JPH11344804A - Pattern forming body and pattern forming method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming body using a photocatalyst. SOLUTION: This pattern forming body 1 has a photocatalyst-contg. layer 41 on a base material 2. The photocatalyst-contg. layer is a layer containing a substance which changes its wettability through the effect of photocatalyst by exposure according to a pattern, or a layer containing a substance which changes the wettability through the effect of a photocatalyst 7 by exposure 6 to a pattern 5 is formed on the photocatalyst-contg. layer. Or the photocatalyst layer is formed on the base material, and a layer which is decomposed and removed by the effect of the photocatalyst by exposure 6 according to the pattern 5 is formed on the photocatalyst-contg. layer. Alternatively a compsn. layer comprising a photocatalyst, binder and substance which is decomposed by the effect of the photocatalyst by exposure according to a pattern is formed on the base material, and a pattern is recorded by having the wettability changed through exposure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel pattern forming body and a pattern forming method which can be used for various uses including printing.

[0002]

2. Description of the Related Art The present invention relates to a pattern formed body having a region having characteristics different from the surroundings formed on a substrate. 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, and in this case, the pattern is transferred to the patterned layer formed on the pattern formed body and transferred according to the change in wettability. 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 a pattern of characters, figures, and the like 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.

[0003] A printing plate for offset printing is developed by exposing the printing plate precursor through a mask on which a pattern is drawn, or by directly exposing the printing plate precursor by electrophotography. And the like. The electrophotographic offset printing plate precursor, as a photoconductor provided with a photoconductive layer mainly composed of photoconductive particles such as zinc oxide and a binder resin on a conductive substrate, exposed by electrophotography, It is manufactured 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 original plate. The hydrophilic portion is immersed in water or the like to make it oleophobic, and the printing ink is received by the lipophilic image portion and transferred to paper or the like. Also, instead of such a method of forming an oleophobic site by immersion in water, by forming a highly oleophobic site without immersion in water or the like,
A printing plate precursor for dry lithographic printing, which forms a portion for receiving ink and a portion for not receiving ink, is also used.

[0004] Further, 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 also been proposed. Have been. The heat mode recording material has a feature that a printing plate can be manufactured only by forming an image with a laser beam without the need for a process such as development.
There were problems in the processing of the residue of the solid substance altered by the laser and the printing durability.

As a method for forming a high-definition pattern, a photoresist layer coated on a substrate is exposed to a pattern, and after the exposed photoresist is developed, etching is further performed. There is known a method by photolithography in which a target pattern is directly formed by exposing a photoresist using a substance having a property.

The formation of a high-definition pattern by photolithography involves forming a colored pattern of a color filter used in a liquid crystal display device, forming a microlens, manufacturing a fine electric circuit board, and exposing a chrome mask used for exposing the pattern. It is used in manufacturing, etc., but depending on these methods, it is necessary to use a photoresist, develop with a liquid developer after exposure, or perform etching, so that it is necessary to treat waste liquid. In addition, when a functional material is used as a photoresist, there is also a problem that the photoresist is deteriorated by an alkali solution or the like used in development.

Although a high-definition pattern such as a color filter is formed by printing or the like, the pattern formed by printing has problems such as positional accuracy, and it is difficult to form a high-definition pattern. Met. 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 using a substance whose wettability is changed by the action of a photocatalyst, as disclosed in Japanese Patent Application No. Hei. The present invention proposes a pattern formed body and a forming method using such a photocatalyst, which have better characteristics, and a method for forming the pattern.

[0008]

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

[0009]

According to the present invention, there is provided a pattern forming body for optically forming a pattern, comprising a photocatalyst containing layer on a substrate, wherein the photocatalyst containing layer is wetted by the action of the photocatalyst by exposure of the pattern. It is a pattern forming body containing a substance whose property changes. A pattern forming body that optically forms a pattern, has a photocatalyst-containing layer on a substrate, and has a layer on the photocatalyst-containing 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 substrate, 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 having a composition layer comprising 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 layer containing a photocatalyst contains a compound having a siloxane bond. The layer containing a photocatalyst is the above-mentioned pattern forming body containing silicone.

[0010] The above-mentioned pattern forming body, wherein a fluoroalkyl group is bonded to a silicon atom of silicone. The pattern forming body as described above, 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 for optically forming a pattern, a pattern formed body provided with a photocatalyst-containing layer containing a substance whose wettability is changed by the action of a photocatalyst on a substrate.
A pattern formed body in which a layer containing a substance whose wettability changes due to the action of a photocatalyst is formed on a photocatalyst-containing layer formed on a base material, and a photocatalyst-containing layer having a photocatalyst-containing layer on a base material is exposed by pattern exposure. Pattern-forming body having a layer that is decomposed and removed by the action of a photocatalyst, or pattern formation in which a composition layer comprising a photocatalyst, a substance that is decomposed by the action of a photocatalyst by exposure of a pattern, and a binder is formed on a substrate This is a pattern forming method in which a body is exposed to a pattern and the wettability of the surface is changed by the action of a photocatalyst. The pattern exposure on 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.

[0012] 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 onto another substrate.

[0013] This is 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, having the pattern formed body 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 described above, onto another base material, and forming a functional layer on the base material This is an element manufacturing method. A step of laminating the functional layer composition on the entire surface of the pattern-formed 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 functional layer composition on the entire surface of a pattern formed body, and forming a functional layer in a pattern by removing an unexposed portion of the functional layer.
A step of laminating the functional layer composition on the entire surface of the pattern-formed 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 functional layer composition on the entire surface of a pattern formed body, and forming a functional layer in a pattern by removing an unexposed portion of the functional layer.

