JP2004199086A - Pattern forming body and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming body using a photocatalyst and a pattern forming method. <P>SOLUTION: The pattern forming body 1 has a photocatalyst-containing layer 4 on a base body. The photocatalyst-containing layer 4 contains a substance which changes the wettability by the effect of the photocatalyst by exposure for patterning, or a layer containing a substance which changes the wettability by the effect of the photocatalyst by exposure for patterning is formed on the photocatalyst-containing layer, or a layer which is decomposed and removed by the effect of the photocatalyst 7 by exposure for patterning is formed on the photocatalyst-containing layer on a base material 2. Or, the pattern forming body has a composition layer comprising the photocatalyst 7, a binder and a substance which is decomposed by the effect of the photocatalyst by exposure for patterning on the base material 2. Thus, the pattern is recorded by changing the wettability by exposure. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a novel pattern forming body and a pattern forming method that can be used for various uses including printing.

  The present invention relates to a pattern formed body in which a region having characteristics different from the surroundings is formed on a base material. When the pattern forming body is used for printing designs, images, characters, and the like, the pattern means a portion that receives or repels ink when the printing ink is transferred. Further, the pattern formed body of the present invention can be used for purposes other than printing, in which case the pattern is transferred to the patterned layer formed on the pattern formed body according to the change in wettability and transferred Means layer.

  To explain by taking printing as an example, a lithographic printing plate used for lithographic printing, which is a type of printing method, forms a lipophilic portion that accepts ink and a portion that does not receive printing ink on the lithographic plate, and forms a lipophilic portion. An image of the ink to be printed is formed on the paper, and the formed image is transferred to paper or the like for printing.

  In such printing, a printing plate is prepared by forming patterns such as characters and figures on a printing plate precursor, and mounted on a printing machine for use. Many printing plate precursors for offset printing, which are typical lithographic printing plates, have been proposed.

  A printing plate for offset printing is manufactured by exposing and developing the printing plate precursor through a mask with a pattern, or by directly exposing the plate by electrophotography and making a plate on the printing plate precursor. can do. An electrophotographic offset printing plate precursor is exposed by an electrophotographic method as a photoconductor provided with a photoconductive layer mainly composed of photoconductive particles such as zinc oxide and a binder resin on a conductive base material, It is produced by a method in which an image having high lipophilicity is formed on the surface of the photoreceptor, followed by treatment with a desensitizing solution to hydrophilize a non-image portion to obtain an offset master. The hydrophilic portion is immersed in water or the like to make it oleophobic, and the lipophilic image portion receives the printing ink and is transferred to paper or the like.

  Also, instead of the method of forming an oleophobic site by immersion in water, a site that receives ink and a site that does not receive ink are formed by forming a highly oleophobic site without immersion in water or the like. A printing plate precursor for dry lithographic printing which forms is also used.

  In addition, a method for producing a lithographic printing plate precursor using a heat mode recording material, which can form a portion having high ink receptivity and a portion having ink repellency by laser irradiation, has been proposed. . The heat mode recording material has the characteristic that a printing plate can be manufactured simply by forming an image with a laser beam without the need for a process such as development, but the intensity of the laser is adjusted, and the quality is changed by the laser. There are problems in the processing of the residue of the solid substance thus obtained, the printing durability, and the like.

  In addition, as a method for forming a high-definition pattern, a photoresist layer applied on a substrate is exposed to a pattern, and after the exposed photoresist is developed, further etching is performed, or the photoresist has functionality. There is known a method by photolithography such as directly forming a target pattern by exposing a photoresist using a substance.

  The formation of high-definition patterns by photolithography includes forming colored patterns for color filters used in liquid crystal display devices, forming microlenses, manufacturing fine electric circuit boards, and manufacturing chrome masks used for pattern exposure. However, depending on these methods, it is necessary to use a photoresist, develop with a liquid developer after exposure, or perform etching, so that there is a problem that it is necessary to treat a waste liquid. Further, when a functional substance is used as a photoresist, there is a problem that the functional substance is deteriorated by an alkaline solution or the like used at the time of development.

  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 disclosed a pattern forming body and a pattern forming method for forming a pattern by using a substance whose wettability changes by the action of a photocatalyst, as disclosed in Japanese Patent Application No. Hei. The present invention proposes a pattern-formed body and a method of forming a pattern using such a photocatalyst, which have more excellent characteristics, as proposed in US Pat.

  An object of the present invention is to provide a novel pattern forming body and a pattern forming method, and when used for a printing plate precursor, can solve the problems of the conventional printing plate precursor. An object of the present invention is to provide a pattern forming body capable of providing a new printing plate precursor, and when used for forming various functional elements, a functional element having excellent characteristics can be provided. It is an object to provide a pattern forming body and a pattern forming method.

  The present invention relates to a pattern forming body for optically forming a pattern, comprising: a photocatalyst-containing layer on a substrate; and a pattern formation having, on the photocatalyst-containing layer, a layer which is decomposed and removed by the action of a photocatalyst upon exposure of the pattern. Body.

  The photocatalyst-containing layer is the above-described pattern formed body formed by forming a photocatalyst alone.

  The layer that is decomposed and removed by the action of the photocatalyst is formed by any one method selected from the group consisting of application of a solution, surface graft treatment, surfactant treatment, and a film formation method using a gas phase. This is the above-mentioned pattern formed body.

  It is a pattern formed body that optically forms a pattern and has a composition layer composed of a photocatalyst, a substance decomposed by the action of the photocatalyst upon exposure of the pattern, and a binder.

  The pattern forming body according to the above, wherein the photocatalyst-containing layer is sensitive to visible and other wavelengths.

It is the above-mentioned pattern forming body in which a metal ion is doped in the photocatalyst containing layer.
The pattern forming body according to the above, wherein a fluorescent substance is added to the photocatalyst containing layer.

It is the above-mentioned pattern formed body in which a photosensitive dye is added to a photocatalyst containing layer.
The pattern forming body is the above-described pattern forming body which is a printing plate precursor.

  Further, in the method of optically forming a pattern, a pattern-forming body having a photocatalyst-containing layer on a substrate and having a layer which is decomposed and removed by the action of a photocatalyst by exposing the pattern on the photocatalyst-containing layer is exposed to the pattern. This is a pattern forming method in which the wettability of the surface is changed by the action of a photocatalyst.

  In the method of optically forming a pattern, a pattern formed body having a composition layer comprising a photocatalyst, a substance that is decomposed by the action of the photocatalyst by exposure of the pattern, and a binder is formed on a substrate, and the pattern is exposed to light. This is a pattern forming method in which the wettability of the surface is changed by the action of a photocatalyst.

  The pattern exposure for the photocatalyst-containing layer is the above-described pattern forming method performed by light drawing irradiation.

  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.

  An element having the pattern formed body on a base material and having a functional layer disposed on a portion corresponding to a pattern of the pattern formed body obtained by the pattern forming method.

  An element formed by transferring a functional layer formed on a portion corresponding to the pattern of the pattern formed body obtained on the pattern formed body by the above-described pattern forming method onto another substrate.

  An element manufacturing method comprising forming the functional layer on a portion corresponding to a pattern of the pattern formed body obtained by the pattern forming method, the pattern forming body being provided on a substrate.

  On the pattern formed body, the functional layer on a portion corresponding to the pattern of the pattern formed body obtained by the pattern forming method, the functional layer on the substrate by transferring to another substrate This is a method for manufacturing the formed element.

  A step of laminating the functional layer composition on the entire surface of the pattern forming body, the step of forming a functional layer in a pattern only on the portion where the wettability of the exposed portion has changed due to the repulsion of the unexposed portion. This is an element manufacturing method.

  The above method for producing an element, comprising the steps of laminating a composition for a functional layer over the entire surface of a pattern-formed body, and forming a functional layer in a pattern by removing a functional layer in an unexposed portion.

  A step of laminating the functional layer composition on the entire surface of the pattern forming body, the step of forming a functional layer in a pattern only on the portion where the wettability of the exposed portion has changed due to the repulsion of the unexposed portion. This is an element manufacturing method.

  The above method for producing an element, comprising the steps of laminating a composition for a functional layer over the entire surface of a pattern-formed body, and forming a functional layer in a pattern by removing a functional layer in an unexposed portion.

  The formation of the functional layer on the pattern-formed body is the above-described device manufacturing method by applying a functional layer composition.

  The formation of the functional layer on the pattern formed body is the above-described element manufacturing method by discharging the functional layer composition 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 applied 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 a vacuum.

  The formation of the functional layer on the pattern formed body is the above-described element manufacturing method by film formation using electroless plating.

  Further, the present invention provides a pattern forming body for optically forming a pattern, wherein a photocatalyst-containing layer is provided on a substrate, and the photocatalyst-containing layer contains a substance whose wettability changes by the action of a photocatalyst upon exposure of the pattern. It is a pattern formed body.

  A pattern forming body that optically forms a pattern, has a photocatalyst-containing layer on a substrate, and has, on the photocatalyst-containing layer, a layer that is decomposed and removed by the action of a photocatalyst upon exposure of the pattern.

  In a pattern forming body for optically forming a pattern, a pattern formation having a photocatalyst-containing layer on a base material, and having, on the photocatalyst-containing layer, a content-containing layer of a substance whose wettability changes by the action of a photocatalyst upon exposure of the pattern Body.

  It is a pattern formed body that optically forms a pattern and has a composition layer composed of a photocatalyst, a substance decomposed by the action of the photocatalyst upon exposure of the pattern, and a binder.

  The above-described pattern forming body, wherein the layer containing a photocatalyst contains a compound having a siloxane bond.

  The layer containing a photocatalyst is the above-mentioned pattern-formed body containing silicone.

  It is the above-mentioned pattern forming body in which a fluoroalkyl group is bonded to a silicon atom of silicone.

  The above pattern-formed 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.

  The pattern forming body is the above-described pattern forming body which is a printing plate precursor.

  Further, in the method of optically forming a pattern, a pattern formed body provided with a photocatalyst containing layer containing a substance whose wettability changes by the action of a photocatalyst on a substrate, on the photocatalyst containing layer formed on the substrate A pattern-formed body having a layer containing a substance whose wettability changes by the action of a photocatalyst, and a layer having a photocatalyst-containing layer on a substrate and having a layer on the photocatalyst-containing layer which is decomposed and removed by the action of the photocatalyst by pattern exposure Exposure of a pattern to a pattern-formed body, or a pattern-formed body in which a composition layer comprising a photocatalyst, a substance decomposed by the action of the photocatalyst by exposure of the pattern, and a binder is formed on the pattern-formed body or the substrate, and the action of the photocatalyst This is a pattern forming method that changes the wettability of the surface.

  The pattern exposure for the photocatalyst-containing layer is the above-described pattern forming method performed by light drawing irradiation.

  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.

  An element having the pattern formed body on a base material and a functional layer disposed on a portion corresponding to a pattern of the pattern formed body obtained by the pattern exposure.

