the present invention, a substance whose wettability changes from oleophobic to lipophilic by the action of a photocatalyst, a layer which is decomposed and removed by the action of a photocatalyst, a substance whose wettability changes from oleophobic to lipophilic by the action of a photocatalyst And a layer having a composition comprising a substance decomposed by the action of a photocatalyst and a binder, etc., to make the exposed portion lipophilic to obtain a pattern-formed body.

In the present invention, oil repellency and lipophilicity are 10 to 50 dyne / cm, preferably 20 to 4 dyne / cm.
In the functional layer composition of 0 dyne / cm, the term “oleophobic” means a substance exhibiting a contact angle of 10 ° or more, and the term “lipophilicity” means 1
Means exhibiting a contact angle of less than 0 °.

The photocatalyst which can be used in the pattern forming body and the pattern forming method of the present invention includes titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO) and titanium Strontium acid (SrTiO ₃ ), tungsten oxide (W
O ₃ ), bismuth oxide (Bi ₂ O ₃ ), iron oxide (Fe ₂ O)
_Although metal oxides such as ₃ ) can be mentioned, titanium oxide is particularly preferable. Titanium oxide has a high band gap energy, is chemically stable, has no toxicity,
It is easy to obtain. As the titanium oxide, both anatase type and rutile type can be used, but anatase type titanium oxide is preferable.

As the anatase type titanium, those having a small particle size are preferable because the photocatalytic reaction occurs efficiently. Those having an average particle size of 50 nm or less are preferable, and those having an average particle size of 20 nm or less are more preferable. For example, an anatase-type titania sol of peptized hydrochloric acid (STS manufactured by Ishihara Sangyo)
-02, average crystallite diameter of 7 nm) and nitrate peptized anatase titania sol (Nissan Chemical Industries, TA-15, average crystallite diameter of 12 nm).

The layer containing the photocatalyst of the present invention can be formed by dispersing the photocatalyst in a binder. Since the photocatalyst may also decompose the binder by photoexcitation, the binder must also have sufficient resistance to the photooxidation action of the photocatalyst. Also, in consideration of using the pattern formed body as a printing plate, printing durability and wear resistance are required. Therefore, as the binder, a silicone resin whose main skeleton has a siloxane bond (—Si—O—) can be used.

In the silicone resin, an organic group is bonded to a silicon atom. As will be described in detail in Examples, when a photocatalyst is photoexcited, the organic group bonded to the silicon atom of the silicone molecule is photocatalyzed. Since it is decomposed, it also functions as a substance that changes from oleophobic to lipophilic. As the silicone resin, the general formula Y _n SiX _4-n (n
= 1 to 3), one or more hydrolytic condensates and co-hydrolytic condensates of the silicon compound can be used. Y can include an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, or an epoxy group, and X can include a halogen, a methoxyl group, an ethoxyl group, or an acetyl group. Trichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl Triisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n
-Propyltriisopropoxysilane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n
-Hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane: n-decyltrichlorosilane,
n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n
Octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; dimethoxydi; Ethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldisilane Bromosilane,
Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane;
Vinyltribromosilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxy Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltrit-butoxysilane .gamma.-aminopropyl methyl dimethoxy silane, .gamma.-aminopropyl methyl diethoxy silane, .gamma.-aminopropyltrimethoxysilane, gamma
-Aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane , Γ-mercaptopropyltriethoxysilane, γ
-Mercaptopropyltriisopropoxysilane, γ-
Mercaptopropyltri-t-butoxysilane; β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; and partial hydrolysates thereof; and mixtures thereof can be used.

In the case where an organoalkoxysilane is used as the binder layer, at least one of the organoalkoxysilanes is used.
It is more preferred to use from 0 to 30% by weight of a bifunctional silicone precursor such as dialkoxydimethylsilane.

Further, the silicone molecule may contain a fluoroalkyl group as an organo group bonded to a silicon atom. In this case, the oil repellency of the unexposed portion is further improved. Accordingly, the repulsion between the ink and the composition for a functional layer and the unexposed portion is improved, and the function of preventing adhesion of the composition for forming a colored layer or the composition for a functional layer is increased. The choice of substances that can be used as layer compositions will increase.

Specifically, it is formed from one or more hydrocondensation products and co-hydrolysis condensates of the following fluoroalkylsilanes. Examples of the compound containing a fluoroalkyl group include the following compounds, and a compound generally known as a fluorine-based silane coupling agent may be used.

CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OC
_{H 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 C _{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 (OC
H ₃ ) ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OC
H ₃ ) ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ (OC
_{H 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 (OC
_{H 3) 2 CF 3 (CF} 2) 5 (C 6 H 4) C 2 H 4 SiCH 3 (OC
_{H 3) 2 CF 3 (CF} 2) 7 (C 6 H 4) C 2 H 4 SiCH 3 (OC
_{H 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) CH 2 CH 2 CH ₂ S
i (OCH ₃ ) _{3 In order to} further improve the repellency with the colored layer forming composition and the functional layer composition, a reactive linear silicone, preferably dimethylpolysiloxane, is crosslinked at a low crosslinking density. The silicone obtained by the above is preferred. Typically, a compound having a repeating unit represented by the following formula A-1 and subjected to a crosslinking reaction is preferable.

[0041]

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Here, n is an integer of 2 or more. R ¹ ,
R ² is a substituted or unsubstituted alkyl, fluoroalkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms. R ¹ and R ² are preferably methyl groups because the surface energy is minimized, and the molar ratio of the methyl groups is preferably 60% or more. Further, the molecular weight is preferably from 500 to 1,000,000. If the molecular weight is small, the amount of R ¹ and R ^{2 is} relatively small, so that oil repellency and the like are hardly exhibited. On the other hand, if the molecular weight is too large, the ratio of X and Y at the ends is relatively small, so that there is a problem that the crosslink density is reduced. X and Y are selected from the following groups,
X and Y may be the same or different, and R is a hydrocarbon chain having 10 or less carbon atoms.

[0043]

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The reactive modified silicone used in the present invention is:
Either one that crosslinks by condensation or one that crosslinks using a crosslinking agent can be used. When the crosslinking reaction is carried out by condensation, tin, zinc, lead, calcium, manganese salts of carboxylic acid, preferably lauryl acid salt, or chloroplatinic acid may be added as a catalyst. When a cross-linking reaction is carried out using a cross-linking agent, isocyanates generally used as a cross-linking agent can be mentioned, and the following compounds are preferable.

[0045]

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As the reactive silicone compound, an aqueous emulsion type may be used. Since the aqueous emulsion type compound uses an aqueous solvent, it is easy to handle. The oil repellency may be increased by mixing a stable organosiloxane compound that does not undergo a cross-linking reaction, such as dimethylpolysiloxane, with the reactive silicone compound used as the binder of the present invention. In this case, it is preferable that at least 60% by weight of the siloxane contained in the layer obtained from the composition containing the reactive silicone compound is obtained from the reactive silicone compound, and if it is less than 60% by weight. Undesirably, the amount of dimethylsiloxane decreases and the oil repellency deteriorates.

Further, as the binder can be used amorphous silica precursor is represented by the general formula SiX _4,
X is preferably a silicon compound such as a halogen, a methoxy group, an ethoxy group or an acetyl group, a silanol hydrolyzate thereof, or a polysiloxane having an average molecular weight of 3000 or less. Specifically, tetraethoxysilane,
Tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, tetramethoxysilane and the like can be mentioned. In this case, the precursor of the amorphous silica and the particles of the photocatalyst are uniformly dispersed in a non-aqueous solvent, and hydrolyzed on the base material with moisture in the air to form silanol, and then cooled to room temperature. To form a photocatalyst-containing layer. If the dehydration-condensation polymerization of silanol is performed at 100 ° C. or higher, the degree of polymerization of silanol increases, and the strength of the film surface can be improved. These binders can be used alone or in combination of two or more.

Further, it is also possible to form a film using titanium oxide alone without using a binder. In this case, amorphous titania is formed on the substrate, and then the phase is changed to crystalline titania by firing. Amorphous titania is, for example, titanium tetrachloride, hydrolysis, dehydration condensation of inorganic salts of titanium such as titanium sulfate, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetrabutoxytitanium, tetramethoxytitanium, etc. The organic titanium compound can be obtained by hydrolysis and dehydration condensation in the presence of an acid.

Then, it is transformed into anatase-type titania by firing at 400 ° C. to 500 ° C.
It is converted to rutile titania by firing at 00 ° C. In the layer containing at least one of organosiloxane and amorphous silica and a photocatalyst, the amount of the photocatalyst is preferably 5% by weight to 60% by weight,
More preferably, it is 20% by weight to 40% by weight.

The photocatalyst and the binder can be dispersed in a solvent to prepare a coating solution for coating. Examples of the solvent that can be used include alcohol-based organic solvents such as ethanol and isopropanol. Also, a titanium-based, aluminum-based, zirconium-based, or chromium-based coupling agent can be used.

The coating solution containing the photocatalyst can be applied to a substrate by a method such as spray coating, dip coating, roll coating, and bead coating. When a UV-curable component is contained as a binder, a layer of a composition containing a photocatalyst can be formed on a substrate by irradiating ultraviolet rays to perform a curing treatment.

Anatase titania has an excitation wavelength of 380
nm or less, and in the case of such a photocatalyst, it is necessary to excite the photocatalyst with ultraviolet light. Mercury lamps, metal halide lamps,
Xenon lamp, excimer lamp, excimer laser,
A YAG laser or another ultraviolet light source can be used, and the wettability of the film surface can be changed by changing the illuminance, the irradiation amount, and the like.

When the exposure is performed with a fine beam such as a laser beam, a desired pattern can be drawn directly without using a mask. Light irradiation is performed using the formed mask to form a pattern. As a mask for pattern formation, a mask formed on a metal plate like a mask for vapor deposition, a photomask formed on a glass plate with metal chromium, or the like can be used. The pattern forming body of the present invention can be made sensitive to visible and other wavelengths by doping metal ions such as chromium, platinum, and palladium, adding a fluorescent substance, and adding a photosensitive dye. For example, cyanine dyes such as cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, hemicyanine dyes, and the like; other useful dyes include crystal violet, and diphenylmethane dyes such as triphenylmethane dyes such as basic fuchsin. And xanthene dyes such as rhodamine B, Victoria blue, brilliant green, malachite green, methylene blue, pyrylium salts, benzopyrylium salts, trimethine benzopyrylium salts, triallylcarbonium salts and the like.

When a mask is used in exposing the pattern-formed body of the present invention, the resolution is increased by exposing the mask to the photocatalyst-containing layer, but the sensitivity is remarkably reduced. Exposure is preferably performed at intervals. Exposure while blowing air into the gap between the mask and the pattern forming body promotes the reaction, improves the sensitivity, and further prevents non-uniformity due to the difference in the position between the central portion and the peripheral portion. Further, the sensitivity can be increased by exposing the pattern formed body while heating it. A fine pattern can also be formed by using a reduction projection exposure method for reducing an image of a mask pattern using a reduction optical system.

Substrates which can be used in the pattern-formed body of the present invention include metals such as glass, aluminum, and alloys thereof, plastics, and fabrics depending on the use of the pattern-formed body or the element on which the pattern is formed. And nonwoven fabrics. In addition, the pattern formed body of the present invention may be used before the application of the photocatalyst-containing layer composition, for the purpose of improving adhesion, improving surface roughness, preventing deterioration of the substrate due to the action of the photocatalyst, preventing reduction in photocatalytic activity, and the like. A primer layer may be formed thereon. Examples of the primer layer include a resin having a siloxane structure as a main component, a fluorine resin, an epoxy resin, and a polyurethane resin.

As one embodiment of the pattern forming body of the present invention, as shown in FIG.
The photocatalyst-containing layer 141 may be formed directly on the base material 102 or after forming the primer layer 103. A predetermined pattern for recording pattern information as shown in FIG. Exposure 106 of 105 is performed, and as shown in FIG. 1C, the lipophilic portion is decomposed by the action of the photocatalyst 107 to form a lipophilic portion 108 on the surface that was oleophobic according to the exposed pattern. Oil repellent part 1
The pattern information is recorded based on the difference in wettability between the pattern information 09 and the wettability.

As a second embodiment of the pattern forming body of the present invention, as shown in FIG.
A primer layer 103 is laminated thereon, and a photocatalyst-containing layer 142 containing a photocatalyst is formed. Further, when the photocatalyst-containing layer is irradiated with light, the wettability changes from oil-repellent to lipophilic by the action of the photocatalyst. The variable material layer 110 is formed. As shown in FIG.
Exposure 106 is used to form a specific lipophilic portion 111 according to the pattern as shown in FIG. 2 (C), and pattern information is recorded.

In the case of the second embodiment, the photocatalyst-containing layer is formed by hydrolyzing or partially hydrolyzing a composition in which a photocatalyst is dispersed in a binder precursor or the like. A method of forming a thin film made of an organic material is also possible, and a film can be formed using only a photocatalyst.
The organic thin film can be formed by a solution coating, a surface grafting treatment, a surfactant treatment, or a film forming method using a gas phase such as PVD or CVD.

As the organic substance, a low molecular weight compound, a high molecular weight compound, a surfactant, or the like, whose wettability is changed by a photocatalyst can be used. Specifically, it is a silane compound in which the oil-repellent site is decomposed, and examples thereof include a silane coupling agent, chlorosilane, alkoxysilane, and two or more kinds of hydrolytic condensates and cohydrolytic condensates thereof.

As a third embodiment, FIG.
As shown in (A), the photocatalyst containing layer 1
43, and on the photocatalyst-containing layer, a substance layer 112 which is decomposed and removed by the action of the photocatalyst when irradiated with light.
Is formed, and exposed 106 using a pattern 105 as shown in FIG. 3B, and a lipophilic portion 113 is formed according to the pattern as shown in FIG. 3C to record pattern information. is there.