The formation of the functional layer on the pattern formed body is the above-described method for producing a device 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 method for producing an element by transfer from a functional layer composition coating 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 forming body is the above-described element manufacturing method by film formation using electroless plating.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a pattern forming body and a pattern forming method for forming a pattern by using a photocatalyst capable of causing a chemical change in a nearby substance by irradiation of light. In the present invention, a pattern means a portion that receives or repels ink when transferring printing ink when the pattern 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 may be a direct reaction with a nearby compound or oxygen,
It is thought that reactive oxygen species generated in the presence of water 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. 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 which is decomposed and removed by the action of a photocatalyst,
Using a layer containing a substance whose wettability changes by the action of a photocatalyst or a composition comprising a substance that is decomposed by the action of a photocatalyst and a binder, etc., and accepting the printing ink or toner in the pattern forming portion. A pattern-formed body is obtained by enhancing the properties, or the ink repellency with respect to a portion where a pattern is not formed.

The photocatalyst that can be used in the pattern forming body and the pattern forming method of the present invention includes titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), and the like, which are known as optical semiconductors. Strontium titanate (SrTiO ₃ ), tungsten oxide (W
O ₃ ), bismuth oxide (Bi ₂ O ₃ ), iron oxide (Fe
_Although metal oxides such as ₂ O ₃ ) can be mentioned, 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 anatase type titanium,
It is preferable that the particle diameter is small because the photocatalytic reaction occurs efficiently. The average particle size is preferably 50 nm or less, more preferably 20 nm or less. For example, hydrochloric acid peptized anatase titania sol (STS-02 manufactured by Ishihara Sangyo, average crystallite diameter 7 nm), nitric acid peptized anatase titania sol (Nissan Chemical, TA-1)
5, average crystallite diameter of 12 nm).

The layer containing the photocatalyst of the present invention can be formed by dispersing the photocatalyst in a binder. Since the photocatalyst may also decompose the binder by photoexcitation, the binder must 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.

In the silicone resin, an organic group is bonded to a silicon atom. As will be described in detail in the examples, when a photocatalyst is photoexcited, the organic group bonded to the silicon atom of the silicone molecule is photocatalyzed. Since it is substituted by an oxygen-containing group to improve the wettability, it also exhibits a function as a substance that changes the wettability. As the silicone resin, one or more hydrolytic condensates and cohydrolytic 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; X is a halogen, a methoxyl group,
An ethoxyl group or an acetyl group can be mentioned.

Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; ethyltrichlorosilane, ethyltribromosilane, ethyltrichlorosilane Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n
-Propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane; n-
Hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyl Tribromosilane,
n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-
Decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n
-Octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri-t-butoxysilane; phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyl Triisopropoxysilane, phenyltri-t-butoxysilane; dimethoxydiethoxysilane; dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, Diphenyldiethoxysilane; phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyl Diethoxy silane; trichlorosilane hydrosilane, tri bromine hydrosilane, trimethoxy hydrosilane, triethoxy hydrosilane, tri-isopropoxy hydrosilane, tri t- butoxy hydrosilane;
Vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriisopropoxysilane, vinyltri-t-butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltri Ethoxysilane, γ
Glycidoxypropyltriisopropoxysilane, γ
-Glycidoxypropyltri-t-butoxysilane; γ-
Methacryloxypropylmethyldimethoxysilane, γ
-Methacryloxypropylmethyldiethoxysilane,
γ-methacryloxypropyltrimethoxysilane, γ
-Methacryloxypropyltriethoxysilane, γ-
Methacryloxypropyltriisopropoxysilane,
γ-methacryloxypropyltri-t-butoxysilane; γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltri-t-butoxysilane;
γ-mercaptopropylmethyldimethoxysilane, γ-
Mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; and partial hydrolysates thereof; and mixtures thereof can be used.

When the binder layer is formed of an organoalkoxysilane, at least 10
More preferably, 30% by weight is composed of a bifunctional silicone precursor, for example dialkoxydimethylsilane. When an organoalkoxysilane is used for 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. In the case where the wettability is made different as described above, the oil repellency can be improved when the dimethylsiloxane component is included more than when the methylsiloxane component is included.

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.
Alternatively, the choice of substances that can be used as the composition for a functional layer is increased.

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 SiC _{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 (OC
H ₃ ) ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OC
H ₃ ) ₂ (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ (OC
_{H 3) 2 CF 3 (C} 6 H 4) C 2 H 4 SiCH 3 (OCH 3) 2 CF 3 (CF 2) 3 (C 6 H 4) C 2 H 4 SiCH 3 (OC
_{H 3) 2 CF 3 (CF} 2) 5 (C 6 H 4) C 2 H 4 SiCH 3 (OC
_{H 3) 2 CF 3 (CF} 2) 7 (C 6 H 4) C 2 H 4 SiCH 3 (OC
_{H 3) 2 CF 3 (CF} 2) 3 CH 2 CH 2 Si (OCH 2 CH 3) 3 CF 3 (CF 2) 5 CH 2 CH 2 Si (OCH 2 CH 3) 3 CF 3 (CF 2) 7 CH _{2 CH 2 Si (OCH 2 CH} 3) 3 CF 3 (CF 2) 9 CH 2 CH 2 Si (OCH 2 CH 3) 3 CF 3 (CF 2) 7 SO 2 N (C 2 H 5) CH 2 CH 2 CH ₂ S
i (OCH ₃ ) ₃

In order to provide better repellency with the ink and the functional layer composition, a reactive linear silicone, preferably a silicone obtained by crosslinking dimethylpolysiloxane with a low crosslinking density, is preferred. . Typically, a compound having a repeating unit shown below and subjected to a crosslinking reaction is preferable.

[0026]

Embedded image

Here, n is an integer of 2 or more. R ¹ ,
R ² is 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 are 60% or more in molar ratio. 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. Further, if the molecular weight is too large, the ratio of terminal X and Y relatively decreases,
There is a problem that the crosslink density is reduced. X and Y are selected from the following groups, X and Y may be the same or different, and R is a hydrocarbon chain having 10 or less carbon atoms.