  An element formed by transferring a functional layer formed on a portion corresponding to the pattern of the pattern formed body obtained by the pattern exposure on the pattern formed body to another substrate.

  An element manufacturing method comprising forming the functional layer on a portion corresponding to a pattern of the pattern formed body obtained by the pattern exposure, the pattern forming body being provided on a substrate.

  Forming a functional layer on a pattern formed body, by transferring a functional layer on a portion corresponding to the pattern of the pattern formed body obtained by the pattern exposure, and transferring the functional layer on another base material This is an element manufacturing method.

  A step of laminating the functional layer composition on the entire surface of the pattern forming body, the step of forming a functional layer in a pattern only on the portion where the wettability of the exposed portion has changed due to the repulsion of the unexposed portion. This is an element manufacturing method.

  The above method for producing an element, comprising the steps of laminating a composition for a functional layer over the entire surface of a pattern-formed body, and forming a functional layer in a pattern by removing a functional layer in an unexposed portion.

  A step of laminating the functional layer composition on the entire surface of the pattern forming body, the step of forming a functional layer in a pattern only on the portion where the wettability of the exposed portion has changed due to the repulsion of the unexposed portion. This is an element manufacturing method.

  The above method for producing an element, comprising the steps of laminating a composition for a functional layer over the entire surface of a pattern-formed body, and forming a functional layer in a pattern by removing a functional layer in an unexposed portion.

  The formation of the functional layer on the pattern-formed body is the above-described device manufacturing method by applying a functional layer composition.

  The formation of the functional layer on the pattern formed body is the above-described element manufacturing method by discharging the functional layer composition 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 applied 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 a vacuum.

  The formation of the functional layer on the pattern formed body is the above-described element manufacturing method by film formation using electroless plating.

  Since the pattern formed body of the present invention has the photocatalyst-containing composition layer formed on the substrate, the pattern can be formed by changing the wettability of the surface by the action of the photocatalyst during light irradiation. A pattern can be formed without going through steps such as development, development, and the like, and can be used in many applications including printing plate precursors and functional elements.

  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 light irradiation. In the present invention, a pattern means a portion that receives or repels ink when transferring printing ink when it is used for printing designs, images, characters, and the like. Further, the pattern formed body of the present invention can be used for purposes other than printing. In this case, the pattern also means a region having characteristics different from the surroundings formed on the pattern forming body according to the change in wettability, and also a case where they are transcripts transferred onto another substrate. I do.

  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 light irradiation is a direct reaction with a nearby compound or an activity generated in the presence of oxygen and water. It is thought that 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 the number of floating bacteria in the air is reduced by providing a photocatalyst-containing layer on the surface of the tile or the like.

  In the present invention, a substance whose wettability changes by the action of a photocatalyst, a layer that is decomposed and removed by the action of a photocatalyst, a layer containing a substance whose wettability changes by the action of a photocatalyst, or a substance that is decomposed by the action of a photocatalyst are combined. A pattern-formed body is obtained by increasing the receptivity of a pattern-formed portion to printing ink or toner, or the ink repellency of a portion where a pattern is not formed, using a layer or the like having a composition comprising an adhesive. It is a thing.

Examples of the photocatalyst that can be used in the pattern forming body and the pattern forming method of the present invention include titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), and strontium titanate, which are known as optical semiconductors. Metal oxides such as (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), and iron oxide (Fe ₂ O ₃ ) can be given, and titanium oxide is particularly preferred. Titanium oxide has high band gap energy, is chemically stable, has no toxicity, and is easily available.

  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, hydrochloric acid peptized anatase titania sol (STS-02 manufactured by Ishihara Sangyo, average crystallite diameter 7 nm) and nitrate peptized anatase titania sol (Nissan Chemical Industries, TA-15, average crystallite diameter 12 nm) are mentioned. Can be.

  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 have sufficient resistance to the photooxidation action of the photocatalyst. Further, in consideration of using the pattern formed body as a printing plate, printing durability and wear resistance are also required.

  Therefore, as the binder, a silicone resin whose main skeleton has a siloxane bond (—Si—O—) can be used.

  Further, in the silicone resin, an organic group is bonded to a silicon atom, and as described in detail in Examples, if a photocatalyst is photoexcited, the organic group bonded to the silicon atom of the silicone molecule becomes an oxygen-containing group by photocatalysis. , And improves the wettability, so that it also functions as a substance that changes the wettability.

As the silicone resin, one or more hydrolyzed condensates and co-hydrolyzed condensates of a silicon compound represented by the general formula Y _n SiX _4-n (n = 1 to 3) can be used. . Y can be an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, or an epoxy group, and X can be a halogen, a methoxyl group, an ethoxyl group, or an acetyl group.

  Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxy Silane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Rutriisopropoxysilane, 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-octadecyltrit-butoxysilane; Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; dimethoxydiethoxy Silane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromo Silane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; vinyltrichlorosilane, vinyltribromosilane, vinyltrisilane Methoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane; γ Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri Ethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloxypropyltri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-A Nopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; and their partial hydrolysates; and mixtures thereof can be used.

  When the binder layer is formed of an organoalkoxysilane, it is more preferable that at least 10 to 30% by weight of the binder layer be formed of a bifunctional silicone precursor such as dialkoxydimethylsilane. When an organoalkoxysilane is used in a sol-gel method or the like, the crosslink density can be improved by using a trifunctional silicone precursor such as trialkoxymethylsilane as a main component. When the wettability is made different as described above, those containing more dimethylsiloxane components can improve the oil repellency than those containing methylsiloxane components.

  Further, the silicone molecule may contain a fluoroalkyl group as an organo group bonded to a silicon atom. In this case, the critical surface tension of the unexposed portion further decreases. Therefore, the repulsion between the ink and the functional layer composition and the unexposed portion is improved, and the function of preventing the adhesion of the ink or the functional layer composition is increased, and the ink or the functional layer composition is used as the ink or the functional layer composition. The choice of possible substances will increase.

Specifically, it is formed from one or more hydrocondensation products or co-hydrolysis condensates of the following fluoroalkoxysilanes. 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 (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃
(CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃
CF ₃ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) _{3
CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 Si (OCH 3) 3
CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
(CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂
CF ₃ (C ₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OCH ₃ ) _{2
CF 3 (CF 2) 3 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2
_{CF 3 (CF 2) 5 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2
_{CF 3 (CF 2) 7 (} C 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2
CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃
CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃
To provide better ink and repellency with the functional layer composition, reactive linear silicones, preferably those obtained by crosslinking dimethylpolysiloxane with a low crosslinking density, are preferred. Typically, a compound having a repeating unit shown below and subjected to a crosslinking reaction is preferable.

Here, n is an integer of 2 or more. R ¹ and R ² are each a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms. Further, it is preferable that R ¹ and R ² are methyl groups because the surface energy is minimized, and it is preferable that the methyl groups have a molar ratio of 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 becomes relatively small, so that there is a problem that the crosslink density becomes small.

  X and Y are selected from the following groups, and X and Y may be the same or different, and R is a hydrocarbon chain having 10 or less carbon atoms.

  As the reactive modified silicone used in the present invention, any of those that crosslink by condensation and those that crosslink 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.

  Further, an aqueous emulsion type may be used as the reactive silicone compound. 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. It is not preferable because dimethylsiloxane is reduced and water repellency is inferior.

Further, as the binder, an amorphous silica precursor can be used, represented by the general formula SiX ₄ , wherein X is a silicon compound such as a halogen, a methoxy group, an ethoxy group or an acetyl group, or a hydrolyzate thereof. Or a polysiloxane having an average molecular weight of 3000 or less is preferable.

  Specific examples include tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, tetramethoxysilane and the like. In this case, the precursor of the amorphous silica and the particles of the photocatalyst are uniformly dispersed in a non-aqueous solvent, and the substrate is hydrolyzed with moisture in the air to form silanol, and then cooled to room temperature. To form a photocatalyst-containing film. 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 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.

  Next, it is transformed into anatase titania by baking at 400 ° C. to 500 ° C., and transformed into rutile titania by baking at 600 ° C. to 700 ° C.

  Further, in the layer containing at least one of organosiloxane and amorphous silica and the photocatalyst, the amount of the photocatalyst is preferably from 5% by weight to 60% by weight, more preferably from 20% by weight to 40% by weight. .

  The photocatalyst and the binder can be dispersed in a solvent to prepare a coating solution and applied. Examples of the solvent that can be used include alcohol-based organic solvents such as ethanol and isopropanol.

  Further, a titanium-based, aluminum-based, zirconium-based, or chromium-based coupling agent can also 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, or bead coating. When an ultraviolet-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 lamps, excimer lamps, excimer lasers, YAG lasers, and other ultraviolet light sources can be used to emit ultraviolet light. By changing the illuminance and irradiation amount, the wettability of the film surface can be improved. Can be changed.

  In addition, when exposure is performed with a fine beam such as a laser, a desired pattern can be directly drawn without using a mask. In the case of other light sources, a mask having a desired pattern is formed. Is used to irradiate light 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 of metal chromium on a glass plate, or a film for plate making for printing 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, and hemicyanine dyes can be mentioned.Other useful dyes include diphenylmethane dyes such as crystal violet and 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 during the exposure of 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 significantly reduced. Exposure is preferred.

  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. 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 that can be used in the pattern-formed body of the present invention include metals such as glass, aluminum, and alloys thereof, plastics, fabrics, and nonwoven fabrics, depending on the use of the pattern-formed body or the element on which the pattern is formed. Can be mentioned. 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. 1 (A), a pattern forming body 1 comprises a photocatalyst-containing composition directly on a substrate 2 or after forming a primer layer 3. The layer 41 may be formed. Exposure 6 of a predetermined pattern 5 is performed to record pattern information as shown in FIG. 1 (B), and the alkyl chain of the silicone compound is converted to an OH group by the action of a photocatalyst 7 as shown in FIG. 1 (C). A hydrophilic portion 8 is formed on a surface which is hydrophobic according to the exposed pattern, and pattern information is recorded by a difference in wettability with the hydrophobic portion 9.

  Further, as a second embodiment of the pattern forming body of the present invention, as shown in FIG. 2A, a primer layer 3 is laminated on a base material 2 and a photocatalyst-containing composition layer 42 containing a photocatalyst is provided. Is formed, and a wettability changing substance layer 10 whose wettability changes by the action of a photocatalyst when irradiated with light is formed on the photocatalyst-containing composition layer. As shown in FIG. 2B, exposure 6 is performed using a pattern 5, and as shown in FIG. 2C, a portion 11 having different wettability according to the pattern is formed, and pattern information is recorded. is there.

  In the case of the second embodiment, the photocatalyst-containing composition layer forms a photocatalyst composition layer in which a composition in which a photocatalyst is dispersed in a binder precursor or the like is hydrolyzed or partially hydrolyzed, There is a method of forming a thin film made of a hydrophobic organic substance, and it is also possible to form a film using only a photocatalyst. The organic thin film can be formed by a solution coating method, a surface graft 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, a silane compound in which an organic group is changed to a hydroxyl group by the action of a photocatalyst, such as a silane coupling agent, chlorosilane, alkoxysilane, or a hydrolyzed condensate or a cohydrolyzed condensate of two or more of these. be able to.