In the case of the third embodiment, the photocatalyst-containing layer forms a photocatalyst composition layer obtained by hydrolyzing or partially hydrolyzing a composition in which a photocatalyst is dispersed in a binder precursor or the like, and then forms an oil-repellent material. There is a method of forming a thin film made of an organic substance, and it is also possible to form a film using only a photocatalyst. The organic thin film can be formed by applying a solution, applying a surface graft treatment, a surfactant treatment, or using a film forming method in a gas phase such as PVD or CVD.

Specifically, Nippon Surfactant Industries: hydrocarbons such as NIKKOLBL, BC, BO and BB series; DuPont: ZONYLFSN, FS
O, Asahi Glass: Surflon S-141, 145, Dainippon Ink: Megafac F-141, 144, Neos: Futagent F-200, F251, Daikin Industries Unidyne DS-401, 402, 3M: Florard F
Examples thereof include fluorine-based or silicone-based nonionic surfactants such as C-170 and 176, and cationic, anionic and amphoteric surfactants can be used.

In addition to the surfactant, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride, polyamide And oligomers and polymers such as polyimide, styrene-butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, and polyisoprene. .

In the fourth embodiment, as shown in FIG. 4A, a primer layer 103 is formed on a base material 102, and then a photocatalyst, a binder, and a photocatalyst when irradiated with light. A photocatalyst containing layer 144 containing an oil-repellent photocatalytic decomposable substance 116 decomposed by the photocatalyst is formed. Instead of the photocatalyst-containing layer, a layer consisting only of a photocatalyst and a photocatalytic decomposable substance may be formed. And FIG.
Exposure 106 with a predetermined pattern 105 as shown in FIG.
I do. As a result, as shown in FIG. 4 (C), the photocatalytic decomposable substance 116 is decomposed by the action of the photocatalyst to form a lipophilic portion 117 in which the oil repellency of the surface has changed according to the pattern exposed 106. It records information.

As a substance for changing the surface from oil repellency to lipophilicity, a substance such as a surfactant capable of arbitrarily setting the oil repellency of the photocatalyst-containing layer in accordance with the type and the amount of addition. Is preferably added. Specifically, as the substance capable of changing the surface from oil repellency to lipophilicity, the surfactant described in Embodiment 3 can be used.

The photocatalyst is used in a composition of 5 to 60% by weight, the amorphous silica is used in an amount of 95 to 40% by weight, and the material for changing the surface from oleophobic to lipophilic is used in an amount of 0.1 to 55% by weight. preferable.

In the pattern-formed body of the present invention, the surface free energy is changed by the action of a catalyst in the composition, and the receptivity of the composition for forming a functional layer is changed in the portion where the oil repellency is changed to lipophilic. Therefore, there is no need for wet development or the like, and the feature is that simultaneous production with exposure is completed. The pattern formation on the pattern forming body of the present invention may be performed by exposing through a photomask or the like, or may be performed by direct drawing with a laser or the like.

If the substrate is likely to be degraded by the photo-oxidizing action of the photocatalyst, such as plastic, a protective layer may be formed by coating the substrate with silicone, fluororesin or the like in advance. Can be used in any form such as a sheet, a ribbon, and a roll.
The formed pattern may be visualized by mixing a photochromic material such as spiropyran or the like which discolors with light or an organic dye decomposed by the action of a photocatalyst into the composition.

When the pattern formed body of the present invention is used for an element having a pattern laminated thereon, various functional layers can be formed on various substrates by adjusting the wettability of the surface of the pattern formed body. Can be formed in a pattern. Functionality refers to optical (refraction, light selective absorption, reflection, light transmission, polarization, light selective transmission, nonlinear optical, luminescence such as fluorescence or phosphorescence, photochromic, etc.), magnetic ( Hard magnetic, soft magnetic, non-magnetic, magnetically permeable, etc.),
Electrical / Electronic (Conductivity, Insulation, Piezoelectricity, Pyroelectricity, Dielectricity, etc.), Chemical (Adsorption, Desorption, Catalytic, Water absorption, Oil absorption, Ion conductivity, Redox, Electricity Chemical properties, electrochromic properties, etc., mechanical properties (friction resistance, etc.), thermal properties (thermal conductivity, heat insulation properties, infrared radiation properties, etc.), biological functions (biocompatibility, antithrombotic properties, etc.) .

The functional element can be produced by applying the composition for a functional layer on a pattern forming body. As the composition for the functional layer, a composition that can be wetted only on the exposed portion of the pattern formed body on which the pattern is formed can be used.

For this pattern, a pattern that changes from oleophobic to lipophilic, which is distinguished into a portion where the functional layer composition adheres to the surface and a portion where the composition does not adhere, can be widely used. The composition for a functional layer is desirably made of a material having a contact angle of 10 ° or more at an unexposed portion of the pattern formed body. In this case, examples of the composition for a functional layer include a liquid composition not diluted with a solvent represented by an ultraviolet curable monomer and the like, a liquid composition diluted with a solvent, and the like.

The lower the viscosity of the composition for a functional layer is, the shorter the pattern can be formed. However, in the case of a liquid composition diluted with a solvent, it is desirable that the solvent has low volatility because the viscosity increases and the surface tension changes due to volatilization of the solvent during pattern formation.

The composition for a functional layer is formed by using a coating means such as dip coating, roll coating, blade coating or the like, a nozzle discharging means including ink jet or the like, or a means such as electroless plating. In addition, when a component curable by ultraviolet light, heat, electron beam, or the like is contained as a binder of the functional layer composition, by performing a curing treatment, various components are formed on the substrate via the pattern forming body. A layer for promoting functions can be formed in a pattern.

Further, after forming the functional layer on the entire surface, utilizing the difference in the adhesive force at the interface between the exposed or unexposed portion and the functional layer, for example, peeling by peeling off the adhesive tape after adhering the adhesive tape The functional layer on the unexposed part is removed by post-processing such as blowing air, processing with a solvent,
Can be patterned. Further, it is not necessary to completely repel or adhere the functional layer to each of the unexposed portion and the exposed portion, and a pattern having a different amount of adhesion can be formed due to a difference in adhesion.

The functional layer can also be formed by using a vacuum film forming means such as PVD or CVD. Even if the entire surface is laminated, if the difference in the adhesive strength between the exposed or unexposed portion and the functional layer is used, for example, patterning is performed by post-processing such as peeling with an adhesive tape, blowing air, and solvent treatment. can do. Further, in the case of using the vacuum film forming means, not only the method of laminating on the entire surface of the pattern formed body, but also utilizing the reactivity with the exposed portion or the unexposed portion,
A functional layer may be selectively formed on an exposed portion or an unexposed portion.

As the composition for a functional layer, not only those which show the properties as a functional layer but only by forming a layer on a pattern formed body, and those which do not show the properties as a functional layer only by forming a layer. , Treatment with chemicals after layer formation,
Also includes those requiring treatment by ultraviolet rays, heat, and the like.

Next, an element which can be manufactured using the pattern formed body of the present invention will be described. A color filter used in a liquid crystal display device or the like has a high-definition pattern in which a plurality of colored pixels such as red, green, and blue are formed. Color filters can be manufactured,
For example, on a photocatalyst containing layer formed on a transparent glass substrate, when applying a composition for a colored layer for forming a color filter after pattern exposure, the exposed portion changes from oleophobic to lipophilic, the exposed portion Since only the coloring layer composition is applied, the amount of the coloring layer composition used can be reduced. In addition, since the layer of the composition for the colored layer is formed only on the pattern, if a photosensitive resin composition is used as the composition for the colored layer, only the photocuring treatment after application,
A high-resolution color filter can be manufactured without performing development or the like.

Further, the pattern forming body of the present invention can be used for manufacturing a micro lens. For example, circular exposure is performed on the photocatalyst-containing layer laminated on the transparent substrate to form a circular pattern changed from oleophobic to lipophilic. Next, when the composition for forming a lens is dropped on a portion that has changed from oleophobic to lipophilic, it wets and spreads only on the exposed portion, and by further dropping, the contact angle of the droplet can be changed. For example, since various shapes or focal lengths can be obtained, a high-definition microlens can be obtained.

Further, a metal film having a desired pattern can be formed by using the pattern forming body of the present invention in a method of forming a metal film by electroless plating. According to this method, a resist pattern is not formed. Since a metal pattern can be formed, a printed circuit board, an electronic circuit element, and the like can be manufactured.

Further, the pattern forming body of the present invention can be used in a method of forming a pattern of a metal or the like using a vacuum film forming technique. For example, a pattern having high adhesiveness is produced by light irradiation, and then a metal component is heated and vapor-deposited under vacuum, and a metal component such as aluminum is vapor-deposited on the entire surface of the pattern forming body to form a metal thin film. . There is a difference in the adhesion strength of the metal thin film between the part where the pattern is formed and the part where it is not.Therefore, a patterned metal thin film is formed by pressing the adhesive against the thin film surface, peeling it with a chemical, etc. can do.

In the case of peeling using an adhesive, the adhesive-coated sheet is brought into contact with the thin film surface, and then the adhesive-coated sheet is peeled off to form a pattern forming portion and a pattern. The thin film other than the pattern forming portion is peeled off due to the difference in the adhesiveness of the non-formed portion, and a metal pattern can be formed. According to this method, it is possible to form a metal pattern without forming a resist pattern, and it is possible to produce a printed circuit board, an electronic circuit element, or the like having a higher definition pattern than by a printing method. it can.

Hereinafter, a method for manufacturing the device of the present invention will be described with reference to the drawings. FIG. 9 is a diagram illustrating an example of a method for manufacturing an element of the present invention, and a diagram illustrating a cross section. In the pattern exposure step of FIG. 9A, as shown in A1, the pattern formed body 101 having the photocatalyst containing layer 104 provided on the base material 102 was formed using a photomask 120 according to the pattern of the element to be formed. Exposure 106 or A2
As shown in (1), direct drawing is performed on the pattern forming body 101 using a laser 121 having a wavelength in the ultraviolet region or the like to form the lipophilic portion 113 on the surface on the pattern forming body.

Next, in the entire film forming step shown in FIG.
A coating using a blade coater 122 as shown in FIG. 1 or a coating using a spin coater 123 as shown in B2, a film forming means 124 using vacuum such as vapor deposition and CVD shown in B3, and the entire surface of the pattern formed body. Functional layer 1
25 are formed. The functional layer 125 formed on the pattern formed body has a difference in adhesive strength between an exposed part and an unexposed part due to a difference in surface free energy caused by exposure of the pattern formed body.

Next, in the peeling step shown in FIG. 9C, a method of peeling off the functional layer formed on the unexposed portion by bringing the adhesive surface of the adhesive tape 126 into close contact with each other and peeling it off from the end portion, The functional layer 128 is removed by removing the functional layer from a portion having a small adhesive force by a method of injecting air from the nozzle 127 or a peeling agent.
To form

FIG. 10 is a view for explaining another manufacturing method of the element of the present invention, and is a view for explaining a cross section. As in FIG. 9, the method shown in FIG. so,
The functional layer 125 is formed on the pattern forming body 101. Next, as shown in FIG. 10B, the element forming base material 129 is closely attached. Next, as shown in FIG. 10C, the functional layer 125 is transferred onto the element forming base material 129 to form an element having the functional layer 128.

FIG. 11 is a diagram for explaining another manufacturing method of the device of the present invention, and is a diagram for explaining a cross section. As shown in FIG. 11A, a pattern forming body 101 having a photocatalyst containing layer 104 provided on a base material 102 is subjected to exposure 106 according to a pattern of an element to be formed by using a photomask 120 to perform an lipophilic portion. 113 is formed. Next, as shown in FIG. 11B, the surface on which the heat-fusible composition layer of the thermal transfer member 132 having the heat-fusible composition layer 131 formed on the sheet 130 is in close contact with the exposed surface of the pattern-formed body. .

Next, as shown in FIG. 11C, the heating plate 133 is pressed from the sheet side of the thermal transfer member 132.
Next, as shown in FIG. 11D, the thermal transfer member 132 was peeled off after cooling, and finally a pattern 105 as shown in FIG. 11E was formed.

FIG. 12 is a view for explaining another manufacturing method of the element of the present invention, and is a view for explaining a cross section. As shown in FIG. 12A, the pattern forming body 101
Was exposed using a photomask 120, and the lipophilic portion 113 was formed by the exposure. As shown in FIG. 12B, the ultraviolet curable resin composition 136 is discharged from the discharge nozzle 135 toward the lipophilic portion 113.

As shown in FIG. 12C, the ultraviolet curable resin composition discharged to the exposed portion rises due to the difference in interfacial tension due to the difference in wettability between the unexposed portion and the exposed portion. Then, as shown in FIG. 12D, the microlenses 138 can be formed by irradiating ultraviolet rays 137 for curing.

Hereinafter, a method for manufacturing a color filter of the present invention will be described with reference to the drawings. FIG. 13 is a longitudinal sectional view showing an example of the embodiment of the color filter of the present invention. FIG.
In the color filter 201 of the present invention, the transparent substrate 202, the photocatalyst containing layer 203 as a wettability changing component layer formed on the transparent substrate 202, and the photocatalyst containing layer 203 changed from oil repellency to lipophilicity. A black matrix (light-shielding layer) 204 formed on the site, a colored layer 205 of a plurality of colors,
04 and a protective layer 206 formed so as to cover the coloring layer 205. In this color filter 201,
The black matrix 204 is located at the boundary of the coloring layer 205.

FIG. 14 is a schematic vertical sectional view showing another example of the embodiment of the color filter of the present invention. In FIG. 14, the color filter 211 of the present invention is
2. Black matrix (light shielding layer) 214 formed on transparent substrate 212, Black matrix 2
Photocatalyst-containing layer 213 as a wettability changing component layer formed on transparent substrate 212 so as to cover 14, and composed of a plurality of colors formed on a portion of photocatalyst-containing layer 213 that has changed from oil-repellent to lipophilic. The color filter 215 includes a coloring layer 215 and a protective layer 216 formed so as to cover the coloring layer 215. In the color filter 211, the black matrix 214 is located at the boundary of the coloring layer 215.