[0028]

Embedded image

The reactive modified silicone used in the present invention comprises:
Either one that crosslinks by condensation or one that crosslinks using a crosslinking agent can be used. When the cross-linking reaction is carried out by condensation, tin, zinc, lead, calcium, manganese salts of carboxylic acid, preferably laurate, 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 preferably the following compounds can be mentioned.

[0030]

Embedded image

As the reactive silicone compound, an aqueous emulsion type may be used. Since the aqueous emulsion type compound uses an aqueous solvent, it is easy to handle. Oil repellency may be increased by mixing a stable organosiloxane compound such as dimethylpolysiloxane that does not undergo a cross-linking reaction with the reactive silicone compound used as the binder of the present invention. In this case, 60% by weight or more of the siloxane contained in the layer obtained from the composition containing the reactive silicone compound is:
It is preferably obtained from a reactive silicone compound, and if it is less than 60% by weight, dimethylsiloxane is reduced and water repellency is deteriorated, which is not preferable.

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; Silanol, which is a hydrolyzate, or 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. Further, in this case, the amorphous silica precursor and the photocatalyst particles are uniformly dispersed in the non-aqueous solvent,
A photocatalyst-containing film can be formed on a substrate by hydrolyzing with water in the air to form a silanol, followed by dehydration-condensation polymerization at room temperature. Dehydration condensation polymerization of silanol is 10
When performed at 0 ° 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.

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

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

The coating solution containing a photocatalyst can be applied to a substrate by a method such as spray coating, dip coating, roll coating, or bead coating. Further, 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 lamp, excimer lamp, excimer laser,
A YAG laser or other ultraviolet light source can be used, and the wettability of the film surface can be changed by changing the illuminance, the irradiation amount, and the like.

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

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

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

As one embodiment of the pattern forming body of the present invention, as shown in FIG.
Alternatively, the photocatalyst-containing composition layer 41 may be formed directly on the base material 2 or after forming the primer layer 3. In order to record pattern information as shown in FIG.
Exposure 6 of a predetermined pattern 5 is performed, and as shown in FIG. 1 (C), an alkyl chain of the silicone compound is converted into an OH group by the action of a photocatalyst 7, and the surface which has been hydrophobic in accordance with the exposed pattern has a hydrophilic property. A portion 8 is formed, and pattern information is recorded based on a difference in wettability with the hydrophobic portion 9.

As a second embodiment of the pattern formed body of the present invention, as shown in FIG. 2A, a primer layer 3 is laminated on a substrate 2 and a photocatalyst-containing composition containing a photocatalyst is contained. The material layer 42 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 using pattern 5
Then, as shown in FIG. 2C, a portion 11 having different wettability according to the pattern is formed, and pattern information is recorded.

In the case of the second embodiment, the photocatalyst-containing composition layer is formed by hydrolyzing or partially hydrolyzing a composition in which a photocatalyst is dispersed in a binder precursor or the like. Then, a method of forming a thin film made of a hydrophobic organic substance can be mentioned, and a film can be formed using only a photocatalyst. Organic thin film is applied by solution coating, surface grafting,
A film formation method using a gas phase such as a surfactant treatment, PVD, or CVD can be used. As the organic substance, a low-molecular compound, a high-molecular compound, a surfactant, or the like, whose wettability is changed by a photocatalyst can be used. Specifically, an organic group is changed to a hydroxyl group by the action of a photocatalyst, a silane compound, a silane coupling agent, chlorosilane,
Alkoxysilanes, or two or more of these hydrolytic condensates and co-hydrolytic condensates can be mentioned.

As a third embodiment, FIG.
As shown in FIG. 1A, a photocatalyst-containing composition layer 43 is formed on a substrate 2, and the photocatalyst-containing composition layer 12 is further decomposed and removed by the action of a photocatalyst when irradiated with light. Is formed, is exposed 6 using the pattern 5 as shown in FIG. 3 (B), and forms portions 13 having different wettability according to the pattern as shown in FIG. 3 (C) to record pattern information. Things.

In the case of the third embodiment, the photocatalyst-containing composition layer is formed by hydrolyzing or partially hydrolyzing a composition in which a photocatalyst is dispersed in a binder precursor or the like. Then, a method of forming a thin film made of a hydrophobic organic substance can be mentioned, 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, treating with a surfactant, or forming a film in a gas phase such as PVD or CVD.

Specifically, Nippon Surfactant Industries: 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:
Non-ionic surfactants of fluorine type or silicone type such as Futergent F-200, F251, Daikin Industries Unidyne DS-401, 402, and 3M: Florade FC-170, 176 can be mentioned.
Cationic, anionic or amphoteric surfactants can be used.

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

In the fourth embodiment, as shown in FIG. 4A, a primer layer 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 photocatalytically decomposable substance 16 composed of a hydrophobic part 14 and a hydrophilic part 15 decomposed by the action of. 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 portion 14 and the hydrophilic portion 15 existing in the predetermined portion is decomposed by the action of the photocatalyst, and the surface wettability is exposed. The portion 17 changed in accordance with the six patterns is formed and pattern information is recorded.

Substances that change the wettability of the surface include:
Like a surfactant, the wettability of the photocatalyst-containing composition layer,
It is preferable to add a substance that can be arbitrarily set according to the type and the amount of addition. As the substance capable of changing the wettability, a surfactant is preferable. Specifically, NIKKOL manufactured by Nippon Surfactant Industries, Ltd .:
Hydrocarbon series such as BL, BC, BO, BB series,
DuPont: ZONYL FSN, FSO, Asahi Glass: Surflon S-141, 145, Dai Nippon Ink: Megafac F-141, 144, Neos: Futergent F
-200, F251, Daikin Industries Unidyne DS-
401, 402, 3M: Florard FC-17
Examples thereof include fluorine-based and silicone-based nonionic surfactants such as 0 and 176, and cationic, anionic and amphoteric surfactants can be used.