  In the third embodiment, as shown in FIG. 3A, when a photocatalyst-containing composition layer 43 is formed on a base material 2 and then the photocatalyst-containing composition layer is irradiated with light. 3B, a material layer 12 which is decomposed and removed by the action of a photocatalyst is formed, and is exposed 6 using a pattern 5 as shown in FIG. 3 (B), and wettability is determined according to the pattern as shown in FIG. 3 (C). A different portion 13 is formed to record pattern information.

  In the case of the third embodiment, the photocatalyst-containing composition 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 a hydrophobic layer. There is a method of forming a thin film made of a conductive organic material, and a film can be formed 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 formation method in a gas phase such as PVD or CVD.

  Specifically, manufactured by Nippon Surfactant Industry: hydrocarbons such as NIKKOL BL, BC, BO, and BB series; DuPont: ZONYL FSN, FSO; Asahi Glass: Surflon S-141, 145; Dainippon Ink: Megafac F-141, 144, Neos: Futagent F-200, F251, Daikin Industries Unidyne DS-401, 402, 3M: Fluorine-based or silicone-based nonionic surfactants such as Florade FC-170, 176. However, 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, polyimide, Examples include oligomers and polymers such as styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, and polyisoprene.

  Further, in the fourth embodiment, as shown in FIG. 4A, a primer layer 3 is formed on a base material 2 and then a photocatalyst, a binder, and a photocatalyst when irradiated with light. A photocatalyst-containing composition layer 44 containing a photocatalytic decomposable substance 16 composed of a hydrophobic part 14 and a hydrophilic part 15 that decompose is formed. Instead of the photocatalyst-containing composition layer, a layer composed of only a photocatalyst and a photocatalytic decomposable substance may be formed. Then, exposure 6 is performed with a predetermined pattern 5 as shown in FIG. As a result, as shown in FIG. 4C, the photocatalytic decomposable substance 16 composed of the hydrophobic part 14 and the hydrophilic part 15 existing in the predetermined part is decomposed by the action of the photocatalyst, and the wettability of the surface is exposed. The portion 17 changed in accordance with the six patterns is formed and pattern information is recorded.

  As the substance that changes the wettability of the surface, it is possible to add a substance that can arbitrarily set the wettability of the photocatalyst-containing composition layer, such as a surfactant, according to its type and the amount added. preferable.

  As the substance capable of changing the wettability, a surfactant is preferable. Specifically, Nippon Surfactant Kogyo Co., Ltd .: hydrocarbon series such as NIKKOL BL, BC, BO, BB series; DuPont: ZONYL FSN , FSO, 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 FC-170, Examples thereof include fluorine-based or silicone-based nonionic surfactants such as 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, polyimide, Examples include oligomers and polymers such as styrene butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, and polyisoprene.

  It is preferable to use a composition of 5 to 60% by weight of the photocatalyst, 95 to 40% by weight of amorphous silica, and 0.1 to 55% by weight of the substance whose wettability changes by the action of the photocatalyst.

  The pattern formed body of the present invention can be used as a printing plate because the surface energy changes due to the action of the photocatalyst in the composition, and the portion where the wettability changes has changed the acceptability of the printing ink. .

  When the pattern forming body of the present invention is used as a printing plate precursor, there is no need for wet development or the like, and the feature is that the production of the printing plate is completed simultaneously with light exposure. The pattern formation on the pattern forming body of the present invention may be performed by exposing through a plate making film or the like, or may be performed directly by laser or the like.

  When preparing a printing plate precursor, a substrate such as aluminum generally used as an offset printing plate can be used, but a photocatalyst-containing composition layer is coated on a screen made of woven fabric, nonwoven fabric, or the like. Alternatively, a pattern may be formed by exposure. In addition, if there is a fear that the base material is deteriorated by the photo-oxidation action of the photocatalyst such as plastic, a protective layer may be formed by coating the base material with silicone, fluororesin, or the like in advance. Any shape such as a sheet shape, a ribbon shape, and a roll shape can be used.

  Further, the formed pattern may be visualized by mixing a photochromic material such as spiropyran, which changes color by light, or an organic dye decomposed by the action of a photocatalyst, into the composition.

  If the unexposed area is designed to have printing ink receptivity and repellency of fountain solution, it can be used as an offset printing plate using ordinary fountain solution.

  When the pattern formed body of the present invention is used for an element having a pattern laminated thereon, by adjusting the wettability of the surface of the pattern formed body, various functional layers can be patterned on various substrates. Can be formed. Functionality includes optical (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, magnetic permeability, etc., electric / electronic (conductive, insulating, piezoelectric, pyroelectric, dielectric, etc.), chemical (adsorbing, desorbing, catalytic, water absorbing, oil absorbing) Properties, ionic conductivity, redox properties, electrochemical 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).

  The functional element can be produced by applying the composition for a functional layer on a pattern forming body. As the composition for a functional layer, a composition in which an unexposed portion of a pattern-formed body on which a pattern is formed exhibits repellency such as water repellency or oil repellency and is wetted only in an exposed portion can be used. In this case, the unexposed portion of the pattern formed body has a critical surface tension of 50 mN / m or less, preferably 30 mN / m or less. Preferred substances include a silicone resin and a silicone resin having a fluorocarbon group. Further, the composition for a functional layer is desirably made of a material having a surface tension equal to or higher than the critical surface tension in an unexposed portion of the pattern formed body.

  In this case, examples of the functional layer composition 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. In the case of a liquid composition diluted with a solvent, it is preferable that the solvent exhibit high surface tension, such as water or ethylene glycol.

  Further, the lower the viscosity of the composition for a functional layer is, the more the pattern can be formed in a shorter time. 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 evaporation of the solvent during pattern formation.

  The composition for a functional layer is formed by using application means such as dip coating, roll coating, and blade coating, nozzle discharging means including inkjet, and means such as electroless plating. When the functional layer composition contains a component that is cured by ultraviolet light, heat, electron beam, or the like as a binder, the curing treatment is performed to form various components on the substrate via the pattern forming body. Layers having various functions can be formed in a pattern.

  Also, after forming the functional layer on the entire surface, utilizing the difference in adhesive force at the interface between the exposed or unexposed portion and the functional layer, for example, peeling by peeling the adhesive tape after the adhesive tape is adhered, air The functional layer on the unexposed portion can be removed and patterned by post-processing such as spraying or processing with a solvent.

  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.

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

  As the functional layer composition, only a layer having a characteristic as a functional layer only by forming a layer on a pattern forming body, and of course, a layer as a functional layer does not exhibit characteristics as a functional layer. After that, those which require treatment with chemicals, treatment with ultraviolet rays, heat, etc. are also included.

  Next, an element that can be manufactured using the pattern forming 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, when a colorant-containing composition for forming a color filter is applied to a photocatalyst-containing layer formed on a transparent glass substrate after pattern exposure, a change in the wettability of the exposed portion causes the colorant-containing composition to be applied only to the exposed portion. Since the object is applied, the amount of the colorant-containing composition used can be reduced. In addition, since the colorant-containing composition layer is formed only on the pattern, if a photosensitive resin composition is used as the colorant-containing composition, only the photocuring treatment after application can be performed without development. Resolution color filters are possible.

  Further, the pattern forming body of the present invention can be used for manufacturing a microlens. For example, circular exposure is performed on the photocatalyst-containing layer laminated on the transparent substrate to form a circular pattern having changed wettability. Next, when the lens-forming composition is dropped on the portion where the wettability has changed, the composition is wetted and spread only on the exposed portion, and by further dropping, the contact angle of the droplet can be changed. When cured, various shapes or focal lengths can be obtained, so that a high-definition microlens can be obtained.

  In addition, a metal film having a desired pattern can be formed by using the pattern forming body of the present invention in a method for forming a metal film by electroless plating.

  For example, by forming a predetermined hydrophilic pattern by light irradiation on the pattern forming body of the present invention, and then immersed in a chemical plating solution after performing the treatment of the portion that has been made hydrophilic by a pretreatment liquid for chemical plating A desired metal can be patterned. According to this method, a metal pattern can be formed without forming a resist pattern, so that a printed 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 evaporated under vacuum, and a metal component such as aluminum is evaporated on the entire surface of the pattern forming body to form a metal thin film. . There is a difference in the adhesive 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 a method of peeling by pressing an adhesive on the thin film surface, a method of peeling with a chemical, etc. can do.

  When peeling using an adhesive, after contacting the adhesive surface of the sheet coated with the adhesive to the thin film surface, peeling the sheet coated with the adhesive, the pattern forming part and the part where the pattern is not formed The thin film other than the pattern forming portion is peeled off due to the difference in the adhesiveness of the above, 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 an element of the present invention will be described with reference to the drawings.

  FIG. 9 illustrates an example of a method for manufacturing an element of the present invention, and illustrates a cross section.

  In the pattern exposure step of FIG. 9A, as shown in A1, the pattern formed body 1 provided with the photocatalyst containing layer 4 on the base material 2 was formed by using the photomask 20 according to the pattern of the element to be formed. As shown in the exposure 6 or A2, a pattern 13 is drawn directly on the pattern forming body 1 using a laser 21 having a wavelength in the ultraviolet region or the like to form a portion 13 having a different wettability on the surface of the pattern forming body.

  Next, in the entire surface film forming step of FIG. 9B, coating using a blade coater 22 as shown by B1, coating using a spin coater 23 as shown by B2, and vacuum such as evaporation and CVD shown by B3 are performed. The functional layer 25 is formed on the entire surface of the pattern formed body by the film forming means 24 used.

  The functional layer 25 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 energy caused by exposure of the pattern-formed body.

  Next, in a peeling step of FIG. 9C, a method of peeling a functional layer formed on an unexposed part by peeling the adhesive surface of the adhesive tape 26 and then peeling the adhesive layer from an end portion. The functional layer 28 is formed by removing the functional layer from a portion having a small adhesive force by a method of injecting air or a peeling agent.

  FIG. 10 is a view for explaining another embodiment of the method for manufacturing an element of the present invention, and is a view for explaining a cross section.

  Similarly to FIG. 9, the functional layer 25 is formed on the pattern forming body 1 by the method shown in FIG. Next, as shown in FIG. 10B, the element forming base material 29 is closely attached.

  Next, as shown in FIG. 10C, the functional layer 25 is transferred onto the element forming base material 29 to form an element having the functional layer 28.

  FIG. 11 is a diagram for explaining another embodiment of the method for manufacturing an element of the present invention, and a diagram for explaining a cross section.

  As shown in FIG. 11A, the pattern forming body 1 in which the photocatalyst containing layer 4 is provided on the base material 2 is exposed using the photomask 20 according to the pattern of the element to be formed, and the wettability is improved. The changed part 13 is formed.