FIG. 15 is a longitudinal sectional view showing another example of the embodiment of the color filter of the present invention. In FIG. 15, the color filter 221 of the present invention is
2. Black matrix (light shielding layer) 224 formed on transparent substrate 222, Black matrix 2
24, formed sequentially on the transparent substrate 222 so as to cover
Photocatalyst containing layer 223a as first wettability changing component layer
A laminate comprising a red coloring layer 225R formed on the portion of the photocatalyst containing layer 223a that has changed from oil repellent to lipophilic, a photocatalyst containing layer 223b as a second wettability changing component layer, and a photocatalyst containing layer. Green colored layer 22 formed on the portion of layer 223b that has changed from oleophobic to lipophilic
5G, a laminate comprising a photocatalyst containing layer 223c as a third wettability changing component layer and a blue colored layer 225B formed on a portion of the photocatalyst containing layer 223c which has changed from oil repellent to lipophilic. Body and coloring layer 225
And a protective layer 226 formed so as to cover. In this color filter 221, the black matrix 2
Reference numeral 24 is located at the boundary of the coloring layer 225.

FIG. 16 is a longitudinal sectional view showing another example of the embodiment of the color filter of the present invention. In FIG. 16, the color filter 231 of the present invention includes a transparent substrate 23.
2. A photocatalyst containing layer 233a as a first wettability changing component layer formed on the transparent substrate 232, and a black matrix formed on a portion of the photocatalyst containing layer 233a which has changed from oil repellent to lipophilic. The light-shielding layer) 234 and the photocatalyst-containing layer 233b as a second wettability changing component layer formed sequentially on the first photocatalyst-containing layer 233a so as to cover the black matrix 234 and the oil repellency of the photocatalyst-containing layer 233b A laminate composed of the red colored layer 235R formed on the portion changed to lipophilic, the photocatalyst containing layer 233c as the third wettability changing component layer, and the lipophilicity of the photocatalyst containing layer 233c is changed from oleophobic to lipophilic. Green colored layer 23 formed on specific wettability site on changed site
5G, a laminate comprising a photocatalyst containing layer 233d as a fourth wettability changing component layer and a blue colored layer 235B formed on a portion of the photocatalyst containing layer 233d which has changed from oil repellent to lipophilic. Body and coloring layer 235
And a protective layer 236 formed so as to cover. In the color filter 231, the black matrix 234 is located at the boundary of the coloring layer 235.

Next, the configuration of the above-described color filter of the present invention will be described. (Transparent substrate) The above color filters 201, 211, 2
Transparent substrates 202, 212, 22 constituting 21, 231
Reference numerals 2 and 232 denote transparent rigid materials having no flexibility such as quartz glass, borosilicate glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. Can be used. Of these, Corning 7059 glass is a material having a low 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 glass. It is suitable for a color filter for a color liquid crystal display device according to the method.

(Wetability changing component layer) The photocatalyst containing layers 203, 213, and 22 as the wettability changing component layers constituting the color filters 201, 211, 221, and 231 are also provided.
Reference numerals 3 and 233 denote a layer composed of at least a binder and a photocatalyst, and changed from oil repellency to lipophilicity by the action of the photocatalyst by light irradiation.

As this layer, the same layer as described in the description of the functional element is used. The photocatalyst-containing layers 203, 213, 223, and 233 constituting the color filters 201, 211, 221, and 231 are formed by dispersing a photocatalyst and a binder in a solvent together with other additives as necessary to prepare a coating solution. It can be formed by applying this coating solution. As the solvent 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, and contains a UV-curable component as a binder. In this case, the photocatalyst-containing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.

The content of the photocatalyst in the photocatalyst containing layer is 5 to 5.
It can be set in the range of 60% by weight, preferably in the range of 20 to 40% by weight.
m or less is preferable.

In the present invention, the color filters 201, 21
As the wettability changing component layer constituting 1, 221, 231, an organic polymer resin layer can be used in addition to the photocatalyst containing layer as described above. Organic polymers such as polycarbonate, polyethylene, polyethylene terephthalate, polyamide, and polystyrene are irradiated with ultraviolet rays, particularly ultraviolet rays containing a large amount of low-wavelength components of 250 nm or less, whereby the polymer chains are cut to reduce the molecular weight. The surface becomes rough and becomes lipophilic. By utilizing this, a large difference is generated in the wettability between the light-irradiated portion and the non-light-irradiated portion, and the color filter is obtained by increasing the receptivity and repulsion with the composition for the light-shielding layer and the composition for the colored layer. be able to.

(Black Matrix) The black matrix 20 constituting the color filters 201 and 231
4 and 234 are formed at portions of the photocatalyst-containing layer 203 and the first photocatalyst-containing layer 233a which have changed from oleophobic to lipophilic, respectively. Located outside the area. Such black matrices 204 and 234 are layers containing carbon fine particles such as carbon black, metal oxides, inorganic pigments, organic pigments and the like in a resin binder, and the thickness is set within a range of 0.5 to 10 μm. As the resin binder that can be used, one or a mixture of two or more of polyimide resin, acrylic resin, epoxy resin, and the like can be used.

The black matrices 214 and 224 forming the color filters 211 and 221 are provided outside the boundaries between the display layers of the colored layers 215 and 225 and outside the region where the colored layers are formed. Such black matrices 214 and 224 are formed by forming a metal thin film of chromium or the like having a thickness of about 100 to 200 nm by a sputtering method, a vacuum evaporation method, or the like, and patterning this thin film, and light-shielding particles such as carbon fine particles. A resin layer made of polyimide resin, acrylic resin, epoxy resin, etc. containing
Any of those formed by forming a photosensitive resin layer containing light-shielding particles such as carbon fine particles and metal oxides and patterning the photosensitive resin layer may be used.

(Coloring layer) Coloring layers 205, 215, 22
Nos. 5, 235 are formed in the photocatalyst-containing layer at the portion where the lipophilicity has changed from oleophobic to lipophilic. It is a layer made of a coloring agent such as a pigment or a dye, or a layer containing these colored layers in a resin binder. As the resin binder, one or a mixture of two or more of polyimide resin, acrylic resin, epoxy resin, and the like can be used. The pattern shape of the red pattern, the green pattern, and the blue pattern constituting the colored layer may be any arrangement such as a stripe type, a mosaic type, a triangle type, and a four-pixel arrangement type.

(Protective Layer) Protective layers 206, 216 and 22
Numerals 6 and 236 are provided to flatten the surface of the color filter and to prevent the coloring layer or components contained in the coloring layer and the photocatalyst from being eluted into the liquid crystal layer. The thickness of this protective layer can be set in consideration of the light transmittance of the material used, the surface condition 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 by using, for example, a known transparent photosensitive resin, a two-component curable transparent resin, or the like having a light transmittance required for the transparent protective layer.

Next, a method of manufacturing a color filter according to the present invention will be described with reference to FIG. 17 using the color filter 201 shown in FIG. 13 as an example. First Embodiment (First Step) First, as a first step, the transparent substrate 20
A photocatalyst containing layer 203 as a wettability changing component layer is formed on 2 (FIG. 17A). The photocatalyst containing layer 203 is formed by dispersing the photocatalyst and the binder as described above together with other additives as necessary in a solvent to prepare a coating solution, applying the coating solution, and then hydrolyzing and dehydrating. It can be formed by advancing the condensation reaction to firmly fix the photocatalyst in the binder. The solvent used is preferably an alcoholic organic solvent such as ethanol or isopropanol, and the coating can be performed by a coating method such as spin coating, spray coating, dip coating, roll coating, or bead coating.

Next, the black matrix forming portion of the photocatalyst containing layer 203 is irradiated with light, and the light irradiated portion 203 'is irradiated.
Is formed from oil repellency to lipophilicity by the action of a photocatalyst (FIG. 17B). This light irradiation is performed by a mercury lamp through a photomask for black matrix,
Pattern irradiation using metal halide lamp, xenon lamp, or the like may be performed, or drawing irradiation may be performed in a black matrix pattern shape using a laser such as excimer or YAG. The wavelength of light used for this light irradiation is 400 n
m, preferably from 380 nm or less, and the irradiation amount in light irradiation is the irradiation amount necessary for the light irradiation part 203 ′ to exhibit lipophilicity by the action of a photocatalyst. .

Next, a black matrix paint is adhered onto the light-irradiated portion 203 'and cured to form a black matrix 204 (FIG. 17C). The adhesion of the black matrix composition on the light irradiation site 203 '
The coating can be performed by applying a coating material on the photocatalyst containing layer 203 by a known coating method such as spray coating, dip coating, roll coating, or bead coating. In this case, the applied paint is repelled and removed at the non-light-irradiated portion exhibiting oil repellency, and selectively adheres only to the light-irradiated portion (specific wettability portion) 203 'exhibiting lipophilicity.

The adhesion of the black matrix composition on the light irradiation site 203 'may be performed by a nozzle discharge method such as ink jet. In this case, the black matrix composition supplied into the light-irradiated portion 203 'by nozzle discharge uniformly diffuses and adheres to the light-irradiated portion 203' showing lipophilicity, and also adheres to the non-light-irradiated portion showing oil repellency. Does not spread. Further, even if the paint supplied by the nozzle discharge protrudes from the light-irradiated portion 203 ', it is repelled by the non-light-irradiated portion exhibiting oil repellency and adheres to the light-irradiated portion 203'.

Further, the formation of the black matrix 204 may be performed by a film forming method utilizing vacuum. That is, a metal thin film is formed on the photocatalyst-containing layer 203 after light irradiation by an evaporation method or the like, and the non-light-irradiated portion and the light-irradiated portion 203 ′ are formed.
Using the difference in the adhesive force of the black matrix 2 to form a pattern by peeling using an adhesive tape, solvent treatment, etc.
04 can be formed.

(Second Step) Next, the photocatalyst containing layer 203
Light irradiation is performed on the formation portion of the upper red pattern 205R,
A specific lipophilic site is formed by making the light irradiation site 203 ′ lipophilic by the action of a photocatalyst (FIG. 17).
(D)). This light irradiation may be any of pattern irradiation and optical drawing irradiation, as in the above-described black matrix forming step (first step). Next, a red pattern paint is supplied to the photocatalyst containing layer 203. The supply of the coating material may be any of a coating method, a nozzle discharge method such as an inkjet method, a film forming method using vacuum, and the like, similarly to the black matrix forming step (first step). The supplied paint is a black matrix 20
4 and the non-light-irradiated portion exhibiting oil repellency are repelled and removed, and selectively adhere to only the light-irradiated portion 203 'exhibiting lipophilicity. Then, the red pattern paint adhered on the light irradiation part 203 ′ is cured to form a red pattern 205R (FIG. 17E). Note that the red pattern 205R
Is formed by a film forming method using a vacuum, a paint thin film for a red pattern is formed on the photocatalyst-containing layer 203 after light irradiation by an evaporation method or the like, and a non-light-irradiated portion and a light-irradiated portion 2 are formed.
Using the difference in adhesive strength of 03 ′, patterning is performed by peeling using an adhesive tape, solvent treatment, etc.
Form 5R.

By repeating the same operation as that for forming the red pattern, the green pattern 205G and the blue pattern 205 are formed.
B, a colored layer 205 composed of a red pattern, a green pattern, and a blue pattern is formed, and the protective layer 206 is formed on the colored layer 205, whereby the color filter 201 shown in FIG. FIG. 17 (F)).
When the nozzle discharge method is used in the second step and the pattern (pixel) of each color is surrounded by the black matrix 204, the photocatalyst containing layer 20 on which the black matrix 204 is formed in the first step is used.
3 is irradiated with light to make it lipophilic by the action of a photocatalyst. Thereafter, a coating material for a colored pattern is supplied from a nozzle to each pattern forming portion of each color to be uniformly diffused and adhered, and then subjected to a curing treatment. A colored layer may be formed. When an organic polymer resin layer is used as the wettability changing component layer, light irradiation is performed using ultraviolet light containing a large amount of low wavelength components of 250 nm or less.

Second Embodiment Next, a second embodiment of the color filter manufacturing method of the present invention will be described with reference to FIG. 18 using the color filter 211 shown in FIG. 14 as an example. (First Step) First, as a first step, a photocatalyst containing layer 213 is formed on a transparent substrate 212 on which a black matrix 214 has been previously formed (FIG. 18A). The formation of the photocatalyst containing layer 213 can be performed in the same manner as the formation of the photocatalyst containing layer in the first embodiment described above.

Next, light is irradiated to the portion where the red pattern is formed on the photocatalyst containing layer 213, and the light irradiation portion 213 ′ is changed from oil repellency to lipophilicity by the action of the photocatalyst to form a specific wettability portion. (FIG. 18B). This light irradiation may be either pattern irradiation or light drawing irradiation, as in the black matrix forming step (first step) in the first embodiment described above.

(Second Step) Next, a paint for a red pattern is supplied to the photocatalyst containing layer 213. This paint is supplied by any of a coating method, a nozzle discharge method such as an inkjet method, a film forming method using a vacuum, and the like, like the black matrix forming step (first step) in the first embodiment described above. The supplied paint, which may be present, is repelled and removed at the non-light-irradiated portions exhibiting oil repellency, and selectively adheres only to the light-irradiated portions 2131 exhibiting lipophilicity. Then, the red pattern paint adhered on the light irradiation part 213 ′ is cured to form a red pattern 215R (FIG. 1).
8 (C)), the same operation as the above-described formation of the red pattern is repeated, and the green pattern 215G and the blue pattern 215 are formed.
B, a colored layer 215 composed of a red pattern, a green pattern, and a blue pattern is formed, and a protective layer 216 is formed on the colored layer 215, thereby obtaining the color filter 211 shown in FIG. FIG. 18 (D)).