In addition to the surfactant, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride, polyamide And oligomers and polymers such as polyimide, styrene-butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, and polyisoprene. . The photocatalyst is preferably 5 to 60% by weight, amorphous silica is 95 to 40% by weight, and the substance whose wettability is changed by the action of the photocatalyst is preferably 0.1 to 55% by weight.

The pattern-formed body of the present invention is used as a printing plate, since the surface energy is changed by the action of the photocatalyst in the composition, and the portion where the wettability is changed changes the acceptability of the printing ink. be able to. 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 by direct drawing with a laser or the like.

When a printing plate precursor is prepared, a substrate such as aluminum generally used as an offset printing plate can be used. A layer may be applied and a pattern may be formed by exposure. Also, if the substrate is likely to be deteriorated by the photooxidation action of the photocatalyst such as plastic, a protective layer may be formed by previously coating the substrate with silicone, a fluororesin, etc. Any shape such as a sheet shape, a ribbon shape, and a roll shape can be used. Alternatively, 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 portion is designed to have printing ink receptivity and dampening solution repellency, it can be used as an offset printing plate using ordinary dampening solution.

When the pattern formed body of the present invention is used for an element having a pattern laminated thereon, various functional layers can be formed on various substrates by adjusting the wettability of the surface of the pattern formed body. Can be formed in a pattern. Functionality refers to optical (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, ion conductivity, redox properties, electrochemical properties, electrochromic properties, etc., mechanical properties (friction resistance, etc.), thermal properties (thermal conductivity, thermal insulation properties, infrared radiation properties, etc.), biological functions (biocompatibility, Thrombotic etc.).

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.
m or less. Preferred substances include
A silicone resin, a silicone resin having a fluorocarbon group, and the like can be given. In addition, 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 composition for a functional layer include a liquid composition not diluted with a solvent represented by an ultraviolet curable monomer and the like, a liquid composition diluted with a solvent, and the like. 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.

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

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

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

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

Next, an element which can be manufactured by 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. A fine color filter 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 photo-curing treatment after application can be performed without performing development or the like. Resolution color filters are possible.

Further, the pattern forming body of the present invention can be used for manufacturing a micro lens. For example, circular exposure is performed on the photocatalyst-containing layer laminated on the transparent substrate to form a circular pattern having changed wettability. Next, when the composition for forming a lens is dropped on the portion where the wettability is 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. If cured, various shapes or focal lengths can be obtained, so that a high-definition microlens can be obtained.

Further, a metal film having a desired pattern can be formed by using the pattern forming body of the present invention in a method 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, since a metal pattern can be formed without forming a resist pattern, 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 for a method of forming a pattern of a metal or the like using a vacuum film forming technique. For example, a pattern having high adhesiveness is produced by light irradiation, and then a metal component is heated and vapor-deposited under vacuum, and a metal component such as aluminum is vapor-deposited on the entire surface of the pattern forming body to form a metal thin film. . There is a difference in the adhesion strength of the metal thin film between the part where the pattern is formed and the part where it is not.Therefore, a patterned metal thin film is formed by pressing the adhesive against the thin film surface, peeling it with a chemical, etc. can do.

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

The method of manufacturing the device of the present invention will be described below 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 a 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 by 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 film forming step of FIG.
A coating using a blade coater 22 as shown in FIG. 1 or a coating using a spin coater 23 as shown in B2, vapor deposition as shown in B3, film forming means 24 using a vacuum such as CVD, etc. Functional layer 25 on the entire surface
To form Functional layer 2 formed on pattern forming body
In No. 5, the adhesive strength differs between the exposed portion and the unexposed portion due to a difference in surface energy caused by exposure of the pattern formed body.

Next, in the peeling step of FIG. 9C, after the adhesive surface of the adhesive tape 26 is brought into close contact with the adhesive tape 26, the adhesive tape 26 is peeled off from the end to peel off the functional layer formed on the unexposed 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 from the nozzle 27 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 a view for explaining a cross section.
Similarly to FIG. 9, the functional layer 25 is formed on the pattern forming body 1 by a method as shown in FIG. Then
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 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.
As shown in FIG. 11A, the photocatalyst containing layer 4
Is exposed 6 according to the pattern of the element to be formed by using the photomask 20 on the pattern forming body 1 provided with the. Then, FIG.
As shown in (B), the surface on which the heat-fusible composition layer of the thermal transfer body 32 having the heat-fusible composition layer 31 formed on the sheet 30 is in close contact with 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 a method for manufacturing an element of the present invention, and is 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. FIG.
As shown in (C), 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. Then, FIG.
As shown in FIG. 2 (D), the microlenses 38 can be formed by irradiating ultraviolet rays for curing 37.

[0070]

The present invention will be described below with reference to examples. Example 1 30 g of Glaska HPC7002 (Nippon Synthetic Rubber), Glaska HPC402H which is an alkylalkoxysilane
(Japan Synthetic Rubber) 10 g was mixed and mixed with a stirrer.
Stirred for minutes. This solution was applied to a glass substrate having an area of 7.5 cm ² by spin coating, and dried at 150 ° C. for 10 minutes to form a sodium ion block layer having a thickness of 2 μm. Next, 15 g of Glasca HPC7002 (Nippon Synthetic Rubber), Glaska HP
5 g of C402H (Japanese synthetic rubber) and titania sol (TA-15 manufactured by Nissan Chemical Industries, Ltd.) were mixed. This solution was applied by spin coating on a substrate on which a sodium ion blocking layer had been formed. This is taken at 150 ° C for 10
By drying for minutes, the hydrolysis and polycondensation reactions were allowed to proceed, and a pattern formed body having a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed by organopolysiloxane was prepared.