  Next, as shown in FIG. 11B, the surface of the thermal transfer member 32 having the heat-fusible composition layer 31 formed on the sheet 30 is closely attached to the exposed surface of the pattern-formed body. .

  Next, as shown in FIG. 11C, the heating plate 33 is pressed from the sheet side of the thermal transfer body 32.

  Next, as shown in FIG. 11D, the thermal transfer member 32 was peeled off after cooling, and finally a pattern 5 as shown in FIG. 11E was formed.

  FIG. 12 is a view for explaining another embodiment of the method for manufacturing an element of the present invention, and a view for explaining a cross section.

  As shown in FIG. 12A, the pattern formed body 1 was exposed using a photomask 20, and an unexposed portion and a portion 13 having changed wettability due to the exposure were formed.

  As shown in FIG. 12B, the ultraviolet curable resin composition 36 is discharged from the discharge nozzle 35 toward a circular pattern.

  As shown in FIG. 12C, due to the difference in wettability between the unexposed portion and the exposed portion, the ultraviolet curable resin composition discharged to the exposed portion rises due to the difference in interfacial tension.

  Next, as shown in FIG. 12D, the microlenses 38 can be formed by irradiating ultraviolet rays for curing 37.

  Hereinafter, the present invention will be described with reference to examples.

Example 1
30 g of Glasca HPC7002 (Nippon Synthetic Rubber) and 10 g of Glaska HPC402H (Nippon Synthetic Rubber), which is an alkylalkoxysilane, were mixed and stirred by a stirrer for 5 minutes. This solution was applied to a glass substrate having an area of 7.5 cm ² by spin coating, and dried at a temperature of 150 ° C. for 10 minutes to form a sodium ion blocking layer having a thickness of 2 μm.

  Next, 15 g of Glasca HPC7002 (Nippon Synthetic Rubber), 5 g of Glasca HPC402H (Nippon Synthetic Rubber), and titania sol (TA-15 manufactured by Nissan Chemical Industries, Ltd.) were mixed. This solution was applied on a substrate on which a sodium ion block layer was formed by a spin coating method. This was dried at a temperature of 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reactions to proceed, thereby producing a pattern formed body having a 3 μm-thick photocatalyst-containing layer in which the photocatalyst was firmly fixed with organopolysiloxane.

The obtained pattern-formed body was irradiated with ultraviolet light at an illuminance of 6.6 mW / cm ^{2 using} a xenon lamp, and the change over time of the contact angle with water was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). FIG. 5 shows the results. From the figure, it can be seen that the contact angle gradually decreases to 10 ° or less. In addition, by irradiating ultraviolet rays through a lattice-shaped mask, irradiation with a xenon lamp at an illuminance of 6.6 mW / cm ² for 6 hours is performed to form a pattern having different wettability at an irradiated portion of 9 ° and an unirradiated portion of 102 °. Was able to do.

Example 2
A 20% by weight dimethylformamide solution of a primer layer forming composition (Kancoat 90T-25-3094 manufactured by Kansai Paint) is applied on a degreased aluminum plate having a thickness of 0.15 mm, dried at 200 ° C. for 1 minute, and dried at 3 μm. Was obtained. The photocatalyst-containing layer described in Example 1 was formed on this primer layer to obtain a waterless printing plate precursor.

Next, a pattern was formed using a Nd: YAG laser (355 nm lambda physics Star Line) with a recording energy of 300 mJ / cm ² . The obtained printing plate was attached to an offset printing press (Alpha New Ace manufactured by Alpha Giken), and a printing speed of 5000 sheets / hour was used using a waterless printing ink (Inktec Waterless S Indigo manufactured by The Inktec). When printing was performed on coated paper, 20,000 good printed matters were obtained.

  In addition, in place of laser, the same printing was performed at 175 lines / inch except that the film was exposed to a xenon lamp through a gradation negative film having 2% to 98% of halftone dots. Obtained.

Example 3
3 g of Glasca HPC7002 (Nippon Synthetic Rubber) as a silica sol and 1 g of HPC402H (Nippon Synthetic Rubber) as an alkylalkoxysilane were mixed and stirred for 5 minutes. This solution was applied to a glass substrate having an area of 7.5 cm ² by spin coating to form a sodium ion blocking layer having a thickness of 2 μm.

  Next, 3 g of isopropyl alcohol, 0.75 g of silica sol (Glaska HPC7002 made by Nippon Synthetic Rubber), 0.25 g of alkylalkoxysilane (Glaska HPC402H made by Nippon Synthetic Rubber), and fluoroalkoxysilane (MF-160E: N- [3 -(Trimethoxysilyl) propyl] -N-ethyl perfluorooctanesulfonamide in 50% by weight of isopropyl ether). The obtained dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. Thereafter, 2 g of titanium oxide (Titanium oxide coating liquid ST-K01: solid content concentration: 10% by weight, manufactured by Ishihara Sangyo) was added, and the mixture was further stirred for 30 minutes.

  This dispersion was applied by spin coating to the base material having the sodium block layer prepared above. This was dried at a temperature of 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reactions to proceed, thereby forming a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed by organopolysiloxane. When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by a stylus method, it was Ra = 2 nm.

Further, a high-pressure mercury lamp was irradiated with ultraviolet light at 70 mW / cm ² for 2 minutes through a lattice-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). Table 4 shows the measurement results.

Example 4
A sodium ion blocking layer was prepared in the same manner as in Example 3, then 3 g of isopropyl alcohol, 0.4 g of organosilane (TSL8113 manufactured by Toshiba Silicone), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3 0.15 g of-(trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in isopropyl ether (50% by weight), titanium oxide (Ishihara Sangyo Co., Ltd. titanium oxide coating liquid ST-K01: solid content concentration: 10% by weight) ) Was added and mixed. The obtained dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on a substrate on which a sodium ion block layer was formed by a spin coating method. This was dried at 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reaction to proceed, thereby forming a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed in organosiloxane. When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by the stylus method in the same manner as in Example 3, Ra was 2 nm. A high pressure mercury lamp was irradiated on the photocatalyst-containing layer with a high-pressure mercury lamp at an illuminance of 70 mw / cm ² for 2 minutes through a lattice-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring device (CA manufactured by Kyowa Interface Science Co., Ltd.). -Z type) are shown in Table 4.

Example 5
A 0.3 μm-thick photocatalyst-containing layer was formed on a polycarbonate substrate by spin coating as described in Example 4, and a high-pressure mercury lamp was applied to the photocatalyst-containing layer via a chart mask having a resolution of 50 lp / mm. Ultraviolet irradiation was performed at an illuminance of 70 mW / cm ² for 2 minutes.

  Various liquids whose surface tension is known are dropped on the obtained photocatalyst-containing layer, the contact angle is measured by a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science), and the critical surface tension is determined by Zisman plot. As a result, the critical surface tension of the unexposed portion was 14.6 mN / m, and that of the exposed portion was 72.3 mN / m.

  Next, a lithographic ink without water (Inktec Waterless S Indigo, manufactured by The Inktec) was applied to the entire surface of the exposed photocatalyst-containing layer using an RI tester (RI-2, manufactured by Ishikawajima Sangyo Kikai). As shown in FIG. 6, the ink is repelled by the oil repellency in the unexposed portion, and is selectively applied only to the exposed portion, and is applied on the transparent polycarbonate substrate 2 via the photocatalyst layer 4 at a blue color of 50 lp / mm. A striped pattern 18 was obtained.

Example 6
3 g of Glasca HPC7002 (Nippon Synthetic Rubber) as a silica sol and 1 g of HPC402H (Nippon Synthetic Rubber) as an alkylalkoxysilane were mixed and stirred for 5 minutes. This solution was applied on a degreased aluminum plate having a thickness of 0.15 mm by spin coating to obtain a primer layer having a thickness of 2 μm.

  Next, the photocatalyst-containing layers described in Examples 3 and 4 were formed on the primer layer to obtain a waterless printing plate precursor.

Next, a pattern was formed using an Nd: YAG laser (355 nm lambda physics Star Line) with a recording energy of 200 mJ / cm ² . The obtained printing plate was attached to an offset printing base (Alpha New Ace manufactured by Alpha Giken), and a printing speed of 5000 sheets / hour was used using a waterless printing ink (Inktec Waterless S Indigo manufactured by The Inktech). When printing was performed on coated paper, 20,000 good printed matters were obtained.

Further, instead of the laser, a high-pressure mercury lamp was irradiated with ultraviolet light at 70 mW / cm ² for 2 minutes through a gradation negative pattern having 2% to 98% of halftone dots at 175 lines / inch, and the printing characteristics were similarly changed. As a result, a good printed matter was obtained.

Example 7
A sodium ion blocking layer was prepared in the same manner as in Example 3, then 3 g of isopropyl alcohol, 2.2 g of organosilane (TSL8113 manufactured by Toshiba Silicone), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3 0.15 g of-(trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether) and 0.2 g of titanium oxide powder (ST-21, manufactured by Ishihara Sangyo, average particle size: 20 nm) were mixed. . The obtained dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on a substrate on which a sodium ion block layer was formed by a spin coating method. This was dried at 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reaction to proceed, thereby forming a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed in organosiloxane. When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by a stylus method, it was Ra = 4 nm. In addition, a high-pressure mercury lamp was irradiated with ultraviolet light at 70 mW / cm ² for 5 minutes on the photocatalyst-containing layer through a lattice-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring device (manufactured by Kyowa Interface Science). Table 4 shows the results of measurement by CA-Z type).

Example 8
An illuminance of 70 mW / cm ² was applied to a photocatalyst-containing layer having a thickness of 0.3 μm produced by the method described in Example 7 using a high-pressure mercury lamp through a mask in which light-shielding layers having a size of 150 × 300 μm were arranged at intervals of 30 μm. For 5 minutes.

  Various liquids whose surface tension is known are dropped on the obtained photocatalyst-containing layer, the contact angle is measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science), and the critical interfacial tension is determined by Zisman plot. As a result, the critical surface tension of the unexposed portion was 15.4 mN / m, and that of the exposed portion was 73.3 mN / m.

  Next, 4 g of carbon black (# 950, manufactured by Mitsubishi Chemical Corporation), 0.7 g of polyvinyl alcohol (Gohsenol AH-26, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and 95.3 g of water were mixed, dissolved by heating, centrifuged at 12000 rpm, and centrifuged at 1 μm. The mixture was filtered through a glass filter to obtain a light-shielding composition.

  When the surface tension of the obtained light-shielding composition was measured with a surface tensiometer (PD-Z type, manufactured by Kyowa Interface Science), it was 37.5 mN / m.

  This was applied to the entire surface of the exposed photocatalyst layer by a blade coater at a blade gap of 40 μm and a speed of 0.6 m / min. As shown in FIG. 7, the unexposed portion repels the light-shielding composition, is selectively applied only to the exposed portion, and is heated at 100 ° C. for 30 minutes to form the photocatalyst layer 4 on the glass substrate 2. Thus, a grid-like light-shielding pattern 19 was obtained.