In the case where the nozzle discharge method is used in the second step and the black matrix 214 is formed so as to surround the pattern (pixel) of each color, the black matrix 214 is covered in the first step. As shown in FIG. 19, the entire surface of the photocatalyst containing layer 213 formed on the transparent substrate 212 is covered with a light-shielding pattern (shaded in FIG. 19) having a line width (w) smaller than the line width (W) of the black matrix 214. Illuminated by a photocatalyst by irradiating light through a mask M having the following formula (1), and thereafter, a colored pattern paint is supplied from a nozzle to each pattern forming portion of each color to be uniformly diffused and adhered, and then cured. A treatment may be performed to form a colored layer. When an organic polymer resin layer is used as the wettability changing component layer, 25
Light irradiation is performed using ultraviolet light containing a large amount of low wavelength components of 0 nm or less.

Third Embodiment Next, a third embodiment of the color filter manufacturing method of the present invention will be described with reference to FIG. 20 using the color filter 221 shown in FIG. 15 as an example. First, a first photocatalyst-containing layer 223a is formed on a transparent substrate 222 on which a black matrix 224 has been formed in advance, and a light-irradiated portion 223′a Is changed from oleophobic to lipophilic by the action of a photocatalyst to form an oleophobic site (FIG. 20A). The formation of the first photocatalyst containing layer 223a is based on the photocatalyst containing layer 203 in the first embodiment described above.
The light irradiation on the first photocatalyst containing layer 223a is performed in the same manner as the black matrix forming step (first step) in the first embodiment described above. Any of optical drawing irradiation may be used. Next, a paint for a red pattern is supplied to the first photocatalyst containing layer 223a. This paint is supplied in the same manner as the black matrix forming step (first step) in the first embodiment described above. And any of a nozzle discharge method such as an inkjet method, a film forming method using a vacuum, and the like. The supplied paint is repelled and removed at the non-light-irradiated portion exhibiting oil repellency, and selectively adheres only to the light-irradiated portion 223'a exhibiting lipophilicity. Then, the red pattern paint adhered on the light irradiation part 223′a is cured to form a red pattern 225R (FIG. 20).
(B)). Thereby, the first photocatalyst containing layer 223a
And a light irradiation site 223′a of the photocatalyst containing layer 223a.
A laminate with the red pattern 225R formed on the transparent substrate 222 is formed on the transparent substrate 222.

In the same manner as in the formation of the red pattern, a second photocatalyst containing layer 223b is formed.
Light is irradiated to the formation part of the green pattern 225G on 3b, and the light irradiation part 223'b is changed from oil repellency to lipophilicity by the action of a photocatalyst to form a lipophilic part (FIG. 20C). A green pattern paint is adhered to the light-irradiated portion 223'b and cured to form a green pattern 225.
G is formed (FIG. 20D). Thereby, a laminate of the second photocatalyst containing layer 223b and the green pattern 225G formed on the light irradiation portion (lipophilic portion) 223′b of the photocatalyst containing layer 223b is formed on the transparent substrate 222. .

By repeating the same operation, the laminate of the third photocatalyst-containing layer 223c and the blue pattern 225B formed on the light-irradiated portion (lipophilic portion) 223'c of the photocatalyst-containing layer 223c is transparently formed. It is formed over a substrate 222.
Thus, a color layer 225 composed of a red pattern, a green pattern, and a blue pattern is formed, and a protective layer 226 is formed on the color layer 225, whereby the color filter 221 shown in FIG. 15 is obtained (FIG. 20). (E)).
When an organic polymer resin layer is used as the wettability changing component layer, light irradiation is performed using ultraviolet light containing a large amount of low wavelength components of 250 nm or less.

Fourth Embodiment Next, a fourth embodiment of the color filter manufacturing method of the present invention will be described with reference to FIG. 21 using the color filter 231 shown in FIG. 16 as an example. (First Step) First, as a first step, the transparent substrate 23
A first photocatalyst containing layer 233a is formed on the photocatalyst 2, and a portion of the black matrix on the photocatalyst containing layer 233a is irradiated with light, and the light irradiated portion 233'a is changed from oleophobic to lipophilic by the action of a photocatalyst. By doing so, a specific wettability site is formed (FIG. 21A). The formation of the first photocatalyst containing layer 233a is performed in the same manner as the formation of the photocatalyst containing layer 203 in the first embodiment. be able to. The light irradiation on the first photocatalyst containing layer 233a is performed by pattern irradiation and light irradiation similarly to the black matrix forming step (second step) in the first embodiment.
Any of optical drawing irradiation may be used.

Next, a black matrix paint is adhered onto the light irradiation site 233'a and cured to form a black matrix 234 (FIG. 21B). The adhesion of the black matrix composition onto the light irradiation site 233′a is performed in the same manner as the black matrix forming step (first step) in the above-described first embodiment, such as a coating method, a nozzle discharge method such as an inkjet method, or the like. Any of a film formation method using a vacuum or the like may be used.

(Second Step) A second photocatalyst containing layer 233b is formed on the first photocatalyst containing layer 233a so as to cover the black matrix 234 formed in the first step.
Light-irradiation is performed on the portion where the red pattern is formed on the photocatalyst-containing layer 233b, and the light-irradiated portion 233'b is changed from oil-repellent to lipophilic by the action of a photocatalyst, thereby forming a lipophilic portion (FIG. C)). Second photocatalyst containing layer 2
The formation of the first photocatalyst-containing layer 233a can be performed in the same manner as the formation of the first photocatalyst-containing layer 233a described above. The light irradiation on the second photocatalyst-containing layer 233b can be performed on the first photocatalyst-containing layer 233a. Like pattern irradiation,
Any of optical drawing irradiation may be used. Next, a paint for a red pattern is supplied to the second photocatalyst containing layer 233b. The supply of the paint may be performed by any of a coating method, a nozzle discharge method such as an inkjet method, a film forming method using a vacuum, and the like in the same manner as the black matrix forming step (second step) in the first embodiment. It may be. The supplied paint is repelled and removed at the black matrix 234 and the non-light-irradiated portion exhibiting oil repellency, and selectively adheres only to the light-irradiated portion 233'b exhibiting lipophilicity. And
The red pattern paint 235R is formed by curing the red pattern paint adhered on the light irradiation site 233'b (FIG. 21).
(D)). Thereby, the second photocatalyst containing layer 233b
And a light irradiation part 233′b of the photocatalyst containing layer 233b.
The laminate with the red pattern 235R formed on the first
Is formed on the photocatalyst containing layer 233a.

By repeating the same operation, the third photocatalyst containing layer 233c and the green pattern 235 'formed on the light irradiated portion 233'c of the photocatalyst containing layer 233c are formed.
G is formed on the second photocatalyst-containing layer 233b, and a fourth photocatalyst-containing layer 233d and a blue pattern 235B formed on a light-irradiated portion 233'd of the photocatalyst-containing layer 233d are formed. A laminate is formed on the third photocatalyst containing layer 233c. Thus, a color layer 235 composed of a red pattern, a green pattern, and a blue pattern is formed, and the protective layer 236 is formed on the color layer 235, whereby the color filter 231 shown in FIG. 16 is obtained (FIG. 21). (E)).

As described above, in the present invention, the black matrix composition and the composition for the colored layer can be selectively adhered only to the portions where the black matrix and the colored layer are to be formed. It will be expensive.

When an organic polymer resin layer is used as the wettability changing component layer, light irradiation is performed using ultraviolet rays containing a large amount of low wavelength components of 250 nm or less. A method for forming a pattern such as a microlens based on a difference in wettability will be described.

(Wetability) The substrate in the present invention has a wettability which is distinguished into a portion to which a liquid containing a material for forming a lens (hereinafter also referred to as a lens composition) adheres and a portion to which no liquid adheres. They have gender differences.

(Method of Changing Wettability) The method of changing the wettability of the substrate surface and forming a pattern includes a method of modifying the surface of the substrate and a method of partially coating a film having different wettability on the surface of the substrate. A method of forming, a method of partially removing the film on the substrate surface to form a portion having different wettability, a method of forming a film on the entire substrate surface and partially modifying the film, and the like.
There is no particular limitation.

Among these, a preferred method is to form a coating on the entire surface of the substrate and partially modify the coating.
In particular, the method of forming a photocatalyst-containing layer whose wettability changes by light irradiation on the entire surface of the base material and forming a pattern by light irradiation does not require development, and does not generate dust accompanying transfer or removal at the time of pattern formation. It is more preferable in that it can form a portion having a different wettability without a large step, has an advantage that the material is inexpensive, and can mass-produce fine lenses with high precision.

(Pattern Shape) The portion to which the lens composition is adhered may be either the portion where the wettability has changed or the portion where the wettability has not changed, and the pattern shape is such that the lens can be formed. It is not particularly limited. Preferably, the pattern shape for attaching the lens composition may be a square, a circle, a regular hexagon, or the like. The number of portions to which the lens composition is adhered can be any number, but it is preferable to provide a large number of adhered portions regularly.

The size of the pattern can be appropriately designed according to the application. The method for manufacturing a lens according to the present invention is also characterized in that a fine microlens can be formed, and the minute one can be, for example, 2 μm in diameter.
In addition, the area ratio between the lens composition adhering portion and the non-adhering portion is not limited, but is, for example, 10,000: 1 to 1: 10000.
Can be

(Lens) (Material for Forming Lens) The material constituting the lens of the present invention can be cured after being attached to the substrate as a liquid, and after curing, functions as a lens according to the intended use. Transparent materials that can be used.

Examples of such a material include a combination of a photocurable resin and a photopolymerization initiator, and a thermosetting resin. Of these, a photocurable resin such as an ultraviolet curable resin is preferable in that curing is easy and quick, and since a heating operation is not required at the time of curing, the temperature of the lens forming material and the substrate does not become high. In addition, when the above-described material is colored with a coloring agent to form a colored lens having a color filter function, the coloring agent may be a dye, an inorganic pigment,
And organic pigments.

Specific examples of such materials include the following. (Ultraviolet curable resin composition) Having at least one or more functional groups, ion polymerization or radical polymerization by ions or radicals generated by irradiating a photopolymerization initiator with a curing energy beam increases the molecular weight. Monomers and oligomers that form a crosslinked structure. The functional group referred to herein is an atomic group such as a vinyl group, a carboxyl group, a hydroxyl group, or a bonding mode.

(Monomer, Oligomer) Examples of such a monomer or oligomer include acrylic type such as epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate and silicone acrylate, and unsaturated polyester-styrene type,
A non-acrylic type such as a polyene-thiol type may be mentioned. In particular, an acrylic type is preferable from the viewpoint of a curing speed and a wide range of physical properties. Representative examples of the acrylic type are shown below.

(Monofunctional group) 2-ethylhexyl acrylate, 2-ethylhexyl ethylene oxide adduct, ethoxydiethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone adduct of 2-hydroxyethyl acrylate, 2 -Phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, nonylphenol ethylene oxide adduct, acrylate obtained by adding caprolactone to nonylphenol ethylene oxide adduct, 2-hydroxy-3-phenoxypropyl acrylate, tetrahydrofurfuryl acrylate, caprolactone adduct of furfuryl alcohol, acryloylmorpholine , Dicyclo Integrators sulfonyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl oxyethyl acrylate, isobornyl acrylate, 4,4
Acrylate of caprolactone adduct of dimethyl-1,3-dioxolan, 3-methyl-5,5-dimethyl-
An acrylate of a caprolactone adduct of 1,3-dioxolane can be exemplified.

(Polyfunctional groups) Hexanediol diacrylate, neopentyl glycol diacrylate,
Polyethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol hydroxypivalate diester diacrylate, caprolactone adduct of neopentyl glycol hydroxypivalate diacrylate, acrylic acid adduct of diglycidyl ether of 1,6-hexanediol , A diacrylate of an acetal compound of hydroxypivalaldehyde and trimethylolpropane, 2,2-bis [4
-(Acryloyloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloyloxydiethoxy) phenyl] methane, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, Trimethylolpropane propylene oxide adduct triacrylate, glycerin propyleneoxy adduct triacrylate, dipentaerythritol hexaacrylate pentaacrylate mixture, dipentaerythritol caprolactone adduct acrylate, tris (acryloyloxyethyl) isocyanurate, 2-acryloy Roxyethyl phosphate and the like can be mentioned.

(Photopolymerization Initiator) As the photopolymerization initiator used in the present invention, various types can be used.
For example, the following can be mentioned. -Carbonyl compounds Examples include acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin ether, benzyldimethyl ketal, benzoin benzoate, and α-acyloxime esters. -Sulfur compounds Tetramethylthiuram monosulfide, thioxanthones and the like can be mentioned. -Phosphorus compound 2,4,6-trimethylbenzoyldiphenylphosphinoxide and the like.

(Thermosetting Resin Composition) It is possible to use a thermosetting resin composition which is cured by the action of thermal energy and has a strength after curing that functions as a light-shielding spacer. Representative examples include polycarbonate, polymethyl methacrylate, methyl phthalate homopolymer or copolymer, polyethylene terephthalate, polystyrene, diethylene glycol bisallyl carbonate, acrylonitrile-styrene copolymer, methyl methacrylate-
Styrene copolymer, poly (4-methylpentene-1) and the like can be mentioned.

(Coloring Agent) The lens of the present invention can be colored by a method such as dissolving a dye or dispersing a pigment in a material forming the lens. The coloring agent that can be used in the present invention may be any of dyes, organic pigments, and inorganic pigments, and those commonly used in colored filters can be used.Among them, a high concentration can be given, and when the lens is cured, A material that does not easily cause fading during use is preferable, and examples thereof include the following.