A xenon lamp was irradiated with ultraviolet light at 6.6 mW / cm ^{2 at} an illuminance of 6.6 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). It was measured. 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-like mask, irradiation is performed with an xenon lamp at an illuminance of 6.6 mW / cm ² for 6 hours to form a pattern having different wettability in an irradiated portion 9 ° and an unirradiated portion 102 °. Was able to do.

Example 2 A composition for forming a primer layer (Kancoat 9 manufactured by Kansai Paint Co., Ltd.) was placed on a degreased aluminum plate having a thickness of 0.15 mm.
0T-25-3094) in dimethylformamide, and dried at 200 ° C. for 1 minute.
A μm primer layer was obtained. The photocatalyst-containing layer described in Example 1 was formed on the primer layer to obtain a waterless printing plate precursor. Then, 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 mounted on an offset printing machine (Alpha New Ace manufactured by Alpha Giken), and at a printing speed of 5000 sheets / hour 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, a good printed matter was obtained by performing printing in the same manner except that a laser beam was exposed at 175 lines / inch through a gradation negative film having 2% to 98% of a halftone dot with a xenon lamp instead of a laser. Obtained.

Example 3 3 g of silica sol, Glasca HPC7002 (Nippon Synthetic Rubber), and HPC40, an alkylalkoxysilane
1 g of 2H (Japanese synthetic rubber) was mixed and stirred for 5 minutes.
The area of this solution is 7.5 c by spin coating.
It was applied to a m ² glass substrate to form a sodium ion blocking layer having a thickness of 2 μm.

Next, 3 g of isopropyl alcohol and silica sol (Glaska HPC7002 manufactured by Nippon Synthetic Rubber) were added.
75g, Alkylalkoxysilane (made by Nippon Synthetic Rubber)
0.25 g of Glasca HPC402H), fluoroalkoxysilane (MF-160E, manufactured by Tochem Products):
0.15 g of N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in isopropyl ether (50% by weight) was mixed. The obtained dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. Then, 2 g of titanium oxide (Titanium oxide coating liquid ST-K01: solid content concentration of 10% by weight, manufactured by Ishihara Sangyo) was used.
Was added and stirred for another 30 minutes.

This dispersion was applied by spin coating to the substrate on which the sodium block layer prepared above was formed. 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. The average roughness of the surface of the obtained photocatalyst-containing layer was measured by a stylus method.
a = 2 nm. In addition, a high-pressure mercury lamp was turned on at 70 mW / cm ² through a lattice-shaped mask. UV irradiation was performed at an illuminance of 2 minutes for 2 minutes, and the contact angle with water and n-octane was measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science).

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 manufactured by Tochem Products)
-160E: N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether solution) 0.15 g,
Titanium oxide (Titanium oxide coating liquid ST-
(K01: 10% by weight solid content).
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 a temperature of 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 applied to the photocatalyst-containing layer through a lattice-like mask at 70 mw /
cm ² UV irradiation for 2 minutes at an illuminance of water and n-
Table 4 shows the results obtained by measuring the contact angle with octane using a contact angle measurement device (CA-Z type, manufactured by Kyowa Interface Science).

Example 5 A 0.3 μm-thick photocatalyst-containing layer was formed on a polycarbonate substrate by spin coating in the same manner as described in Example 4, and a chart mask having a resolution of 50 lp / mm was formed on the photocatalyst-containing layer. Through a high-pressure mercury lamp of 70 mW / cm ² UV irradiation was performed at an illuminance of 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 72.3 mN / m in the exposed part. 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 the ink is selectively applied only to the exposed portion, and the photocatalyst layer 4 is formed on the transparent polycarbonate substrate 2.
A blue stripe pattern 18 of 50 lp / mm was obtained.

Example 6 3 g of silica sol, Glaska HPC7002 (Nippon Synthetic Rubber), and HPC40, an alkylalkoxysilane
1 g of 2H (Japanese synthetic rubber) was mixed and stirred for 5 minutes.
This solution is spin-coated to a thickness of 0.15 m.
m on a degreased aluminum plate to obtain a primer layer having a thickness of 2 μm. Then, on this primer layer,
The photocatalyst-containing layers described in Examples 3 and 4 were formed to obtain a waterless printing plate precursor. Next, an Nd: YAG laser (3
Pattern formation was performed using a 55 nm lambda physical Star Line) with a recording energy of 200 mJ / cm ² . The printing plate obtained was attached to an offset printing base (Alpha New Ace, manufactured by Alpha Giken), and 5,000 sheets / sheet were prepared using a waterless printing ink (Inktec Waterless S Indigo, manufactured by The Inktec).
When printing was performed on coated paper at the printing speed at the time, 20,000 good printed matters were obtained. Also, instead of a laser, 1
70 mW high pressure mercury lamp at 75 lines / inch through a gradation negative pattern with 2% to 98% halftone dots
/ Cm ² Irradiation with ultraviolet light for 2 minutes at the same illuminance and evaluation of the printing characteristics in the same manner gave good printed matter.

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 manufactured by Tochem Products)
-160E: N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether solution) 0.15 g,
Titanium oxide powder (ST-21 average particle size 2 manufactured by Ishihara Sangyo)
0 nm). 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 is heated at 150 ° C for 1
By drying for 0 minutes, the hydrolysis and polycondensation reactions proceeded, and a photocatalyst-containing layer having a thickness of 3 μm in which the photocatalyst was firmly fixed in the organosiloxane was able to be formed. When the average roughness of the surface of the obtained photocatalyst-containing layer was measured by a stylus method, it was Ra = 4 nm. Also,
A high-pressure mercury lamp was applied on the photocatalyst-containing layer through a lattice-like mask at 70 mW / cm ^2. UV irradiation for 5 minutes at the illumination of
Table 4 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).