Example 9
A sodium ion blocking layer was prepared in the same manner as in Example 3, then 3 g of isopropyl alcohol, 2.2 g of organosilane (TSL8113 manufactured by Toshiba Silicone), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3 0.15 g of-(trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether) and 0.2 g of titanium oxide powder (ST-21, manufactured by Ishihara Sangyo, average particle size: 20 nm) were mixed. . The resulting dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on a substrate on which a sodium ion block layer was formed by a spin coating method. This was dried at 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reaction to proceed, thereby forming a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed in organosiloxane. When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by the stylus method in the same manner as in Example 1, Ra was 4 nm. In addition, a high-pressure mercury lamp was irradiated with ultraviolet light at 70 mW / cm ² for 5 minutes on the photocatalyst-containing layer through a lattice-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring device (manufactured by Kyowa Interface Science). Table 4 shows the results of measurement by CA-Z type).

Example 10
A sodium ion blocking layer was formed on a glass substrate in the same manner as in Example 3. Next, a photocatalyst-containing layer was formed in the same manner as in Example 9, and exposure was performed in the same manner as in Example 9.

  Elemental analysis was performed on the unexposed portion and the exposed portion using an X-ray photoelectron spectrometer (ESCALAB220-I-XL, manufactured by VG Scientific). Quantitative calculation was performed by the correction of Charlie's background and the correction of Scofield's relative sensitivity coefficient, and the obtained results are shown in Table 1 as relative values by weight when Si is set to 100.

  Exposure shows that the proportions of carbon and fluorine are reduced and the proportion of oxygen is increased. From the results of Example 9, considering that the contact angle to water is reduced, the result of the exposure is It is considered that an organic group such as a methyl group or a fluoroalkyl group bonded to a silicon atom was replaced with an oxygen-containing group such as a hydroxyl group.

Example 11
A sodium ion blocking layer was prepared in the same manner as in Example 3, then 3 g of isopropyl alcohol, 0.4 g of organosilane (TSL8113 manufactured by Toshiba Silicone), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3 0.75 g of-(trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether, titanium oxide (Ishihara Sangyo Co., Ltd. titanium oxide coating solution ST-K01: solid content concentration 10% by weight) ) 2 g were mixed. The resulting dispersion was stirred for 60 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on a substrate on which a sodium ion block layer was formed by a spin coating method. This was dried at 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reaction to proceed, thereby forming a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed in organosiloxane. In addition, a high pressure mercury lamp was irradiated on the photocatalyst-containing layer with a high-pressure mercury lamp at an illuminance of 70 mW / cm ² for 10 minutes through a lattice-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring instrument (CA manufactured by Kyowa Interface Science Co., Ltd.). -Z type) are shown in Table 4.

Example 12
A photocatalyst-containing layer having a thickness of 0.3 μm was formed in the same manner as in Example 4. Ultraviolet irradiation was performed with a high-pressure mercury lamp at an illuminance of 70 mW / cm ² for 2 minutes through a mask having a light-shielding layer having a pitch of 100 μm. When the photosensitive resin composition for forming a colored pixel of the color filter was dropped with a dispenser (1500XL manufactured by EFD), the exposed portion became wet and spread to form a pixel.

Example 13
3 g of isopropyl alcohol, 0.3 g of organosilane (TSL8113 manufactured by Toshiba Silicone), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctane sulfonamide 0.45 g of a 50% by weight solution of isopropyl ether) and 2 g of titanium oxide (solution ST-K01 for titanium oxide coating manufactured by Ishihara Sangyo Co., Ltd .: solid content concentration: 10% by weight) were mixed. The obtained dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on an aluminum substrate having a thickness of 0.3 mm by spin coating. This was dried at a temperature of 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reaction to proceed, thereby forming a 0.5 μm-thick photocatalyst-containing layer in which the photocatalyst was firmly fixed in organosiloxane.

In a state where the obtained pattern formed body was heated to various temperatures on a hot plate, a heat ray was removed from an ultra-high pressure mercury lamp (UXM-3500, ML-40D type lamp house manufactured by Ushio Inc.) to give an ultraviolet ray of 241 nm to 271 nm. Only light was irradiated at an intensity of 8.1 mW / cm ² for 300 seconds, and the contact angle with water was measured with a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science Co., Ltd.). Shows that the photocatalytic reaction is promoted.

Example 14
In the same manner as in Example 3, a photocatalyst-containing layer was formed on quartz glass having a length of 10 cm and a width of 10 cm. Negative photomasks having a size of a light transmitting portion of 150 μm × 300 μm and arranged at intervals of 30 μm are arranged on the pattern forming body with close contact and a gap of 100 μm, and are 320 nm to 390 nm with a high-pressure mercury lamp. Was irradiated at an illuminance of 70 mW / cm ² for 2 minutes, and then the contact angle with water was measured with a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science). The results are shown in Table 3.

Example 15
When a gap of 100 μm was provided in the same manner as in Example 14, and exposure was similarly performed in a state where air was blown on the exposed surface of the pattern formed body, the exposed portion was 70 seconds, and the contact angle of water was 5 ° or less. .

Example 16
A primer layer and a photocatalyst containing layer were formed on a glass substrate having a length of 10 cm, a width of 10 cm, and a thickness of 0.1 cm in the same manner as in Example 10. Ultraviolet light of 320 nm to 390 nm was irradiated from a high-pressure mercury lamp at an illuminance of 70 mW / cm ² for 7 minutes from a high-pressure mercury lamp through a photomask in which light-shielding portions of 100 μm vertically and horizontally were formed at intervals of 20 μm.

Then, on a polyester film having a thickness of 10 μm, as a heat-fusible ink layer, the following composition: carbon black (manufactured by Mitsubishi Chemical Corporation # 25): 20 parts by weight ethylene-vinyl acetate copolymer (manufactured by DuPont Mitsui Polychemicals): 10 parts by weight Carnauba wax: 10 parts by weight Paraffin wax (HNP-11, manufactured by Nippon Seiro): An ink ribbon formed with a heat-fusible ink composition layer consisting of 60 parts by weight is brought into close contact with the pattern-exposed photocatalyst-containing layer. After heating to 90 ° C., the ink ribbon was peeled off at a speed of 150 mm / sec at an angle of 70 °.

The ink did not adhere to the unexposed portions of the pattern formed body, and the ink was transferred only to the exposed portions, so that a light-shielding pattern could be formed.

Example 17
In the same manner as in Example 10, a pattern formed body having a primer layer and a photocatalyst-containing layer formed on a glass substrate having a length of 10 cm, a width of 10 cm, and a thickness of 0.1 cm. A high-pressure mercury lamp is used to irradiate ultraviolet light of 320 to 390 nm at an illuminance of 70 mW / cm ² for 7 minutes from a high-pressure mercury lamp through a photomask formed by forming lines having a width of 5 μm on the obtained pattern formed body at the same interval as the line width. did.

  Next, the light-irradiated pattern-formed body was rocked at 25 ° C. for 20 seconds at 25 ° C. to a liquid having a concentration of 12.5 ml / l obtained by diluting a sensitizer solution for chemical plating (S-10X for glass and ceramic manufactured by Uemura Kogyo). After immersion, washing with water, immersion in a 12.5 ml / l concentration diluted solution of a reducing catalyst-applied solution (Palladium colloidal catalyst A-10X manufactured by Uemura Kogyo) at 25 ° C for 20 seconds while shaking, followed by 80 ° C By performing rocking immersion treatment for 1 hour in an electroless nickel plating solution (Nimden LPX manufactured by Uemura Kogyo Co., Ltd.), a nickel layer having a thickness of 0.5 μm could be formed on the exposed portion.

  Further, it was immersed in a 90 ° C. electroless gold plating bath (ELGB511 manufactured by Uemura Kogyo) while rocking for 5 minutes to form a gold layer having a thickness of 0.1 μm on the nickel pattern. In a non-electrolytic gold plating bath for use (GOBEL2M manufactured by Uemura Kogyo Co., Ltd.), it was immersed for 1 hour while oscillating to form gold having a thickness of 2 μm.

Example 18
The same composition as in Example 4 was spin-coated on a quartz glass substrate having a length of 10 cm, a width of 10 cm and a thickness of 0.1 cm to form a photocatalyst layer having a thickness of 0.4 μm. Next, through a photomask having a rectangular pattern of 23 μm × 12 μm, the opening is exposed to a mercury lamp at an illuminance of 70 mW / cm ² for 90 seconds to form a rectangular pattern having a high surface energy on the photocatalyst-containing layer. A transparent substrate was obtained.

Next, a thin film of a perylene-based pigment having the following chemical structural formula was vacuum-deposited on the entire surface of the obtained transparent substrate at a degree of vacuum of 1 × 10 ⁻⁵ Torr and a deposition rate of 1 nm / sec. Then, when the surface of the thin film was washed with acetone, the deposited film was peeled off only in the unexposed portions due to the difference in adhesiveness between the exposed portions and the unexposed portions, and a rectangular pattern of a 23 μm × 12 μm rectangular red pigment was formed. We were able to.

Example 19
A composition similar to that of Example 4 was spin-coated on a 100 μm-thick polyimide film to form a 0.4 μm-thick photocatalyst-containing layer. This was exposed through a negative photomask having a circuit pattern drawn with a width of 50 μm with a mercury lamp at an illuminance of 70 mW / cm ² for 90 seconds to form a portion having high surface energy on the photocatalyst-containing layer. A transparent substrate was obtained.

Next, aluminum was vacuum-deposited on the entire surface of the obtained transparent substrate at a degree of vacuum of 1 × 10 ⁻⁵ Torr and a deposition rate of 4 nm / sec. Next, when the surface of the aluminum thin film was peeled off at a speed of 135 ° and 300 mm / sec with a cellophane adhesive tape (JIS Z 1522 manufactured by Sekisui), the exposed portion was exposed due to the difference in adhesion between the exposed portion and the unexposed portion. Due to the difference in the adhesiveness between the aluminum thin film in the unexposed part and the transparent substrate, the vapor-deposited film is peeled off only in the unexposed part to obtain a circuit pattern having a width of 50 μm and a thickness of 0.1 μm. Was completed.

Example 20
The same composition as in Example 4 was spin-coated on quartz glass to form a 0.3 μm-thick photocatalyst-containing layer. Ultraviolet irradiation was performed on the photocatalyst-containing layer at an illuminance of 70 mW / cm ² for 2 minutes by a mercury lamp through a mask having an opening having a diameter of 5 mm.

  Various liquids whose surface tension is known are dropped on the obtained photocatalyst-containing layer, and the contact angle is measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science), and the critical surface tension is determined by Zisman plot. Was determined, the critical interfacial tension of the unexposed portion was 14.6 mN / m, and that of the exposed portion was 72.3 mN / m.