Azo dyes, anthraquinone dyes, indigoid dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, quinoline dyes, nitro dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes Dyes, perinone dyes,
Dyes such as pyrylium dyes, thiapyrylium dyes, azurenium dyes, and squarylium salt dyes; Dianthraquinone, halogenated copper phthalocyanine, copper phthalocyanine, other phthalocyanine pigments, perylene pigments, polycyclic quinone pigments such as pyranthrone pigments, indigo pigments, quinacridone pigments, pyrrole pigments, pyrrolopyrrole pigments, azo pigments Organic pigments such as pigments. Any other materials that meet the conditions as a colorant can be used. The above colorants can be used in any combination and in any ratio unless otherwise specified.

(Lens Composition) The lens composition is not particularly limited as long as it contains a raw material for forming the above-described lens. Examples of the form of the lens composition include a liquid composed of a monomer and a polymerization initiator, a liquid in which the monomer and the polymerization initiator are dissolved or dispersed, a liquid composed of an oligomer and a polymerization initiator, and a liquid composed of an oligomer and a polymerization initiator. Examples thereof include those in which the monomer or oligomer is dissolved or dispersed and those in which the polymerization initiator is dissolved or dispersed. In addition, as a raw material liquid for forming a colored lens, a liquid in which a coloring agent is dissolved or dispersed in the above-described raw material liquid is used.

(Adjustment of Lens Focal Length) One of the major features of the lens manufacturing method of the present invention is that it is extremely easy to adjust the focal length of the lens, that is, to change the curvature.

Adjustment of the focal length of the lens according to the present invention will be described with reference to FIG. A photocatalyst containing layer 303 that is oil-repellent to the lens composition on the transparent substrate 301.
Is formed on a part of the photocatalyst-containing layer 303. The photocatalyst-containing layer (hereinafter, denatured) has a high lipophilicity with the lens composition and has a changed wettability corresponding to a portion to which the lens composition is adhered. A photocatalyst containing layer 303 ′) is provided. Further, a lens composition 302 is attached on the modified photocatalyst containing layer 303 '. FIG. 22 (A)
Is an example in which a small amount of the lens composition 302 is adhered,
Even if the amount of the lens composition 302 is small, the composition spreads over the entire modified photocatalyst containing layer 303 ', so that a microlens with a small curvature and a long focal length can be formed. FIG.
FIG. 22B is an example in which a medium amount of the lens composition is attached, and a microlens having a higher curvature and a shorter focal length is formed as compared with FIG. 22A. Is
This is an example in which the lens composition is adhered in a large amount. Even when the lens composition 302 is in a large amount, the lens composition does not spread to the oil-repellent photocatalyst-containing layer 303, and the focal length with a high curvature is short. A micro lens is formed.

As described above, according to the lens manufacturing method of the present invention, there is an advantage that the focal length of the microlens can be easily controlled by the amount of adhesion of the lens composition per one place. In addition, since the size of the bottom surface is determined by the size of the pattern, there is an advantage that the size of the bottom surface does not change even when the amount of the lens composition changes. In addition, even if the position where the lens composition is initially attached is slightly shifted, the position of the lens composition is corrected to the position of the pattern due to the difference in wettability, so that a microlens array with extremely high positional accuracy is manufactured. It is excellent in that it can.

(Adhesion of Lens Composition by Coating) In the method for producing a lens of the present invention, the lens composition can be attached by coating the surface of a substrate. In performing this coating, specifically, for example, dip coating, roll coating, bead coating, spin coating, air doctor coating, blade coating, knife coating, rod coating, gravure coating, rotary screen coating,
Kiss coating, slot orifice coating,
Methods such as spray coating, cast coating, and extrusion coating can be used, and these are advantageous in that a large amount of lens shapes can be produced in a short time.

In the case of a colored lens array of a plurality of colors, a step of forming a pattern due to the difference in wettability on the surface of the base material and the step of attaching the colored lens composition by the coating method according to each of the above methods. It can be manufactured by repeating the step of curing and, if necessary, the step of curing the lens composition one by one for the required number of colors.

(Adhesion of Lens Composition by Nozzle Discharge)
In the method for producing a lens of the present invention, the lens composition can be attached to the surface of the base material by nozzle discharge. In performing this ejection, specifically, for example, a micro-syringe, a dispenser, an ink jet, a method in which the lens composition is ejected from the needle tip by an external stimulus such as an electric field, and a vibration element such as a piezo element that vibrates by the external stimulus is used. A method of flying the lens composition from the element, a method of attaching the lens composition attached to the needle tip to the base material surface, and the like, which have a large contact angle and a high height. This is advantageous in that a lens-shaped object is created.

When a colored lens array of a plurality of colors is manufactured, nozzles of the required number of colors are used by the above-described methods, and a colored material containing a material for forming a lens of each color from each nozzle is used. The composition for a lens thus obtained can be attached to the surface of a base material by nozzle discharge.

In the case of manufacturing a colored lens array of a plurality of colors using a single-color nozzle, a step of forming a pattern due to a difference in wettability on the surface of the base material and a nozzle discharge by each of the above-described methods. It can also be manufactured by repeating the step of attaching the colored lens composition and, if necessary, the step of curing the lens composition for the required number of colors.

(Microlens Array) In the method of manufacturing a lens of the present invention, a microlens array can be manufactured preferably by arranging microlenses regularly. The arrangement of the microlens array corresponds to the pattern due to the difference in wettability, and the shape of the bottom surface of the microlens also corresponds to the pattern due to the difference in wettability. The precision of the shape is high. In addition, since the lens composition can be attached only to the lipophilic portion, a microlens with stronger adhesion and higher strength can be manufactured in that case. In addition, since the contact surface can be designed not only in a circular shape but also in a polygonal shape, it is possible to reduce the area of parts other than the lens-shaped object compared to a circular lens, and to achieve a high aperture ratio of a micro lens. Arrays can be easily manufactured.

By attaching the colored lens composition, a colored microlens array having high position and shape accuracy, high adhesion and strength, and high aperture ratio can be easily manufactured in the same manner as the above-mentioned microlens. be able to.

FIG. 23 is a sectional view of a microlens array according to a preferred embodiment of the present invention. Substrate 301
A photocatalyst containing layer 303 and a modified photocatalyst containing layer 303 ′ having changed wettability are formed thereon, and a lens 302A is formed on the unmodified photocatalyst containing layer 303.

FIG. 24 is a sectional view of a colored microlens array according to a preferred embodiment of the present invention.
1, a photocatalyst containing layer 303 and a modified photocatalyst containing layer 303 ′ having changed wettability are formed, and a colored first color lens 31 is formed on the unmodified photocatalyst containing layer 303.
5, a second color lens 316 and a third color lens 317 are formed.

(Substrate) The material constituting the substrate is not particularly limited as long as it can form a pattern due to the difference in wettability on the surface by itself or by forming a layer and can form a microlens. Not limited. If a transparent material is used as the base material to make it a light-transmitting base material, there is no need to remove the lens from the base material in a later step, which is very effective for manufacturing a microlens array. As a material of such a base material, any of an inorganic material and an organic material may be used as long as it is generally used for manufacturing a microlens array. For example, preferably, soda glass, quartz glass, optical Glass, (such as BSC7 made by HOYA), glass for electronics (such as non-alkali glass) and translucent ceramics, polycarbonate, methyl methacrylate homopolymer or copolymer, polyethylene terephthalate,
Examples thereof include a plastic film such as polystyrene, and a plastic sheet.

The shape and thickness of the base material can be changed according to the intended use, and can be in the form usually used. The photocatalyst-containing layer can be manufactured using the same layer as described above for the formation of the functional layer.

FIG. 25 is a diagram illustrating an example of a method for manufacturing a microlens using the photocatalyst of the present invention. FIG.
As shown in (A), a photocatalyst containing layer 303 is formed on a substrate 301, and irradiation light 305 is irradiated from above on the substrate 301 through a photomask 304, and the modified photocatalyst containing layer 303 ′ is formed.
To form Next, as shown in FIG.
By discharging the lens composition from the discharge nozzle 306 and attaching it to the metamorphic photocatalyst containing layer 303 ', the lens 302
A can be formed.

(Light-Shielding Layer) The light-shielding layer suitably used for the lens of the present invention is formed corresponding to the position and shape of the lens, and is provided so that unnecessary light rays around the lens do not enter the lens. Things. The light shielding layer is more preferably provided on the microlens array.

In a preferred embodiment of the present invention, the method for forming the light-shielding layer is not limited, but preferably the light-shielding layer is formed by using a difference in wettability similarly to the formation of the lens. Specifically, on the back surface of the transparent substrate on which the lens is not formed, a pattern due to a difference in wettability is formed to form a light-shielding layer pattern corresponding to the lens pattern,
A liquid containing a material for forming the light-shielding layer is attached to a portion of the base material where the light-shielding layer pattern has changed from oil-repellent to lipophilic, and light is blocked by curing the liquid containing the material for forming the light-shielding layer. A lens having a layer is manufactured. Examples of the material for forming the light-shielding layer include a light-shielding resin thin film formed using a coating material made of an acrylic thermoplastic resin containing carbon black.

FIG. 26 is a cross-sectional view showing an example of a microlens array having a light shielding layer, which is a preferred embodiment of the present invention. In FIG. 26, a photocatalyst containing layer 303 is provided on a base material 301, a lens 302A is formed on a portion other than the modified photocatalyst containing layer 303 ', and a surface of the base material 301 on which the lens 302A is not formed. A photocatalyst containing layer 303 is also formed on the (back side), and a light shielding layer 307 is provided on the modified photocatalyst containing layer 303 ′.

FIG. 27 is a plan view of a microlens array having such a light-shielding layer as viewed from the surface on which the light-shielding layer is provided. An opening of the light shielding layer 307 is provided corresponding to the center of the lens 302A.

(Application to Imaging Device) The microlens array according to a preferred embodiment of the present invention can be suitably used as a component adjacent to or in close contact with an imaging device such as a CCD in order to enhance the light sensitivity of the imaging device. In this case, it is preferable to provide a light-shielding layer for the purpose of avoiding adverse effects on characteristics such as a decrease in contrast due to stray light. Further, it is preferable to make the photocatalyst-containing layer thinner for the purpose of enhancing the light transmittance or preventing the color formation of the photocatalyst-containing layer due to light interference, and preferably the thickness is 1 μm or less, more preferably 0.1 μm or less. 2μ
m or less.

FIG. 28 is a sectional view showing an example of an image pickup apparatus using a microlens array having such a light-shielding layer. Colored filter 309 and photoelectric conversion element 310
A microlens array 320 having a light-blocking layer 307 is provided on an imaging element portion 318 made of. Incident light 3
08 denotes an imaging element unit 318 via a microlens array.
Incident on.

Further, the colored microlens array according to the preferred embodiment of the present invention can have both the function of the colored filter which is a constituent element of the image pickup device and the function of the microlens array, and has a simple configuration without using the colored filter. Thus, an imaging element having a function of a microlens array can be realized. In this case, it is preferable to provide a light-shielding layer for the purpose of avoiding adverse effects on characteristics such as a decrease in contrast and a decrease in chroma due to stray light. Further, it is preferable to reduce the thickness of the photocatalyst-containing layer, preferably 1 μm, for reasons such as enhancing the light transmittance or preventing the color formation of the photocatalyst-containing layer due to light interference.
FIG. 29 is a cross-sectional view showing an example of an imaging device using a colored microlens array 321 having such a light-blocking layer 307. A light-blocking layer is formed on a photoelectric conversion element. And a colored microlens provided. The incident light 308 enters the photoelectric conversion element 310 via the colored microlens array.

Use for Display The microlens array, which is a preferred embodiment of the present invention, can be suitably used as a component adjacent to or in close contact with a display such as a liquid crystal display in order to increase the luminance in the direction of the viewer. In this case, it is preferable to provide a light-shielding layer in order to suppress the influence of ambient external light such as room illumination and sunlight and to improve display image quality. Also,
In order to enhance the light transmittance, it is preferable to reduce the thickness of the photocatalyst-containing layer for reasons such as preventing color formation of the photocatalyst-containing layer due to light interference, preferably 1 μm or less, more preferably 0.2 μm or less. is there.

FIG. 30 is a cross-sectional view showing an example of a liquid crystal display using the microlens array 320 having such a light shielding layer 307. A microlens having a light shielding layer is provided on a liquid crystal display. Light emitted from the liquid crystal display unit 319 is emitted to the outside through a microlens array as transmitted light 311. Further, a colored microlens array according to a preferred embodiment of the present invention includes a colored filter which is a constituent element of a display; A display having the function of the microlens array can be realized with a simple configuration that does not use a color filter because it can have the functions of the microlens array. It is preferable to provide a light-shielding layer in order to suppress adverse effects and improve display image quality. Further, in order to enhance light transmittance, it is preferable to reduce the thickness of the photocatalyst containing layer for reasons such as preventing color formation of the photocatalyst containing layer due to light interference, and preferably the thickness is 1 μm or less, more preferably 0.2 μm or less.
m or less.

FIG. 31 is a sectional view showing an example of a liquid crystal display using a colored microlens array having such a light shielding layer. A light source 314, a liquid crystal element 313,
Colored microlens array 321 having light shielding layer 307
The light emitted from the light source 314 through the liquid crystal element 313 is emitted to the outside through the colored microlens array 321 as light emission 311.