Example 8 A 0.3 μm-thick photocatalyst-containing layer prepared by the method described in Example 7 was provided with three light-shielding layers having a size of 150 × 300 μm.
A high-pressure mercury lamp was passed through a mask arranged at 0 μm intervals.
0 mW / cm ² UV irradiation was performed at an illuminance of 5 minutes. Various liquids having a known surface tension are dropped on the obtained photocatalyst-containing layer, and the contact angle is measured using a contact angle measuring device (manufactured by Kyowa Interface Science).
CA-Z type), and the critical interfacial tension was determined by Zisman plot.
m. Then, carbon black (Mitsubishi Chemical
# 950) 4 g, polyvinyl alcohol (Nippon Synthetic Chemical Co., Gohsenol AH-26) 0.7 g, water 95.3
g were mixed and dissolved by heating, centrifuged at 12000 rpm, and filtered through a 1 μm glass filter to obtain a light-shielding composition.

The surface tension of the obtained light-shielding composition was measured with a surface tensiometer (PD-Z type, manufactured by Kyowa Interface Science) and found to be 37.5 mN / m. This was applied over 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 base material 2 made of glass. Thus, a grid-like light-shielding pattern 19 was obtained.

Example 9 A sodium ion blocking layer was formed in the same manner as in Example 3.
And then 3 g of isopropyl alcohol,
2.2 g of orchid (TSL8113 made by Toshiba Silicone)
Fluoroalkoxysilane (MF manufactured by Tochem Products)
-160E: N- [3- (trimethoxysilyl) propyl
] -N-ethyl perfluorooctanesulfonamide
0.15 g of a 50% by weight solution of isopropyl ether
Titanium oxide powder (ST-21 average particle size 2 manufactured by Ishihara Sangyo)
0 nm). The obtained dispersion is allowed to stand for 20 minutes.
While maintaining the temperature at 100 ° C., the mixture was stirred. Spin this dispersion
Sodium ion blocking layer
It was applied on the formed substrate. This is heated at 150 ° C for 1
Hydrolysis and polycondensation reactions proceed by drying for 0 minutes.
And the photocatalyst is firmly fixed in the organosiloxane
3 μm thick photocatalyst containing layer can be formed.
Was. The average roughness of the surface of the obtained photocatalyst-containing layer was determined in Examples.
When measured by the stylus method in the same manner as in Example 1, Ra = 4n
m. In addition, a grid-like mask is formed on the photocatalyst containing layer.
Through a high-pressure mercury lamp of 70 mW / cm ^Two For 5 minutes
UV irradiation and contact with water and n-octane
Angle is measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science)
Table 4 shows the measurement results.

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. The unexposed portion and the exposed portion are separated by an X-ray photoelectron spectrometer (VG Sientific ESCALAB22).
0-I-XL). Quantitative calculation was performed using Shari's background correction and Scofield's relative sensitivity coefficient correction.
Table 1 shows relative values by weight when the value is set to 0.

[0084]

[Table 1]

The results show that exposure reduces the proportion of carbon and fluorine and increases the proportion of oxygen. From the results of Example 9, considering that the contact angle with water is reduced, As a result of the exposure, it is considered that an organic group such as a methyl group or a fluoroalkyl group bonded to the 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 manufactured by Tochem Products)
-160E: N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight isopropyl ether solution) 0.75 g,
Titanium oxide (Titanium oxide coating liquid ST-
K01: 10% by weight solid content). The obtained 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 a temperature of 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. Further, a high-pressure mercury lamp was applied to the photocatalyst-containing layer through a lattice-like mask at 70 mW / cm ^2. UV irradiation at an illuminance of 10 minutes, 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 12 In the same manner as in Example 4, a 0.3 μm thick photocatalyst was contained.
A layer was formed. A mask having a light shielding layer with a pitch of 100 μm
70mW / cm high pressure mercury lamp through a screen^Two At illuminance
Ultraviolet irradiation was performed for 2 minutes. Color filter color painting
Dispenser (EFD)
Wet the exposed area when dropped with 1500XL)
It spread and a pixel was able to be formed.

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):
0.45 g of N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in isopropyl ether (50% by weight), titanium oxide (Ishihara Sangyo Co., Ltd. titanium oxide coating solution ST-K01: solid content) (Concentration 10% by weight) were mixed. The resulting dispersion was stirred for 20 minutes while maintaining the temperature at 100 ° C. This dispersion was applied on a 0.3 mm-thick aluminum substrate by spin coating. This is heated at 150 ° C for 1
Hydrolysis and polycondensation reactions were allowed to proceed by drying for 0 minutes to form a 0.5 μm-thick photocatalyst-containing layer in which the photocatalyst was firmly fixed in the organosiloxane. An ultra-high pressure mercury lamp (UXM-350 manufactured by Ushio Inc.) is used while heating the obtained pattern formed body to various temperatures on a hot plate.
0, ML-40D type lamp house) by removing the heat rays and allowing only the ultraviolet light of 241 nm to 271 nm to be 8.1.
Irradiation was performed for 300 seconds at an intensity of mW / cm ^{2, and} the contact angle with water was measured by a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science). As shown in Table 2, the photocatalytic reaction was promoted by heating. Which indicates that.

[0089]

[Table 2]

Example 14 In the same manner as in Example 3, a photocatalyst-containing layer was formed on quartz glass 10 cm long and 10 cm wide. Negative photomasks having a size of a light transmitting portion of 150 μm × 300 μm and arranged at an interval 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 by a high-pressure mercury lamp. 70mW of UV light
After irradiation for 2 minutes at an illuminance of / cm ^2, 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.