  Next, a composition was prepared by mixing 100 parts by weight of an ultraviolet curable monomer (Arakawa Kogyo Beam Set 770) and 5 parts by weight of a curing initiator (Irgacure 1700 manufactured by Ciba Specialty Chemicals).

  The surface tension of the obtained ultraviolet-curable monomer composition was measured by a surface tensiometer (PD-Z type, manufactured by Kyowa Interface Science) and found to be 35 mN / m. The viscosity was measured with a viscometer (CJV5000, manufactured by Chichibu Onoda) and found to be 4.3 mPa · s. This UV-curable monomer was applied to the entire surface of the exposed photocatalyst-containing layer by spin coating.

The unexposed portions repelled the ultraviolet-curable monomer composition and were selectively applied only to the exposed portions. Next, when a high-pressure mercury lamp was used to irradiate ultraviolet rays at an illuminance of 70 mW / cm ² for 3 minutes, a resin-cured circular pattern having a diameter of 5 mm was obtained.

Comparative Example 1
The properties were evaluated in the same manner as in Example 3 using a commercially available original plate for offset printing using a thermal plate Pearl dry (manufactured by Presstek), and the results are shown in Table 4.

Comparative Example 2
The properties were evaluated in the same manner as in Example 3 using a commercially available offset printing plate using a waterless offset plate HGII (manufactured by Toray Industries Inc.), and the results are shown in Table 4.

Comparative Example 3
A photocatalyst-containing layer was formed in the same manner as in Example 4 except that no fluoroalkylsilane was used, and the characteristics of the photocatalyst-containing layer were evaluated in the same manner as in Example 4. The results are shown in Table 4.

Comparative Example 4
A sodium ion blocking layer was prepared in the same manner as in Example 3, then 3 g of isopropyl alcohol, 2.2 g of organosilane (TSL8113 manufactured by Toshiba Silicone), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3 0.15 g of-(trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in isopropyl ether (50% by weight) and 0.2 g of titanium oxide powder (ST-41 manufactured by Ishihara Sangyo Co., Ltd., average particle size: 50 nm) were mixed. . The obtained dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on a substrate on which a sodium ion block layer was formed by a spin coating method. This was dried at 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reaction to proceed, thereby forming a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed in organosiloxane. When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by the stylus method in the same manner as in Example 1, Ra = 30 m. In addition, a high pressure mercury lamp was irradiated on the photocatalyst-containing layer with a high-pressure mercury lamp at 70 mW / cm ² for 5 minutes through a grid-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring device (CA manufactured by Kyowa Interface Science Co., Ltd.). -Z type) are shown in Table 4.

Example 21
A 20% by weight dimethylformamide solution of a primer layer forming composition (Kancoat 90T-25-3094 manufactured by Kansai Paint) is applied on a degreased aluminum plate having a thickness of 0.15 mm, dried at 200 ° C. for 1 minute, and dried at 3 μm. Was obtained.

  Next, 3 g of isopropyl alcohol, 4.2 g of organosilane (TSL8113, manufactured by Toshiba Silicone) and 0.2 g of titanium oxide powder (ST-01, average particle size 7 nm, manufactured by Ishihara Sangyo) were mixed. The resulting dispersion was stirred for 60 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on a substrate on which a primer layer had been formed by a spin coating method. This was dried at a temperature of 150 ° C. for 5 minutes to allow hydrolysis and polycondensation reactions to proceed, thereby forming a film.

Next, the high-pressure mercury lamp was irradiated with ultraviolet light at an illuminance of 70 mW / cm ² for 10 minutes, and the contact angle with water and n-octane was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). Show.

  The lithographic printing plate precursor with water was exposed at 175 lines / inch using a mercury lamp through a gradation positive mask having 2% to 98% halftone dots to form a pattern.

  Next, the obtained printing plate was attached to an offset printing machine (Alpha New Ace manufactured by Alpha Giken), and a printing ink (Across Red, manufactured by The Inktec) and a fountain solution (diluted by 20 times with a clean etch solution manufactured by Niken Kagaku) When printing was performed on coated paper at a printing speed of 5000 sheets / hour using, a good printed matter of 20,000 sheets was obtained.

Example 22
2.7 g of tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , 38.7 g of ethanol and 4.5 g of 2N hydrochloric acid were mixed and stirred for 10 minutes. This solution was applied to a substrate by a spin coating method, and dried at a temperature of 80 ° C. for 30 minutes to form a 0.2 μm thick sodium ion blocking layer.

0.62 g of tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , 0.96 g of titania sol (TA-15 manufactured by Nissan Chemical), 26.89 g of ethanol, and 0.32 g of pure water were mixed and stirred for 10 minutes. This dispersion was applied on a substrate on which a sodium ion blocking layer was formed by a spin coating method. This is dried at a temperature of 150 ° C. for 30 minutes to promote hydrolysis and polycondensation reactions, and has a high surface energy and a 0.2 μm thick photocatalyst-containing composition in which the photocatalyst is firmly fixed in silica. The layer was formed and used as Sample 1.

Next, a solution having a concentration of 5% by weight in which olive oil was dissolved in cyclohexanone was applied onto the photocatalyst-containing composition layer of Sample 1 by a spin coating method so that the application amount was 1 g / m ^2, and a temperature of 80 ° C. For 10 minutes to produce an organic layer having a low surface energy.

The obtained sample 1 and sample 2 were irradiated with ultraviolet light at an illuminance of 230 mW / cm ² for 5 minutes using a mercury lamp, and the contact angle with water was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). Table 6 shows the results. It was found that the organic layer of Sample 2 was decomposed and removed by the photocatalytic action, and returned to the state of Sample 1 before the application of the organic substance. Gender did not change.

Further, a 2% by weight aqueous solution of polyvinyl alcohol (Gohsenol AH-26 manufactured by Nippon Synthetic Chemical Industry) was applied on the surface of the sample 1 with a thickness of 0.2 μm by a spin coater, and then heated at 80 ° C. for 45 minutes to form a film. Next, ultraviolet irradiation was performed for 8 minutes at an illuminance of 230 mW / cm ² using a mercury lamp, and the contact angle of water was measured with a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science). Was 5 ° or less.

Example 23
99.99% by weight of hydroxyl-terminated polydimethylsiloxane (polymerization degree: 700), 5% by weight of methyltriacetoxysilane, 0.01% by weight of dibutyltin dilauryllate in 5% by weight dissolved in Isopar E (manufactured by Exxon). The solution having the concentration was applied on the sample 1 described in Example 22 so as to have a film thickness of 0.2 μm by a spin coating method, and dried at a temperature of 100 ° C. for 10 minutes to form a film.

Next, when irradiation was performed with a mercury lamp at an illuminance of 50 mW / cm ² for 1 minute, the wettability changed from 130 ° to 5 ° or less as the contact angle of water.

  A 20% by weight dimethylformamide solution of a primer layer forming composition (Kancoat 90T-25-3094 manufactured by Kansai Paint) is applied on a degreased aluminum plate having a thickness of 0.15 mm, dried at 200 ° C. for 1 minute, and dried at 3 μm. Was obtained.

  Next, on this primer layer, the photocatalyst-containing layer described in Example 22 and a material layer whose wettability was changed were formed to obtain a waterless printing plate precursor.

Next, a pattern was formed using an Nd: YAG laser (355 nm lambda physics Star Line) with a recording energy of 200 mJ / cm ² . The obtained printing plate was attached to an offset printing machine (Alpha New Ace manufactured by Alpha Giken), and a printing speed of 5000 sheets / hour was used using a waterless printing ink (Ink Tech Waterless S Yellow manufactured by The Ink Tech). When printing was performed on coated paper, 20,000 good printed matters were obtained.

Example 24
A sodium block layer similar to that of Example 22 was formed on a soda lime glass substrate having a length of 10 cm, a width of 10 cm, and a thickness of 0.1 cm. A solution obtained by mixing 1 g of tetraethoxytitanium (Ti (OC ₂ H ₅ ) ₄ ), 9 g of ethanol and 0.1 g of hydrochloric acid was applied on the obtained layer by spin coating.

  Next, heating was performed at 150 ° C. for 10 minutes to form an amorphous titania layer having a thickness of 0.1 μm. The amorphous titania layer was heated at 400 ° C. for 10 minutes to change the phase to an anatase type titania layer.

Next, a layer having a change in wettability was formed on the titania layer in the same manner as in Example 23, and irradiation was performed with a mercury lamp at an illuminance of 50 mW / cm ² for 2 minutes using a chart mask having a resolution of 50 lp / mm.

  Next, an ink for waterless printing (Inktec Waterless S Yellow manufactured by The Inktech Co., Ltd.) is applied on the entire exposed pattern formed body obtained using an RI tester (RI-2 type manufactured by Ishikawajima Sangyo Kikai). did. As a result, the unexposed portions repelled the ink due to oil repellency, and a yellow pattern selectively applied only to the exposed portions was obtained.

Example 25
A glass substrate having a sodium ion blocking layer was produced in the same manner as in Example 1. Next, 0.14 g of a surfactant (BL-2 manufactured by Nippon Surfactant Industries), 0.62 g of tetraethoxysilane Si (OC ₂ H ₅ ) ₄ , 0.96 g of titania sol (TA-15 manufactured by Nissan Chemical), ethanol 26. 89 g and 0.32 g of water were mixed and stirred for 10 minutes. This dispersion was applied on a substrate having a sodium ion blocking layer having a thickness of 0.2 μm by a spin coating method.

Next, by drying at a temperature of 150 ° C. for 30 minutes, the hydrolysis and the polycondensation reaction are allowed to proceed, and a 0.2 μm-thick photocatalyst-containing composition layer in which the photocatalyst and the surfactant are firmly fixed in silica is formed. Produced. The obtained sample was irradiated with ultraviolet light from a xenon lamp at an illuminance of 3 mW / cm ² , and the time-dependent change of the contact angle with water was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). FIG. 8 shows the results. From the figure, it was confirmed that the contact angle, which was 63 ° before irradiation, decreased with irradiation time, and dropped to 6 ° in about 80 minutes.

Example 26
3 g of Glasca HPC7002 (Nippon Synthetic Rubber) as a silica sol and 1 g of HPC402H (Nippon Synthetic Rubber) as an alkylalkoxysilane were mixed and stirred for 5 minutes. This solution was applied to an aluminum substrate having a thickness of 0.15 mm by spin coating to form a 2 μm-thick primer layer.

  Next, the photocatalyst-containing layer described in Example 23 was formed on the primer layer to obtain a printing plate precursor.

  The resulting printing plate precursor was exposed as a lithographic printing plate precursor with water at 175 lines / inch through a gradation positive film having 2 to 98% halftone dots by the xenon lamp to form a pattern.

  Next, the obtained printing plate was attached to an offset printing machine (Alpha New Ace, manufactured by Alpha Giken), and a printing speed of 5000 sheets / hour was used using an offset printing ink (Across Red, manufactured by The Inktec) and a fountain solution. When printing was performed on coated paper, 20,000 good printed matters were obtained.