[0164]

The present invention will be described below with reference to examples. Example A-1 3 g of isopropanol, fluoroalkylsilane (MF-160E manufactured by Tochem Products: 50% by weight solution of N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in isopropyl ether) 0.0014 g, 2 g of a titanium oxide sol inorganic coating agent (STS-03 manufactured by Ishihara Sangyo), and
Stirred at 00 ° C. for 20 minutes. The obtained liquid is 0.7 m thick
m of a non-alkali glass substrate by spin coating to form a photocatalyst-containing layer having a thickness of 0.15 μm. The surface of the obtained photocatalyst-containing layer was 15 mW /
UV irradiation was performed at an illuminance of cm ² (254 nm) for 30 seconds, and the contact angles of the exposed and unexposed portions with respect to n-octane were measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). Shown in

Example A-2 Titanium oxide sol inorganic coating agent (ST manufactured by Ishihara Sangyo Co., Ltd.)
S-01) was applied on an alkali-free glass substrate having a thickness of 0.7 mm by a spin coating method, and a thickness of 0.15 μm was applied.
m of the photocatalyst containing layer was formed. Next, a nonionic surfactant (3M: Florade FC-170) was applied on the photocatalyst-containing layer by a spin coating method, and a thickness of 0.1 nm was applied.
A 1 μm layer was formed. The surface of the photocatalyst-containing layer was 15 m from an ultra-high pressure mercury lamp through a grid-shaped photomask.
UV irradiation was performed at an illuminance of W / cm ² (254 nm) for 120 seconds, and the contact angle with respect to the exposed portion and the unexposed n-octane was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). It is shown in Table 1.

Example A-3 Titanium oxide sol inorganic coating agent (ST manufactured by Ishihara Sangyo Co., Ltd.)
S-01) was applied on an alkali-free glass substrate having a thickness of 0.7 mm by a spin coating method, and a thickness of 0.15 μm was applied.
m of the photocatalyst containing layer was formed. Next, 3 g of isopropanol and fluoroalkylsilane (MF-160E manufactured by Tochem Products: 50% by weight solution of N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in isopropyl ether) were added. 00
14 g and 1 g of water were mixed and stirred at 100 ° C. for 20 minutes. The obtained liquid was applied on the previously prepared photocatalyst-containing layer by spin coating to form a layer having a thickness of 0.11 μm.

The surface of the photocatalyst-containing layer was 15 mW / cm ² by a super-high pressure mercury lamp through a grid-shaped photomask.
(254 nm) for 100 seconds with UV irradiation,
Table 1 shows the results obtained by measuring the contact angle of the exposed portion and the unexposed portion with respect to n-octane using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science).

Example A-4 27 g of isopropanol, 0.15 g of a fluorinated surfactant (ZONYL FSN, DuPont), 0.62 g of tetraethoxysilane, and titanium oxide sol (T
A-15) 0.96 g was mixed and stirred at 100 ° C for 20 minutes. The obtained liquid was applied on a 0.7 mm-thick non-alkali glass substrate by spin coating to form a photocatalyst-containing layer having a thickness of 0.15 μm. The surface of the photocatalyst-containing layer was irradiated with an illuminance of 15 mW / cm ² (254 nm) by an ultra-high pressure mercury lamp through a grid-shaped photomask.
UV irradiation was performed for 0 seconds, and the contact angle of the exposed portion and the unexposed portion to n-octane was measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science), and the results are shown in Table 1.

[0169]

Table 1 Example 1 Example 2 Example 3 Example 4 Exposed part 45 ° 32 ° 43 ° 34 ° Unexposed part 5 ° or less 5 ° or less 5 ° or less 5 ° or less

Example A-5 15% was added to the photocatalyst-containing layer prepared by the method described in Example A-1.
15 mW / cm ² (2) using a mercury lamp through a mask in which light-shielding layers of 0 × 300 μm are arranged at intervals of 30 μm.
Ultraviolet irradiation was performed at an illuminance of 54 nm for 30 seconds. Next, a composition for a light-shielding layer (CK, manufactured by Fuji Film Ohlin)
-2000) was applied to the entire surface of the exposed photocatalyst-containing layer by a blade coater at a blade interval of 40 μm and a speed of 0.6 m / min. In addition, when the surface tension of this composition was measured with a surface tensiometer (PD-Z manufactured by Kyowa Interface Science), it was 32 dyne / cm.

As shown in FIG. 7, the uncoated portion of the obtained coating material was repelled by the composition for a light-shielding pattern, and was selected only for the exposed portion. After irradiation with ultraviolet rays of 300 mJ / cm ² (365 nm), By heating at 200 ° C. for 30 minutes, a grid-like light-shielding pattern was obtained on the glass substrate 102 via the photocatalyst layer 104.

Example A-6 The unexposed and exposed portions of the photocatalyst-containing layer produced by the method described in Example A-1 were subjected to X-ray photoelectron spectroscopy (VG Si).
Element analysis was performed by ESCALAB220-I-XL (entific). Quantitative calculation was performed by the correction of the background of Shary and the correction of the relative sensitivity coefficient of Scofield, and the obtained results are shown in Table 2 as relative values by weight when Ti is set to 100.

[0173]

[Table 2]

Example A-7 15 mW / cm ² by a mercury lamp through a photomask in which a light-shielding layer is arranged at a pitch of 100 μm at a width of 10 μm on the photocatalyst-containing layer prepared by the method described in Example A-1.
(254 nm) for 30 seconds.
Next, a red coloring composition (C
R-2000) with a dispenser (15 made by EFD).
00XL), a red pixel can be formed by spreading only on the exposed portion. The surface tension of this composition was measured using a surface tensiometer (PD-Z manufactured by Kyowa Interface Science).
Was 31 dyne / cm.

Example A-8 Example A-8 was formed on a polyimide film having a thickness of 100 μm.
The same composition as in Example 1 was applied by a spin coater to form a photocatalyst-containing layer having a thickness of 0.15 μm. In addition, width 5
15 mW / cm ² by a mercury lamp through a negative photomask having a circuit pattern drawn at 0 μm.
UV irradiation was performed at an illuminance of (254 nm) for 70 seconds.
Next, the degree of vacuum was 1 × 10 ⁻⁵ T over the entire surface of the obtained transparent substrate.
Aluminum was vacuum deposited at a rate of 4 nm / sec at orr. Further, when the surface of the aluminum thin film was peeled off at a speed of 300 ° / sec at 135 ° using a cellophane adhesive tape (JISZ1522 manufactured by Sekisui), the difference in adhesion between the exposed and unexposed portions of the aluminum thin film and the transparent substrate was observed. Thereby, only the unexposed part peels off the deposited film,
A circuit pattern in which a circuit having a width of 50 μm and a thickness of 0.1 μm was formed was obtained.

Example B-1 (Preparation of Photocatalyst-Containing Layer Composition) First, a coating solution (photocatalyst-containing layer composition) for a photocatalyst-containing layer having the following composition was prepared. (Composition of layer composition containing photocatalyst) ・ Titanium oxide sol solution (ST-K03, manufactured by Ishihara Sangyo): 2 parts by weight ・ Fluoroalkylsilane: 0.3 parts by weight (MF-160E, manufactured by Tochem Products) ・ Isopropanol: 3 parts by weight After mixing these substances, the mixture was heated at 100 ° C. for 60 minutes to obtain a coating solution. The obtained liquid was applied on a 0.7 mm-thick non-alkali glass substrate by a spin coating method to obtain a 0.15 μm-thick photocatalyst-containing layer.

The surface of the photocatalyst-containing layer was 15 mW / cm ² by an ultra-high pressure mercury lamp through a grid-shaped photomask.
UV irradiation was performed at an illuminance of (254 nm) for 50 seconds, and the contact angles of the exposed portion and the unexposed portion with respect to n-octane were measured with a contact angle measuring instrument (CA-Z type manufactured by Kyowa Interface Science). The unexposed area was 52 °, but the exposed area was 5 ° or less.

(Formation of Black Matrix) Next, a photocatalyst containing layer was formed on a transparent substrate as shown in FIG. 17A in the same manner as described above. This photocatalyst-containing layer was irradiated with an ultra-high pressure mercury lamp through a photomask for black matrix provided with a matrix-shaped opening pattern having an opening line width of 30 μm and an illuminance of 15 mW / cm ² (254 nm) as shown in FIG. UV irradiation was performed for 50 seconds as shown. Next, a composition for black matrix (CK-2000, manufactured by Fuji Film Orin) was applied to the entire surface of the photocatalyst-containing layer by a blade coater. The black matrix composition applied in this manner was repelled in the unexposed areas and selectively adhered only to the exposed areas.

This was heated at 80 ° C. for 3 minutes. Subsequently, ultraviolet irradiation was performed at an intensity of 100 mJ / cm ² .
Then, heating was performed at 200 ° C. for 30 minutes to obtain FIG.
The black matrix shown in (C) was formed. Table 4 shows the contact angles of the exposed portions and the unexposed portions of the black matrix composition.

(Formation of Colored Layer) Next, the red pattern region of the photocatalyst-containing layer on which the black matrix was formed was irradiated with ultraviolet rays at an illuminance of 15 mW / cm ² (254 nm) for 50 seconds. Next, when the red pattern composition (CR-2000 manufactured by Fuji Film Orin) was ejected to the exposed portion by an inkjet method, the composition spread out only on the exposed portion and selectively adhered. Similarly, a green pattern composition (CG-2000, manufactured by Fuji Film Orin) and a blue pattern composition (CB-2000, manufactured by Fuji Film Orin)
Was attached. This is heated at 80 ° C. for 3 minutes, then
Ultraviolet irradiation was performed at an intensity of 00 mJ / cm ² . Then
The colored layer was formed by heating at 200 ° C. for 30 minutes. Table 4 shows the contact angles of the exposed and unexposed portions of the colored layer composition.
Shown in

[0181]

[Table 4] CK-2000 CR-2000 CG-2000 CB-2000 Unexposed part 30 ° 32 ° 34 ° 37 ° Exposed part 5 ° or less 5 ° or less 5 ° or less 5 ° or less

(Formation of Protective Layer) Next, a two-part mixed type thermosetting agent (SS7265 manufactured by JSR) is used as the protective layer.
Is applied on the coloring layer with a spin coater,
A hardening treatment was performed for 0 minutes to form a protective layer as shown in FIG. 17 (F), and a color filter of the present invention having the structure shown in FIG. 13 was obtained.

Example B-2 (Formation of Photocatalyst-Containing Layer) Opening 140 μm × 260 μm
The same photocatalyst-containing layer composition as in Example B-1 was applied by a spin coating method onto a 0.7 mm thick non-alkali glass substrate having a black matrix composed of a chromium thin film pattern having a line width of 30 μm. .15 μm
The photocatalyst containing layer shown in FIG. 18A was obtained.

(Formation of Colored Layer) Next, a light-shielding pattern having a line width (20 μm) smaller than the line width (30 μm) of the black matrix was formed with a pattern pitch of 155 μm × 275 μm.
After aligning a mask having a lattice shape on the black matrix by using the above, as shown in FIG. 18 (B), 15 mW / cm ² through an ultra-high pressure mercury lamp through this mask.
UV irradiation was performed at an illuminance of (254 nm) for 50 seconds.

Next, when the red pattern composition (CR-2000, manufactured by Fuji Film Orin) is discharged to the exposed portion by the ink jet method, it spreads only to the exposed portion and spreads out.
It selectively adhered as shown in (C). Similarly, a green pacoon composition (CG-200 manufactured by Fuji Film Olin)
0), blue pattern composition (Fujifilm Olin C
B-2000).

This was heated at 80 ° C. for 3 minutes,
Ultraviolet irradiation was performed at an intensity of 00 mJ / cm ² . Then
The colored layer was formed by heating at 200 ° C. for 30 minutes.

(Formation of Protective Layer) Next, as the protective layer, a two-part mixed type thermosetting agent (SS7265 manufactured by JSR)
Is applied on the coloring layer with a spin coater,
A hardening treatment for 0 minutes was performed to obtain a color filter of the present invention having the structure shown in FIG.

(Evaluation) Observation of each color filter produced in Examples B-1 and B-2 by an optical microscope revealed that defects such as discoloration, color mixture, white spots, and uneven color were observed in the black matrix and the colored layer. I couldn't.

Example C-1 Isopropanol (3 g), fluoroalkylsilane (MF-160E, manufactured by Tochem Products): N- [3- (trimethoxysilyl) propyl] -N-ethyl perfluorooctanesulfonamide isopropyl ether 50 wt. % Solution) and 2 g of a titanium oxide sol inorganic coating agent (STS-03 manufactured by Ishihara Sangyo Co., Ltd.)
Stirred at 0 ° C. for 20 minutes. The obtained liquid is 0.7 mm thick.
Was applied by a spin coating method to form a photocatalyst-containing layer having a thickness of 0.7 mm.

The resulting photocatalyst-containing layer surface was irradiated with an ultrahigh-pressure mercury lamp through a grid-shaped photomask.
UV irradiation was performed for 50 seconds at an illuminance of mW / cm ² (254 nm), and the contact angle of the exposed portion and the unexposed portion to n-octane was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science).
Was measured by The unexposed portion was 56 °, but the exposed portion was 5 ° or less.

Example C-2 A quartz glass transparent substrate was coated with the photocatalyst described in Example C-1.
A layer was formed by a spin coating method. Opening to this
A plurality of circular patterns with a diameter of 50 μm are arranged at intervals of 2 μm
By a mercury lamp through a negative photomask
15mW / cm ^Two (254 nm) exposure for 50 seconds
Transparent base with a highly wettable circular pattern on the surface
Wood was obtained. UV curable monomer (bifunctional acrylate
Monomer: Nippon Kayaku KAYARADPEG400D
A) 500 g, polymerization initiator (Ciba Specialty Chemicals)
Mix 25 g of Darocur 1173 made by Luz and mix for 3 minutes
Stirred.

The obtained liquid mixture was applied to a transparent substrate having a circular pattern having a different wettability by the bead coating method (slide coating method) to a film thickness of 12 μm.
As a result, the mixed solution adhered only to the exposed portion (circular pattern portion). 70m with a mercury lamp
Exposure for 5 seconds at an illuminance of W / cm ² gives a diameter of 50
Example C-3 A microlens array having a micrometer and a focal length of 1 mm was obtained. Example C-3 The photocatalyst-containing layer described in Example C-1 was formed on a quartz glass transparent substrate by a spin coating method. This was exposed to mercury lambs for 90 seconds at an illuminance of 15 mW / cm ² (254 nm) through a negative photomask in which a plurality of circular patterns having an opening diameter of 200 μm were arranged at intervals of 100 μm, and the surface was highly wettable. A transparent substrate having a circular pattern was obtained.