[0091]

[Table 3] Unexposed area Exposed area Closely adhered 113 ° 97 ° or less With a 100 μm gap 113 ° 5 ° or less

Example 15 In the same manner as in Example 14, a gap of 100 μm was provided, and exposure was performed in a state where air was blown onto the exposed surface of the pattern-formed body. 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. A light-shielding part with a length of 100 μm and a width of 20 μm
UV light of 320 nm to 390 nm from a high pressure mercury lamp through a photomask formed at intervals of 70 mW / cm.
Irradiation was performed at an illuminance of ² for 7 minutes. Then, on a 10 μm-thick polyester film, as a hot-melt ink layer, the following composition: carbon black (Mitsubishi Chemical Industries # 25) 20 parts by weight Ethylene-vinyl acetate copolymer (Mitsui DuPont Polychemical) 10 parts by weight Part Carnauba wax 10 parts by weight Paraffin wax (Nippon Seiwa Co., Ltd. HNP-11) 60 parts by weight An ink ribbon formed with a heat-fusible ink composition layer was brought into close contact with the pattern-exposed photocatalyst-containing layer by 9 parts.
After heating to 0 ° 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 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 in the same manner as in Example 10. A line having a width of 5 μm was formed on the obtained pattern formed body at a distance equal to the line width from a high-pressure mercury lamp through a photomask.
0 to 390 nm ultraviolet light at 70 mW / cm ² illuminance
Irradiated for minutes. Next, the light-irradiated pattern formed body is used as a sensitizer solution for chemical plating (Glass
12.5ml / l diluted S-10X for ceramic)
Immersed in a solution having a concentration of 25 ° C. while shaking for 20 seconds, washed with water, and diluted with a reducing catalyst-provided solution (Palladium colloid catalyst A-10X manufactured by Uemura Kogyo).
After being immersed in a solution having a concentration of ml / l while shaking at 25 ° C. for 20 seconds, it was immersed in an electroless nickel plating solution (Nimden LPX manufactured by Uemura Kogyo Co., Ltd.) at 80 ° C. for 1 hour to be exposed to the exposed portion. A nickel layer having a thickness of 0.5 μm was formed.

Further, the substrate was immersed in a 90 ° C. electroless gold plating bath (ELGB511 manufactured by Uemura Kogyo) while rocking for 5 minutes to form a 0.1 μm thick gold layer on the nickel pattern. Was immersed in an electroless gold plating bath (GOBEL2M, manufactured by Uemura Kogyo Co., Ltd.) for 1 hour while shaking to form gold having a thickness of 2 μm.

Example 18 A photocatalytic layer having a thickness of 0.4 μm was formed on a quartz glass substrate having a length of 10 cm, a width of 10 cm and a thickness of 0.1 cm by spin coating the same composition as in Example 4. Next, a mercury lamp was used to pass 70 mW / cm ² through a photomask having a rectangular pattern with an opening of 23 μm × 12 μm.
For 90 seconds to obtain a transparent substrate having a rectangular pattern having a high surface energy formed on the photocatalyst-containing layer.

Next, a thin film of a perylene 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. Next, 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, forming a rectangular pattern of a 23 μm × 12 μm rectangular red pigment. We were able to.

[0098]

Embedded image

Example 19 A photocatalyst-containing layer having a thickness of 0.4 μm was formed by spin-coating the same composition as in Example 4 on a polyimide film having a thickness of 100 μm. This was exposed to a mercury lamp at an illuminance of 70 mW / cm ² for 90 seconds through a negative photomask having a circuit pattern drawn with a width of 50 μm 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 at a deposition rate of 4 nm / sec. Next, the surface of the aluminum thin film is coated with a cellophane adhesive tape (JIS Z manufactured by Sekisui).
1522), the film was peeled off at 135 ° at a speed of 300 mm / sec. Due to the difference, the vapor-deposited film was peeled off only in the unexposed portions, and a circuit pattern having a circuit having a width of 50 μm and a thickness of 0.1 μm was obtained.

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 having a known surface tension were dropped on the obtained photocatalyst-containing layer, and the contact angle was measured with a contact angle measuring instrument (CA-Z type, manufactured by Kyowa Interface Science).
When the critical surface tension was determined by an plot, the critical interfacial tension of the unexposed portion was 14.6 mN / m, and that of the exposed portion was 72.3 mN / m. Subsequently, a composition was prepared by mixing 100 parts by weight of an ultraviolet-curable monomer (Beamset 770 manufactured by Arakawa Kogyo) 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. Also,
The viscosity was measured with a viscometer (CJV5000, manufactured by Chichibu Onoda) 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 circular pattern having a diameter of 5 mm of the resin cured by the ultraviolet rays was obtained.

Comparative Example 1 A commercially available original plate for offset printing was used with a thermal plate Pea.
Example 3 using rl dry (manufactured by Presstek)
The characteristics were evaluated in the same manner as described above, and the results are shown in Table 4.

Comparative Example 2 A commercially available offset printing master plate without water, H offset plate
The properties were evaluated in the same manner as in Example 3 using GII (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. Table 4
Shown in

Comparative Example 4 A sodium ion blocking layer was formed in the same manner as in Example 3.
And then 3 g of isopropyl alcohol,
2.2 g of orchid (TSL8113 made by Toshiba Silicone)
Fluoroalkoxysilane (MF manufactured by Tochem Products)
-160E: N- [3- (trimethoxysilyl) propyl
] -N-ethyl perfluorooctanesulfonamide
0.15 g of a 50% by weight solution of isopropyl ether
Titanium oxide powder (ST-41 manufactured by Ishihara Sangyo) Average particle size 5
0 nm). The obtained dispersion is allowed to stand for 20 minutes.
During the stirring, the mixture was stirred at 100 ° C. Spin this dispersion
Sodium ion blocking layer
It was applied on the formed substrate. This is heated at 150 ° C for 1
Hydrolysis and polycondensation reactions proceed by drying for 0 minutes.
And the photocatalyst is firmly fixed in the organosiloxane
3 μm thick photocatalyst containing layer can be formed.
Was. The average roughness of the surface of the obtained photocatalyst-containing layer was determined in Examples.
When measured by the stylus method in the same manner as in Example 1, Ra = 30
m. In addition, a grid-like mask is formed on the photocatalyst containing layer.
High pressure mercury lamp through 70mW / cm^Two Purple for 5 minutes
External irradiation, contact angle with water and n-octane
With a contact angle measuring instrument (CA-Z type manufactured by Kyowa Interface Science)
Table 4 shows the measurement results.