Example 27
A 0.4 μm-thick photocatalyst-containing layer was formed on a quartz glass transparent substrate by spin coating with the same composition as in Example 4. Next, exposure was performed with a mercury lamp at an illuminance of 70 mW / cm 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.

  1000 g of a water-soluble ultraviolet-curable ester acrylate resin (AQ-7 manufactured by Arakawa Kogyo), 50 g of a curing initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals), and 25 g of water were mixed and stirred for 3 minutes. Using a microsyringe, 30 μl of the obtained mixture was dropped at the center of circular patterns having different wettabilities formed on the transparent substrate.

Then, irradiation was performed with a mercury lamp at an illuminance of 70 mW / cm ² for 10 seconds to produce a lens having a diameter of 9 mm and a focal length of 45 mm.

Example 28
A 0.4 μm-thick photocatalyst-containing layer was formed on a quartz glass transparent substrate by spin coating with the same composition as in Example 4. Next, exposure was performed for 90 seconds with a mercury lamp at an illuminance of 70 mW / cm ² through a mask having a circular pattern having an opening diameter of 1 mm to obtain a transparent substrate having a surface with a highly wettable circular pattern.

1000 g of a water-soluble ultraviolet-curable ester acrylate resin (AQ-7 manufactured by Arakawa Kogyo), 50 g of a curing initiator (Irgacure 184 manufactured by Ciba Specialty Chemicals), and 125 g of water were mixed and stirred for 3 minutes. When the obtained mixed solution was applied to a circular pattern having a different wettability formed on a transparent substrate by spin coating to a thickness of 20 μm, the mixed solution adhered only to the circular portion. Then, irradiation was performed with a mercury lamp at an illuminance of 70 mW / cm ² for 3 seconds to produce a lens having a diameter of 1 mm and a focal length of 2.5 mm.

Example 29
A degreased aluminum plate having a thickness of 0.23 mm is coated with a 20% by weight dimethylformamide solution of a primer (a primer paint for metal, Kankoto 90T-25-3094, manufactured by Kansai Paint), dried at 200 ° C. for 1 minute, and a 3 μm primer layer is formed. Formed.

  Next, 9 g of OH-modified polydimethylsiloxane (X-22-160AS, functional group equivalent 112, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 g of a cross-linking agent (polyisocyanate, Coronate L, manufactured by Nippon Polyurethane), 1 g of butyltin dilaurate 0.05 g, 1 g of titanium oxide powder (Ishihara Sangyo ST-01, particle size 7 nm), 5 g of 1,4-dioxane, 5 g of isopropanol were applied, dried at 120 ° C. for 2 minutes, and a photocatalyst-containing layer having a thickness of 1 μm. Was formed to obtain a printing plate precursor. When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by a stylus method, it was Ra = 2 nm.

Next, an excimer laser of 248 nm was irradiated at an intensity of 200 mJ / cm ² to form a pattern and cause a photocatalytic reaction.

  When the contact angle of the irradiated portion with water and n-octane was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science), a difference in wettability could be confirmed. Table 7 shows the measurement results.

Example 30
The printing plate prepared in Example 29 was attached to an offset printing machine (Komori Sprint 4-color machine), and printing was performed on coated paper using printing ink (Dryo Color Indigo Ink manufactured by Dainippon Ink and Chemicals, Incorporated). A printed matter was obtained.

Example 31
In the same manner as in Example 29, a primer layer was formed on an aluminum substrate having a thickness of 0.23 mm, and then, on this primer layer, polydimethylsiloxane modified with OH at both ends (X-22- manufactured by Shin-Etsu Chemical Co., Ltd.) 160AS) 8 g, polydimethylsiloxane (KF96 manufactured by Shin-Etsu Chemical) 1 g, crosslinking agent (polyisocyanate Coronate L manufactured by Nippon Polyurethane) 1 g, dibutyltin dilaurate 0.05 g, titanium oxide powder (Ishihara Sangyo ST-01 particle size 7 nm) 1 g , 5 g of toluene and 5 g of isopropanol were applied and dried at 150 ° C. for 2 minutes to form a photocatalyst-containing layer having a thickness of 1 μm to obtain a printing plate precursor.

  When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by a stylus method, Ra was 2 nm.

Next, an excimer laser of 248 nm was irradiated at an intensity of 200 mJ / cm ² to form a pattern and cause a photocatalytic reaction.

  When the contact angle of water and n-octane of the light irradiation part was measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science), a difference in wettability could be confirmed. Table 7 shows the measurement results.

  Further, in the same manner as in Example 30, the printing plate was attached to an offset printing press (Komori Sprint 4-color press), and printing was performed on coated paper using a printing ink (Dai Nippon Ink and Chemicals' dry color indigo ink). However, good printed matter was obtained.

Example 32
3 g of silica sol (Glaska HPC7002 made by Japan Synthetic Rubber) and 1 g of alkylalkoxysilane (HPC402H made by Japan Synthetic Rubber) were mixed and stirred for 5 minutes. This solution was applied to a glass substrate having an area of 7.5 cm ² by spin coating to form a sodium ion blocking layer having a thickness of 2 μm.

  Next, 3 g of isopropyl alcohol, 0.75 g of silica sol (Glaska HPC7002 made by Nippon Synthetic Rubber), 0.25 g of alkylalkoxysilane (Glaska HPC402H made by Nippon Synthetic Rubber), and fluoroalkoxysilane (MF-160E: N- [3 -(Trimethoxysilyl) propyl] -N-ethyl perfluorooctanesulfonamide in 50% by weight of isopropyl ether). The obtained dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. Thereafter, 2 g of titanium oxide (Titanium oxide coating liquid ST-K01 manufactured by Ishihara Sangyo; solid content concentration: 10% by weight) was added, and the mixture was further stirred for 30 minutes.

  This dispersion was applied by spin coating to the substrate on which the sodium block layer had been formed previously. This was dried at a temperature of 150 ° C. for 10 minutes to allow hydrolysis and polycondensation reactions to proceed, thereby forming a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed by organopolysiloxane.

  Next, on the photocatalyst-containing layer, 1 g of OH-modified polydimethylsiloxane (X-22-160AS manufactured by Shin-Etsu Chemical), 2 g of silica sol (Glaska HPC7002 manufactured by Nippon Synthetic Rubber), and 1 g of alkylalkoxysilane (HPC402H manufactured by Nippon Synthetic Rubber) were added. The dispersion liquid which was mixed and stirred for 5 minutes was applied and dried at a temperature of 150 ° C. for 20 minutes to obtain a pattern formed body having a dry film thickness of 0.5 μm.

  When the average roughness of the surface of the obtained pattern formed body was measured by a stylus method, Ra was 2 nm.

Next, a 365 nm YAG laser was irradiated at an intensity of 200 mJ / cm ² to form a pattern and cause a photocatalytic reaction.

  The contact angle of the light irradiation part to water and n-octane was measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science), and the measurement results are shown in Table 7.

  Further, in the same manner as in Example 27, the printing master was attached to an offset printing machine (Komori Sprint 4-color machine), and printing was performed on coated paper using printing ink (Dai Nippon Ink and Chemicals' dry-color indigo ink). As a result, a good printed matter was obtained.

Example 33
A primer layer was formed on an aluminum substrate having a thickness of 0.23 mm in the same manner as in Example 29, and an emulsion-type addition-reaction-type polydimethylsiloxane (KM-768 available from Shin-Etsu Chemical Co., Ltd.) was formed on the primer layer. (Component 30%) 0.76 g, water 1.34 g, titanium oxide sol (Ishihara STS-01 particle size 7 nm) 1 g, addition reaction type catalyst (PM-6A) 0.008 g, addition reaction type catalyst (PM-6B) ), And dried at 160 ° C for 1 minute to obtain a photocatalyst-containing layer having a thickness of 1 µm.

Further, after the mask was brought into close contact and a high pressure mercury lamp was irradiated with ultraviolet light at an illuminance of 70 mw / cm ² for 10 minutes to cause a photocatalytic reaction, the contact angle with water and n-octane was measured with a contact angle measuring instrument (CA-Kyowa Interface Science Co., Ltd.). Table 7 shows the results of measurement by Z-type).

Example 34
A primer (Kansai Paint Metal Coat 90T-25-3094) 20% by weight dimethylformamide solution is applied on a degreased aluminum plate having a thickness of 0.23 mm, dried at 200 ° C. for 1 minute, and dried with a 3 μm primer layer. Was formed.

  3 g of silica sol (Glaska HPC7002 manufactured by Nippon Synthetic Rubber) and 1 g of alkylalkoxysilane (HPC402H manufactured by Nippon Synthetic Rubber) were mixed and stirred by a stirrer for 5 minutes. This solution was applied on the previously formed primer layer with a blade coater and dried at 100 ° C. for 10 minutes.

  Next, 3 g of isopropyl alcohol, 0.75 g of silica sol (Glaska HPC7002 manufactured by Nippon Synthetic Rubber, solid content 12%), 0.25 g of alkylalkoxysilane (HPC402H manufactured by Nippon Synthetic Rubber, solid content 50%), and fluoroalkoxysilane (MF manufactured by Tochem Products) -160E: 0.15 g of N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether) and 0.15 g of dimethoxydimethylsilane (TSL8112 manufactured by Toshiba Silicone) are mixed. did. This solution was stirred for 20 minutes while maintaining the temperature at 100 ° C. Thereafter, 2 g of a titanium oxide coating solution (ST-K01 manufactured by Ishihara Sangyo: solid content concentration: 10%) was added, and the mixture was further stirred for 30 minutes, and the obtained dispersion was applied by spin coating.

  Next, by drying at 150 ° C. for 10 minutes, hydrolysis and polycondensation reactions were allowed to proceed, and a layer having a film thickness of 3 μm in which the photocatalyst was firmly fixed with organopolysiloxane was formed to obtain a pattern-formed body.

  The dimethylsiloxane unit in the formed layer was 40%. In addition, when the obtained pattern formed body was measured by a stylus method, the surface roughness Ra was 2 nm.

Next, the pattern formed body was irradiated with ultraviolet light at 70 mW / cm ² illuminance for 5 minutes with a high-pressure mercury lamp through a grid-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring device (CA manufactured by Kyowa Interface Science Co., Ltd.). -Z type) are shown in Table 1. In addition, the pattern-formed body on which the pattern was formed was attached to an offset printing machine (Komori Sprint 4-color machine), and printing was performed on coated paper using a waterless printing ink (Dai Nippon Ink Chemical Industries dry-color indigo ink). As a result, a good printed matter was obtained.

Example 35
The pattern formed body produced in the same manner as in Example 34 was irradiated with a 355 nm YAG laser in a pattern at an intensity of 200 mJ / cm ² to perform a photocatalytic reaction. Table 7 shows the results obtained by measuring the contact angles of the light irradiation section with water and n-octane using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science).

  In addition, the pattern-formed body on which the pattern was formed was attached to an offset printing machine (Komori Sprint 4-color machine), and printing was performed on coated paper using a waterless printing ink (Dai Nippon Ink Chemical Industries dry-color indigo ink). As a result, a good printed matter was obtained.