UV curable monomers (polyoxide denaturation)
Glycerin acrylate: Arakawa Chemical Industries beam set
720) 1000 g, a curing initiator (Ciba Specialty)
Mix 50g of Irgacure 184)
And stirred for 3 minutes. Precise liquid quantitative dispensing of the resulting mixture
Dispenser (Dispenser 1500XL-1 manufactured by EFD)
In 5), the above-mentioned circular patterns having different wettability are applied.
0.0001 at the center of the circular pattern on the transparent substrate
ml was discharged. At this time, the discharged liquid is only in the circular pattern part
Spread did not spread to other parts. this
70mW / cm by mercury lamp^Two Exposure for 10 seconds at
200μm diameter, 500μm focal length by light
Example C-4 A photocatalyst containing the photocatalyst described in Example C-1 on a quartz glass transparent substrate was obtained.
The amount was formed by a spin coating method. This has an opening
Multiple circular patterns with a diameter of 200 μm are spaced at 100 μm intervals
By mercury lamp through a line of negative photomasks
15mW / cm ^Two (254nm) exposure for 90 seconds
Transparent base with a highly wettable circular pattern on the surface
Wood was obtained.

UV-curable monomer (bifunctional acrylate monomer: KAYARADPEG400D manufactured by Nippon Kayaku)
A) 500 g, 25 g of a polymerization initiator (Darocur 1173 manufactured by Ciba Specialty Chemicals) and 0.5 g of a red dye (Rose Bengal manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 3 minutes to obtain a red lens composition. UV curable monomer (bifunctional acrylate monomer: Nippon Kayaku KAYAR
ADPEG400DA) 500 g, polymerization initiator (manufactured by Ciba Specialty Chemicals: Darocure 1173) 25
g, green dye (Villiant Green manufactured by Tokyo Kasei)
5 g were mixed and stirred for 3 minutes to obtain a green lens composition. UV-curable monomer (bifunctional acrylate monomer: Nippon Kayaku KAYARADPEG 400DA) 50
0 g, 25 g of a polymerization initiator (Darocur 1173 manufactured by Ciba Specialty Chemicals) and 0.5 g of a blue dye (Victoria Blue manufactured by Tokyo Chemical Industry) were mixed and stirred for 3 minutes to obtain a blue lens composition.

The obtained lens composition was designated as red, green, and blue on a transparent substrate on which a circular pattern having a different wettability as described above was formed by a liquid precision discharge device (EED dispenser 1500XL-15). 0.0001 ml was ejected to the center of the circular pattern portion. At this time, the discharged liquid spread only to the circular pattern portion, and did not spread to other portions. This was exposed to an illuminance of 70 mW / cm ² for 10 seconds using a mercury lamp to obtain a colored microlens array having a diameter of 200 μm and a focal length of 500 μm.

Example C-5 The photocatalyst-containing layer described in Example C-1 was formed on a quartz glass transparent substrate by a spin coating method. 15 mW / cm ² by a mercury lamp through a negative photomask in which a plurality of circular patterns having an opening diameter of 200 μm are arranged at intervals of 100 μm in the vertical direction and 700 μm in the horizontal direction.
(254 nm) exposure for 90 seconds to obtain a transparent substrate having a circular pattern with high wettability on the surface, 400 g of an ultraviolet-curable monomer (bifunctional acrylate monomer: KAYARADPEG400DA manufactured by Nippon Kayaku), ultraviolet-curable Type monomer (1,6-hexanediol diacrylate: KS-HDDA manufactured by Nippon Kayaku) 100 g, polymerization initiator (Darocur 11 manufactured by Ciba Specialty Chemicals)
73) 25 g and a red dye (Rose Bengal, manufactured by Tokyo Kasei) 0.5 g were mixed and stirred for 3 minutes to obtain a red lens composition.

UV-curable monomer (bifunctional acrylate monomer: KAYARADPEG400D manufactured by Nippon Kayaku)
A) 400 g, UV curable monomer (1,6-hexanediol diacrylate: KS-HDD manufactured by Nippon Kayaku)
A) 100 g, 25 g of a polymerization initiator (Darocur 1173 manufactured by Ciba Specialty Chemicals), and 0.5 g of a green dye (Villiant Green manufactured by Tokyo Kasei) were mixed and stirred for 3 minutes to obtain a lens composition for green. UV-curable monomer (bifunctional acrylate monomer: Nippon Kayaku KAY
ARAPPEG400DA) 400 g, UV-curable monomer (1,6-hexanediol diacrylate: KS-HDDA manufactured by Nippon Kayaku) 100 g, polymerization initiator (Darocur 1173 manufactured by Ciba Specialty Chemicals) 25
g, blue dye (Tokyo Kasei Victoria Blue) 0.5
g was mixed and stirred for 3 minutes to obtain a blue lens composition.

The composition for red lens obtained was applied by a dip coating method to a transparent substrate having a circular pattern having a different wettability as described above at 12 μm.
The mixed solution adhered only to the exposed portions (circular pattern portions). This is carried out by a mercury lamp under nitrogen atmosphere.
The resin was cured by exposing to light of 0 mW / cm ² for 10 seconds. A photocatalyst-containing layer is formed on the substrate on which the red lens is formed in the same manner as described above, and a circular pattern having high wettability is formed at a distance of 100 μm from the vertical row of the red lens under the same conditions as above. did. Using the composition for a green lens, a green lens was formed by performing the same operation as for the red. The same operation was performed using the blue lens composition to form a blue lens at a distance of 100 μm between the vertical columns of the red and green lenses to obtain a colored microlens array having a diameter of 200 μm and a focal length of 1 mm. Was.

Example C-6 The photocatalyst-containing layer described in Example C-1 was formed on the back surface of quartz glass having a diameter of 100 μm and supporting microlens arrays arranged at intervals of 10 μm. Next, after aligning the photomask and the lens, each having an opening diameter of 10 μm and arranged at intervals of 100 μm, pattern exposure was performed using a mercury lamp. Next, 500 g of an ultraviolet-curable monomer (bifunctional acrylate monomer: KAYARADPEG400DA manufactured by Nippon Kayaku) and a polymerization initiator (Darocur 11 manufactured by Ciba Specialty Chemicals)
73) 100 g of carbon black was dispersed in 25 g of the mixture to prepare a light-shielding layer composition.

When this light-shielding layer composition is applied to the entire surface of the exposed photocatalyst-containing layer by a blade coater, the unexposed portion repels and selectively adheres only to the exposed portion. Then 15
The mixture was heated at 0 ° C. for 30 minutes to form a light-shielding layer.

Example C-7 The photocatalyst-containing layer described in Example C-1 was formed on the back surface of quartz glass having a diameter of 700 μm and arranged at intervals of 10 μm, which was the base material of the microlens array. After alignment with a lens through a photomask having a diameter of 10 μm and arranged at an interval of 700 μm, pattern exposure was performed using a mercury lamp. Next, the light-shielding layer composition described in Example C-6 was discharged onto the exposed portion by a dispenser (manufactured by EFD), so that the light-shielding layer composition was adhered only to the exposed portion. Next, heating was performed at 150 ° C. for 30 minutes to form a light-shielding layer. Example C-8 The photocatalyst-containing layer described in Example C-1 was formed on a quartz glass transparent substrate by a spin coating method. This was exposed to a mercury lamp at an illuminance of 15 mW / m ² for 90 seconds through a mask having a circular pattern with an opening diameter of 9 mm to obtain a transparent substrate having a highly wettable circular pattern on the surface. UV-curable monomer (bifunctional acrylate monomer: Nippon Kayaku KAYARADPEG 400DA) 50
0 g and 25 g of a polymerization initiator (Darocur 1173 manufactured by Ciba Specialty Chemicals) were mixed and stirred for 3 minutes.

[0202] The obtained mixed solution was placed in a microsyringe.
15 to 55 μl was discharged to the center of the circular pattern portion on the transparent substrate on which the circular patterns having different wettability were applied. At this time, the discharged liquid spreads only to the circular pattern portion and does not spread to other portions, and the contact angle with the base material increases as the amount of dripping increases, and this is measured with a mercury lamp at an illuminance of 70 mW / cm ² . By exposing for 10 seconds, a lens having a diameter of 9 mm and a focal length of 27 to 90 mm is formed.
By controlling the discharge amount of the resin mixture, it was possible to design and create.

On the other hand, for comparison, 15 to 55 μl of the above resin mixture was discharged onto a quartz glass (substrate having no wettability pattern) having no photocatalyst containing layer. At this time, the discharged liquid became wet and spread as the discharge amount increased, and its shape was not stable, but took various shapes. The contact angle with the substrate did not change in accordance with the discharge amount. This was exposed for 10 seconds with a mercury lamp at an illuminance of 70 mW / cm ² , but the obtained lens-shaped product was not one whose shape, diameter, and focal length were controlled. In the above example,
The contact angle between the resin solution (lens composition) dripping amount and the substrate,
The relationship between the diameter and the focal length of the generated lens-shaped object is shown in the table below.

[0204]

[Table 5] Substrate on which wettability pattern is formed Amount under resin mixed droplet Contact angle with substrate Generated lens radius Generated lens focal length (μL) (°) (mm) (mm) 15.0 12.4 9.0 90.4 20.0 16.3 9.0 52.0 30.0 19.5 9.0 46.3 40.0 22.6 9.0 40.3 50.0 33.4 9. 0 31.2 55.0 38.4 9.0 27.8 Substrate on which wettability pattern is formed Amount under resin mixed droplet Contact angle with substrate Generated lens radius Generated lens focal length (μL) (°) (Mm) (mm) 15.0 18.9 8.0 70.0 20.0 22.6 7.0 68.3 30.0 18.4 9.0 70.5 40.0 24.1 10. 0 66.5 50.0 22.6 11.0 68.0 55.0 22.6 12.0 68.0

According to the third aspect of the present invention, a method of manufacturing a lens by a simple process. Particularly, in manufacturing a microlens and a microlens array, the positional accuracy and the shape accuracy are high, and the manufacturing of a microlens is difficult. Can,
It is possible to provide a method for manufacturing a lens in which the focal length can be easily controlled. Further, a simple method of forming the lens light-shielding layer can be provided.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining an embodiment of the present invention.

FIG. 2 is a diagram illustrating another embodiment of the present invention.

FIG. 3 is a diagram for explaining another embodiment of the present invention.

FIG. 4 is a diagram for explaining another embodiment of the present invention.

FIG. 5 is a diagram for explaining another embodiment of the present invention.

FIG. 6 is a diagram for explaining another embodiment of the present invention.

FIG. 7 is a diagram illustrating an embodiment of a method for manufacturing an element of the present invention.

FIG. 8 is a view for explaining another embodiment of the method for manufacturing an element of the present invention.

FIG. 9 is a view for explaining another embodiment of the method for manufacturing an element of the present invention.

FIG. 10 is a diagram illustrating another embodiment of the method for manufacturing an element of the present invention.

FIG. 11 is a schematic sectional view showing an example of an embodiment of a color filter of the present invention.

FIG. 12 is a schematic sectional view showing another example of the embodiment of the color filter of the present invention.

FIG. 13 is a schematic sectional view showing another example of the embodiment of the color filter of the present invention.

FIG. 14 is a schematic sectional view showing another example of the embodiment of the color filter of the present invention.

FIG. 15 is a process chart for explaining one embodiment of a color filter manufacturing method of the present invention.

FIG. 16 is a process chart for explaining another embodiment of the color filter manufacturing method of the present invention.

FIG. 17 is a plan view showing a state of a mask when irradiating the photocatalyst-containing layer with light in the color filter manufacturing method of the present invention shown in FIG. 18;

FIG. 18 is a process chart for explaining another embodiment of the color filter manufacturing method of the present invention.

FIG. 19 is a process chart for explaining another embodiment of the color filter manufacturing method of the present invention.

FIG. 20 is an explanatory diagram of a method of adjusting a focal length in the method of manufacturing a lens according to the present invention.

FIG. 21 is a sectional view showing an example of a microlens array according to a preferred embodiment of the present invention.

FIG. 22 is a cross-sectional view illustrating an example of a colored microlens array according to a preferred embodiment of the present invention.

FIG. 23 is an explanatory diagram of a method for manufacturing a microlens using a photocatalyst according to a preferred embodiment of the present invention.

FIG. 24 is a cross-sectional view showing an example of a microlens array having a light-shielding layer, which is a preferred embodiment of the present invention.

FIG. 25 shows an example of a microlens array having a light-shielding layer, which is a preferred embodiment of the present invention, and is a plan view seen from a surface provided with the light-shielding layer.

FIG. 26 is a cross-sectional view showing an example of an imaging device using a microlens array having a light-shielding layer, which is a preferred embodiment of the present invention.

FIG. 27 is a cross-sectional view illustrating an example of an imaging device including a colored microlens array having a light-shielding layer according to a preferred embodiment of the present invention.

FIG. 28 is a cross-sectional view showing an example of a display using a microlens array having a light-shielding layer, which is a preferred embodiment of the present invention.

FIG. 29 is a cross-sectional view showing an example of a liquid crystal display which is a preferred embodiment of the present invention and is configured using a colored microlens array having a light-shielding layer.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 101 ... Pattern forming body, 102 ... Substrate, 103 ... Primer layer, 104 ... Photocatalyst containing layer, 141 ... Photocatalyst containing layer, 142 ... Photocatalyst containing layer, 144 ... Photocatalyst containing layer, 1
05: pattern, 106: exposure, 107: photocatalyst, 10
8: lipophilic portion, 109: oleophobic portion, 110: wettability changing material layer, 111: lipophilic portion, 113: lipophilic portion, 116: photocatalytic decomposable material, 117: portion changed according to pattern, 120 ... Photo mask, 121 ... Laser, 122 ... Blade coater, 123 ... Spin coater, 124 ... Film forming means, 125 ... Functional layer, 126 ... Adhesive tape, 127 ... Air jet nozzle, 128 ... Functional layer, 129 ... Element formation Base material, 130 ... sheet, 131
... heat-fusible composition layer, 132 ... thermal transfer body, 135 ... discharge nozzle, 136 ... ultraviolet curable resin composition, 137 ... ultraviolet light for curing, 138 ... microlens, 201 ... color filter, 202 ... transparent substrate, 203 ... Photocatalyst containing layer,
204: black matrix, 205: colored layer, 20
6 Protective layer, 211 color filter, 212 transparent substrate, 213 photocatalyst containing layer, 214 black matrix, 215 colored layer, 216 protective layer, 221 color filter, 222 transparent substrate, 223a photocatalyst containing Layer, 223b photocatalyst containing layer, 223c photocatalyst containing layer, 224 black matrix, 225R red coloring layer, 225G green coloring layer, 225B blue coloring layer, 225 coloring layer, 226 protection layer, 231 ... color filter, 232 ... transparent substrate, 233a ... photocatalyst containing layer, 233b ... photocatalyst containing layer, 233c ... photocatalyst containing layer, 233d ... photocatalyst containing layer, 234 ... black matrix, 235R ... red colored layer, 235R ... red Colored layers, 235G: green colored layers, 235B: blue colored layers, 235: colored layers, 36 ... protective layer, 203 '... light irradiation site, 213' ... light irradiation site, W ... black matrix line width of w shielding pattern, M ... mask, 223'A
... Light irradiation part, 233'a ... Light irradiation part, 233'b ...
Light irradiation part, 233'c: Light irradiation part, 233'd: Light irradiation part, 301: Transparent substrate, 303: Photocatalyst containing layer,
303 ': layer containing modified photocatalyst, 302: composition for lens, 302A: lens, 304: photomask, 305
... Irradiation light beam, 306 discharge nozzle, 309 colored filter, 310 photoelectric conversion element, 305 irradiation light beam, 306
.., Discharge nozzle, 307, light shielding layer, 308, incident light, 30
9: colored filter, 310: photoelectric conversion element, 311: transmitted light, 313: liquid crystal element, 314: light source, 315: first
Color lens, 316: second color lens, 317: third color lens, 318: imaging element section, 319: liquid crystal display section, 320: micro lens array, 321: colored micro lens array

Continued on the front page (72) Inventor Masato Okabe 1-1-1 Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dai-Nippon Printing Co., Ltd. F-term (reference) 2H048 BA54 BB14 BB46 2H123 AD00 AD06 AD11 AD26 AD30 BA00 BA14 BB00 BB02 BC00 BC01 BC05 CA00 CA15 CB00 CB02 DA10 EA11

Claims (49)

[Claims] 1. A pattern forming body for optically forming a pattern, comprising a photocatalyst-containing layer on a substrate, wherein the photocatalyst-containing layer changes from oil-repellent to lipophilic by the action of a photocatalyst upon exposure of the pattern. A pattern-forming feature characterized by containing a substance to be formed. 2. A pattern forming body for optically forming a pattern, comprising a photocatalyst-containing layer on a substrate, and a layer which is decomposed and removed by the action of a photocatalyst by exposure of the pattern on the photocatalyst-containing layer. A pattern forming body characterized in that the pattern forming body has lipophilicity as a result thereof. 3. A pattern forming body for optically forming a pattern, comprising a photocatalyst-containing layer on a base material, and a substance which changes from oleophobic to lipophilic by exposure of the pattern on the photocatalyst-containing layer. A pattern formed body having a containing layer. 4. A pattern forming body for optically forming a pattern, comprising a composition layer comprising a photocatalyst, a substance decomposed by the action of the photocatalyst upon exposure of the pattern, and a binder, A pattern forming body characterized by changing from oil repellency to lipophilicity. 5. The pattern forming body according to claim 1, wherein the photocatalyst-containing layer contains a compound having a siloxane bond. 6. The pattern forming body according to claim 1, wherein the photocatalyst containing layer contains silicone. 7. The pattern forming body according to claim 6, wherein a fluoroalkyl group is bonded to a silicon atom of the silicone. 8. The pattern forming body according to claim 6, wherein the silicone is obtained from a composition containing an organoalkoxysilane. 9. The pattern forming body according to claim 6, wherein the silicone is obtained from a composition containing a reactive silicone compound. 10. The pattern forming body is any one of a functional element, a color filter, and a microlens in which a functional layer is disposed on a portion corresponding to a pattern of the pattern forming body obtained by pattern exposure. A pattern formed body characterized by the above. 11. A method for optically forming a pattern, comprising: a pattern-formed body having a photocatalyst-containing layer containing a substance that changes from oil-repellent to lipophilic by the action of a photocatalyst on a substrate; A patterned body in which a layer containing a substance that changes from oleophobic to lipophilic by the action of a photocatalyst is formed on the photocatalyst-containing layer formed on the photocatalyst-containing layer, and the pattern is formed on the photocatalyst-containing layer by exposing the pattern to Pattern-forming body having a layer that is decomposed and removed by the action of a photocatalyst, or pattern formation in which a composition layer comprising a photocatalyst, a substance that is decomposed by the action of a photocatalyst by exposure of a pattern, and a binder is formed on a substrate Expose the pattern on the body,
A pattern forming method, wherein the surface is changed from oleophobic to lipophilic by the action of a photocatalyst. 12. The method according to claim 11, wherein the pattern exposure on the photocatalyst-containing layer is performed by light drawing irradiation.
4. The pattern forming method according to 1. 13. The pattern forming method according to claim 11, wherein the pattern exposure of the photocatalyst-containing layer is performed by exposure through a photomask. 14. The pattern forming method according to claim 11, wherein the pattern exposure on the photocatalyst-containing layer is performed while heating the pattern formed body. 15. A pattern having a pattern formed body according to any one of claims 1 to 9 on a base material and obtained by pattern exposure according to any one of claims 11 to 14. An element, wherein a functional layer is disposed on a portion corresponding to a pattern of a formed body. 16. The method according to claim 11, wherein the pattern forming body is formed on the pattern forming body.
The functional layer formed on a portion corresponding to the pattern of the pattern formed body obtained by the pattern exposure according to any one of the above, is formed by transferring the functional layer onto another substrate An element characterized by the above-mentioned. 17. The pattern obtained by pattern exposure according to any one of claims 11 to 14, comprising a pattern forming body according to any one of claims 1 to 9 on a substrate. A method for manufacturing an element, comprising forming a functional layer on a portion corresponding to a pattern of a formed body. 18. The method according to claim 11, wherein the pattern forming body is
A functional layer is formed on a substrate by transferring the functional layer onto another substrate on a portion corresponding to the pattern of the pattern-formed body obtained by the pattern exposure according to any one of Items 4 to 4. A method for producing an element, comprising: 19. A step of laminating a composition for a functional layer over the entire surface of a pattern-formed body, wherein the functional layer is formed into a pattern only on a portion where the oil repellency of the exposed portion changes from oleophobic to lipophilic due to the repulsion of the unexposed portion. 18. The device manufacturing method according to claim 17, further comprising the step of: 20. A method of forming a functional layer in a pattern by removing a functional layer in an unexposed portion by laminating a functional layer composition on the entire surface of a pattern formed body. The method for producing an element according to claim 17, wherein 21. A step of laminating a composition for a functional layer on the entire surface of a pattern-formed body, wherein a functional layer is formed in a pattern only on a portion where the oil repellency of the exposed portion has changed from oleophilic to lipophilic due to the repulsion of the unexposed portion. 19. The method according to claim 18, further comprising the step of: 22. A method comprising the steps of: laminating a functional layer composition on the entire surface of a pattern-formed body; and forming a functional layer in a pattern by removing unexposed portions of the functional layer. The method for manufacturing an element according to claim 18, wherein 23. The element manufacturing method according to claim 19, wherein the formation of the functional layer on the pattern forming body is performed by applying a functional layer composition or discharging from a nozzle. 24. The element manufacturing method according to claim 19, wherein the formation of the functional layer on the pattern formed body is performed by transfer from a functional layer composition applied film by heat or pressure. 25. The element manufacturing method according to claim 19, wherein the formation of the functional layer on the pattern formed body is performed by vacuum film formation means or film formation using electroless plating. 26. A transparent substrate, and at least one of a plurality of colored layers formed in a predetermined pattern on the transparent substrate, is formed through a specific portion of the layer that changes from oleophobic to lipophilic. A color filter formed on a substrate. 27. A transparent substrate and a light-shielding layer at a boundary between colored layers formed of a plurality of colors formed in a predetermined pattern on the transparent substrate, wherein at least one of the colored layer and the light-shielding layer is provided. Is formed on the transparent substrate through a specific portion of a layer that changes from oleophobic to lipophilic. 28. A transparent substrate provided with a light-shielding layer in a predetermined pattern, and a layer that changes from oil-repellent to lipophilic on the transparent substrate so as to cover the light-shielding layer, A layered body with a colored layer formed in a predetermined pattern on a specific portion of the changing layer is provided by laminating a desired number of colors, or a light shielding layer formed in a predetermined pattern is provided, The color filter, wherein the layer that changes from lipophilic to lipophilic is a photocatalyst-containing layer composed of a photocatalyst and a binder. 29. The color filter according to claim 26, wherein the binder contains a composition containing chlorosilane or alkoxysilane or an organopolysiloxane obtained from a composition containing reactive silicone. . 30. A photocatalyst layer comprising a binder and a photocatalyst substance is formed on a transparent substrate, and the photocatalyst layer is exposed in a predetermined pattern to form a portion that changes from oleophobic to lipophilic.
A method for producing a color filter, wherein a colored layer is formed by adhering either a light-shielding material or a paint for a colored layer on the site. 31. A photocatalyst-containing layer comprising at least a binder and a photocatalyst is formed on a transparent substrate, the photocatalyst-containing layer is irradiated with light, and the light-irradiated portion is changed from oleophobic to lipophilic by the action of the photocatalyst. The method for manufacturing a color filter according to claim 30, wherein the color filter is formed. 32. A photocatalyst-containing layer formed on a transparent substrate and comprising a binder and a photocatalyst, is irradiated with light in a predetermined pattern to the photocatalyst-containing layer, and the light-irradiated portion is changed from oil-repellent to lipophilic by the action of the photocatalyst. To form the changed part,
A color filter, wherein a light-shielding layer is formed by adhering a light-shielding layer paint on the portion, or a light-shielding layer or a colored layer is formed by performing at least one operation of adhering the coloring layer paint. Manufacturing method. 33. The light irradiation on the photocatalyst containing layer,
The method for producing a color filter according to any one of claims 30 to 32, wherein the method is performed by one of pattern exposure through a mask and light drawing irradiation. 34. The method according to claim 30, wherein at least one of the light-shielding layer paint and the colored layer paint is applied by any one of a coating method, a nozzle discharging method, and a vacuum thin film forming method. 2. The method for producing a color filter according to claim 1. 35. A method of forming a vacuum thin film, comprising the step of removing a thin film made of a light-shielding layer paint or a colored layer paint adhered to a portion other than a portion changed from oleophobic to lipophilic after forming the thin film. 35. The method for manufacturing a color filter according to claim 34, wherein: 36. A method for manufacturing a lens, comprising irradiating a photocatalyst-containing layer containing a photocatalyst and a binder formed on the surface of a base material with light, whereby the surface of the base material is changed from oleophobic to lipophilic by photocatalysis. After a pattern is formed by a difference in wettability by forming a portion that changes to a shape, a liquid containing a material for forming a lens is attached, and then the liquid is cured according to the pattern to form a lens. A method for manufacturing a lens, comprising: 37. The method according to claim 36, wherein the photocatalyst-containing layer contains at least an optical semiconductor substance as a photocatalyst and a binder component. 38. A liquid containing a material for forming the lens is attached to a portion of the base material changed from oleophobic to lipophilic by light irradiation.
7. The method for producing a lens according to 6. 39. The method for manufacturing a lens according to claim 36, wherein a liquid containing a material for forming the lens is applied to the base material or attached by nozzle discharge. 40. A colored microlens array is obtained by applying a liquid containing a material for forming the colored lens to the base material by a required number of colors by discharging from a nozzle for each color. The method for producing a lens according to claim 36, wherein 41. The method of manufacturing a lens according to claim 36, wherein a colored microlens array of a plurality of colors is obtained by repeating the process for one substrate for each color of the lens. 42. The lens according to claim 36, wherein the focal length of the lens is adjusted by changing an amount of a liquid containing a material for forming the lens on the substrate. Production method. 43. A step of forming a pattern by changing from oleophobic to lipophilic by irradiating light to form a light-shielding layer pattern corresponding to a lens pattern on the back surface of the transparent substrate on which the lens is not formed. Attaching a liquid containing a material for forming a light-shielding layer to a lipophilic portion of the light-shielding layer pattern of the base material; and curing the liquid containing a material for forming the light-shielding layer by curing the light-shielding layer. 37. The method for manufacturing a lens according to claim 36, wherein a light-shielding layer is formed by the step of forming a lens. 44. The method for manufacturing a lens according to claim 36, further comprising a light-shielding layer, wherein a liquid containing a material for forming the light-shielding layer is applied by application or ejection from a nozzle. . 45. A lens formed on a transparent base material, on a surface of the transparent base material where the lens is not formed, on a portion which is changed from oil-repellent to lipophilic by an action of the photocatalyst by light irradiation on the photocatalyst. A lens, wherein a light-shielding layer pattern corresponding to the lens pattern is formed. 46. The lens according to claim 45, wherein the lens is a microlens or a microlens array arranged in an array. 47. The lens according to claim 45, wherein the lens is a colored lens of at least one color. 48. An imaging apparatus using the microlens or the microlens array according to claim 46 or 47. 49. A display device using the microlens or the microlens array according to claim 46 or 47.