Example 36
A pattern forming body was prepared in the same manner as in Example 31 except that the amount of dimethoxydimethylsilane (TSL8112 manufactured by Toshiba Silicone) used in the photocatalyst-containing layer was 0.03 g and the dimethylsiloxane unit was 10%. Evaluation was performed in the same manner as in No. 31, and the results are shown in Table 7.

  Further, when printing was performed on coated paper in the same manner as in Example 31, a good printed matter without background smear was obtained.

Example 37
On a degreased aluminum plate having a thickness of 0.23 mm, apply a 20% by weight dimethylformamide solution of a primer (Kansai Paint primer coat Cancoat 90T-25-3094), dry at 200 ° C. for 1 minute, and dry a 3 μm primer layer. Was formed.

  3 g of silica sol (Glaska HPC7002 manufactured by Nippon Synthetic Rubber) and 1 g of alkylalkoxysilane (HPC402H manufactured by Nippon Synthetic Rubber) were mixed and stirred by a stirrer for 5 minutes. This solution was applied on the previously formed primer layer with a blade coater and dried at 100 ° C. for 10 minutes.

  Next, 3 g of isopropyl alcohol, 0.75 g of silica sol (Glaska HPC7002 manufactured by Nippon Synthetic Rubber), 0.25 g of alkylalkoxysilane (HPC402H manufactured by Nippon Synthetic Rubber), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3- (Trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether) and 0.15 g of dimethoxydimethylsilane. The solution was stirred for 20 minutes while maintaining the temperature at 100 ° C. Thereafter, 2 g of a titanium oxide coating solution (ST-K01 manufactured by Ishihara Sangyo: solid content concentration: 10%) was added, and the mixture was further stirred for 30 minutes, and the obtained dispersion was applied by spin coating.

  Further, 3 g of isopropyl alcohol, 3 g of silica sol (Glaska HPC7002, manufactured by Nippon Synthetic Rubber) and 1 g of alkylalkoxysilane (HPC402H, manufactured by Nippon Synthetic Rubber) were mixed on the obtained layer and stirred for 5 minutes. The obtained dispersion was applied to form a 0.2 μm coating layer to obtain a patterned product.

Next, the obtained pattern-formed body was exposed to YAG laser at an energy density of 200 mJ / cm ² through a lattice-like mask to produce a printing plate on which a pattern was formed. Table 1 shows the results obtained by measuring the contact angle with water and n-octane with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science).

  In addition, the pattern-formed body on which the pattern was formed was attached to an offset printing machine (Komori Sprint 4-color machine), and printing was performed on coated paper using a waterless printing ink (Dai Nippon Ink Chemical Industries dry-color indigo ink). As a result, a good printed matter was obtained.

Comparative Example 5
A printing plate was prepared in the same manner as in Example 29, except that the substrate was not treated with the primer, and attached to a printing machine in the same manner as in Example 30. The layer peeled off and the adhesion was insufficient. In addition, when a peeling test was performed using a mending tape (Scotch Mending Tape manufactured by Sumitomo 3M) cross-cut with a cutter, those with a primer layer did not peel, but those without a primer layer did peel. .

Comparative Example 6
The properties were evaluated in the same manner as in Example 29 using a commercially available original plate for offset printing using a thermal plate Pearl dry (manufactured by Presstek), and the results are shown in Table 7.

Comparative Example 7
The properties were evaluated in the same manner as in Example 29 using a commercially available original plate for offset printing using a waterless offset plate HGII (manufactured by Toray Industries Inc.), and the results are shown in Table 7.

Comparative Example 8
A pattern forming body was prepared in the same manner as in Example 34 except that the amount of dimethoxydimethylsilane (TSL8112 manufactured by Toshiba Silicone) used in the photocatalyst-containing layer was 0.2 g, and the dimethylsiloxane unit was 50%. When the film surface of the layer was measured by the stylus method, the surface roughness Ra was 500 nm, and the surface of the photocatalyst-containing layer was disturbed, so that a printing plate could not be produced.

Comparative Example 9
A pattern forming body was prepared in the same manner as in Example 31 except that the amount of dimethoxydimethylsilane (TSL8112 manufactured by Toshiba Silicone) used in the photocatalyst-containing layer was 0.01 g and the dimethylsiloxane unit was 5%. Evaluation was performed in the same manner as in No. 31, and the results are shown in Table 7. The surface roughness Ra measured by the stylus method was 50 nm.

  Further, when printing was performed on coated paper in the same manner as in Example 34, background staining was generated.

FIG. 1 is a diagram for explaining an embodiment of the present invention. FIG. 2 is a diagram for explaining 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 illustrating the relationship between the light irradiation time and the wettability of the pattern forming material of the present invention. FIG. 6 is a diagram for explaining another embodiment of the present invention. FIG. 7 is a diagram for explaining another embodiment of the present invention. FIG. 8 is a diagram illustrating the relationship between the light irradiation time and the wettability of the pattern forming material of the present invention. FIG. 9 is a diagram illustrating an embodiment of a method for manufacturing an element of the present invention. FIG. 10 is a view for explaining another embodiment of the method for manufacturing an element of the present invention. FIG. 11 is a view for explaining another embodiment of the method for manufacturing an element of the present invention. FIG. 12 is a view for explaining another embodiment of the method for manufacturing an element of the present invention.

Explanation of reference numerals

  DESCRIPTION OF SYMBOLS 1 ... Pattern forming body, 2 ... Substrate, 3 ... Primer layer, 4, 41, 42, 43, 44 ... Photocatalyst containing layer, 5 ... Pattern, 6 ... Exposure, 7 ... Photocatalyst, 8 ... Hydrophilic part, 9 ... Hydrophobic part, 10 ... wettability changing material layer, 11 ... part having different wettability, 12 ... material layer to be decomposed and removed, 13 ... part having different wettability, 14 ... hydrophobic part, 15 ... hydrophilic part, 16 ... Photocatalytic decomposable substances, 17... Sites changed according to patterns, 18... Stripe patterns, 19... Lattice light-shielding patterns, 20. 24: film forming means using vacuum, 25: functional layer, 26: adhesive tape, 27: air jet nozzle, 28: functional layer, 29: substrate for element formation, 30: sheet, 31: heat-fusibility Composition layer, 32 ... Body, 34 ... heating plate 35 ... discharge nozzle, 36 ... UV curable resin composition, 38 ... curing ultraviolet ray, 38 ... microlenses

Claims (27)

In a pattern forming body for optically forming a pattern, a pattern comprising a photocatalyst-containing layer on a substrate, and a layer on the photocatalyst-containing layer, the layer being decomposed and removed by the action of a photocatalyst upon exposure of the pattern. Formed body. 2. The pattern forming body according to claim 1, wherein the photocatalyst containing layer is formed of a single photocatalyst. The layer that is decomposed and removed by the action of the photocatalyst is formed by any one method selected from the group consisting of solution coating, surface grafting, surfactant treatment, and a film forming method using a gas phase. The pattern forming body according to claim 1, wherein What is claimed is: 1. 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. 5. The pattern forming body according to claim 1, wherein the photocatalyst-containing layer is sensitive to visible light and other wavelengths. The pattern forming body according to claim 5, wherein the photocatalyst containing layer is doped with metal ions. The pattern forming body according to claim 5, wherein a fluorescent substance is added to the photocatalyst containing layer. The pattern forming body according to claim 5, wherein a photosensitive dye is added to the photocatalyst containing layer. The pattern forming body according to any one of claims 1 to 8, wherein the pattern forming body is a printing plate precursor. In the method of optically forming a pattern, a pattern formed body having a layer that is decomposed and removed by the action of the photocatalyst by exposure of the pattern on the photocatalyst containing layer having a photocatalyst containing layer on the substrate, and exposing the pattern, A pattern forming method, wherein the wettability of a surface is changed by the action of a photocatalyst. In the method of optically forming a pattern, a pattern formed body having a composition layer comprising a photocatalyst, a substance that is decomposed by the action of the photocatalyst by exposure of the pattern, and a binder is formed on a substrate, and the pattern is exposed to light. And a wettability of the surface is changed by the action of a photocatalyst. The pattern forming method according to claim 10, wherein the pattern exposure on the photocatalyst-containing layer is performed by light drawing irradiation. The pattern forming method according to claim 10, wherein the pattern exposure on the photocatalyst-containing layer is performed by exposure through a photomask. 14. The pattern forming method according to claim 10, wherein the pattern exposure on the photocatalyst-containing layer is performed while heating the pattern forming body. A pattern forming body according to any one of claims 1 to 8 is provided on a substrate, and is obtained by the pattern forming method according to any one of claims 10 to 14. An element, wherein a functional layer is disposed on a portion corresponding to the pattern of the pattern formed body. A functional layer formed on a portion corresponding to the pattern of the pattern formed body obtained by the pattern forming method according to any one of claims 10 to 14 on the pattern formed body, An element formed by transferring onto a base material as described above. A pattern forming body according to any one of claims 1 to 8 is provided on a substrate, and is obtained by the pattern forming method according to any one of claims 10 to 14. Forming a functional layer on a portion corresponding to the pattern of the pattern formed body. A functional layer is formed on a portion of the pattern formed body corresponding to the pattern of the pattern formed body obtained by the pattern forming method according to any one of claims 10 to 14; A method for producing an element, wherein a functional layer is formed on a substrate by transferring onto a material. A step of laminating the functional layer composition over the entire surface of the pattern formed body, and a step of forming a functional layer in a pattern only on the portion where the wettability of the exposed portion has changed due to the repulsion of the unexposed portion. The device manufacturing method according to claim 17, wherein 18. The method according to claim 17, further comprising a step of laminating the functional layer composition on the entire surface of the pattern formed body, and a step of forming the functional layer in a pattern by removing the unexposed portion of the functional layer. Element manufacturing method. A step of laminating the functional layer composition over the entire surface of the pattern formed body, and a step of forming a functional layer in a pattern only on the portion where the wettability of the exposed portion has changed due to the repulsion of the unexposed portion. 19. The method for manufacturing an element according to claim 18, wherein: 19. The method according to claim 18, further comprising the steps of: laminating the functional layer composition on the entire surface of the pattern formed body; and forming a functional layer in a pattern by removing the unexposed functional layer. Element manufacturing method. 23. The device manufacturing method according to claim 19, wherein the formation of the functional layer on the pattern formed body is performed by applying a composition for a functional layer. 23. The device manufacturing method according to claim 19, wherein the formation of the functional layer on the pattern formed body is performed by discharging a functional layer composition from a nozzle. 23. The 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-coated film by heat or pressure. Element manufacturing method. 23. The device manufacturing method according to claim 19, wherein the formation of the functional layer on the pattern forming body is performed by film formation using a vacuum. 23. The device manufacturing method according to claim 19, wherein the formation of the functional layer on the pattern formed body is performed by film formation using electroless plating.

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