[0108]

Table 4 Exposed portion Unexposed portion Water n-octane Water n-octane Example 3 5 ° or less 5 ° or less 113 ° 16 ° Example 4 5 ° or less 5 ° or less 107 ° 47 ° Example 7 5 ° or less 5 105 ° or less 105 ° 40 ° Example 9 5 ° or less 5 ° or less 100 ° 30 ° Example 11 5 ° or less 5 ° or less 151 ° 77 ° Comparative Example 1 84 ° 5 ° or less 105 ° 11 ° Comparative Example 2 104 ° 5 ° 116 ° 13 ° Comparative Example 3 5 ° or less 5 ° or less 86 ° 10 ° Comparative Example 4 10 ° 10 ° 105 ° 26 °

Example 21 On a degreased aluminum plate having a thickness of 0.15 mm, a composition for forming a primer layer (Kancoat 9 manufactured by Kansai Paint Co., Ltd.)
0T-25-3094) in dimethylformamide, and dried at 200 ° C. for 1 minute.
A μm primer layer was obtained. Next, 3 g of isopropyl alcohol and organosilane (TSL manufactured by Toshiba Silicone Co., Ltd.)
8113) 4.2 g, titanium oxide powder (Ishihara S.
T-01 (average particle size: 7 nm) 0.2 g. The obtained 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. Then, the high pressure mercury lamp was
0 mW / cm ² Table 5 shows the results obtained by irradiating with ultraviolet light at an illuminance of 10 minutes for 10 minutes and measuring the contact angle with water and n-octane using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science).
Shown in

[0110]

[Table 5]

The lithographic printing plate precursor with water has 175
Exposure with said mercury lamp through a gradation positive mask with 2% to 98% halftone dots per line per inch;
A pattern was formed. Next, the obtained printing plate was mounted on an offset printing machine (Alpha New Ace, manufactured by Alpha Giken), and printing ink (Across Red, manufactured by The Inktec) and a fountain solution (diluted with a 20-fold water solution from Niken Kagaku clean etch solution) When printing was performed on coated paper at a printing speed of 5000 sheets / hour using, good prints of 20,000 sheets were obtained.

Example 22 2.7 g of tetraethoxysilane Si (OC ₂ H ₅ ) ₄ was prepared.
38.7 g of ethanol and 4.5 g of 2N hydrochloric acid were mixed, and 1
Stirred for 0 minutes. This solution was applied to a substrate by spin coating, and dried at a temperature of 80 ° C. for 30 minutes to form a 0.2 μm-thick sodium ion blocking layer. Tetraethoxysilane Si (OC ₂ H ₅ ) ₄ 0.62
g, titania sol (TA-15, manufactured by Nissan Chemical Industries) 0.96
g, 26.89 g of ethanol and 0.32 g of pure water were mixed and stirred for 10 minutes. This dispersion was applied by spin coating onto a substrate on which a sodium ion blocking layer had been formed. This is dried at a temperature of 150 ° C. for 30 minutes to promote hydrolysis and polycondensation reaction, and has a high surface energy, and a photocatalyst-containing composition having a photocatalyst firmly fixed in silica and having a thickness of 0.2 μm. Make a layer,
Sample 1 was obtained. 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 in an amount of 1 g.
/ M ^2, and dried at a temperature of 80 ° C. for 10 minutes to produce an organic layer having a low surface energy.

A mercury lamp was applied to each of the obtained samples 1 and 2 using a mercury lamp.
UV irradiation was performed for 5 minutes at an illuminance of 30 mW / cm ² , and the contact angle with water was measured with a contact angle measuring instrument (CA manufactured by Kyowa Interface Science Co., Ltd.)
-Z type). Table 6 shows the results. It was found that the organic material layer of Sample 2 was decomposed and removed by photocatalysis, and returned to the state of Sample 1 before the application of the organic material. Gender did not change.

[0114]

[Table 6]

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. Was. Then
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 by a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science).
° and 5 ° or less after exposure.

Example 23 Polydimethylsiloxane having hydroxyl groups at both ends (degree of polymerization: 700)
Example 22 A solution of 99.99% by weight, 5% by weight of methyltriacetoxysilane, and 0.01% by weight of dibutyltin dilauryllate dissolved in Isopar E (manufactured by Exxon) at a concentration of 5% by weight was applied to Example 22 by spin coating. Was applied on the sample 1 described in the above to a film thickness of 0.2 μm.
The film was dried at a temperature of 10 ° C. for 10 minutes to form a film. Then, 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.

On a degreased aluminum plate having a thickness of 0.15 mm, a composition for forming a primer layer (Kansai Paint Co., Ltd.)
A 20% by weight solution of Cancoat 90T-25-3094) in dimethylformamide was applied and dried at 200 ° C. for 1 minute to obtain a 3 μm primer layer. Next, a photocatalyst-containing layer and a material layer having a variable wettability described in Example 22 were formed on the primer layer, and a waterless printing plate precursor was obtained.

Next, an Nd: YAG laser (355n)
The pattern was formed using a recording energy of 200 mJ / cm < ² > using m lambda physics Star Line). The obtained printing plate was attached to an offset printing machine (Alpha New Ace manufactured by Alpha Giken),
When printing was performed on coated paper at a printing speed of 5000 sheets / hour using a waterless printing ink (Inktec Waterless S Yellow manufactured by The Inktec), 20,000 sheets of good printed matter 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. By heating the amorphous titania layer at 400 ° C. for 10 minutes,
The phase changed to an anatase-type titania layer.

[0120] Next, a layer of the same wettability as in Example 23 on the titania layer is changed, 50 mW / cm ² with a mercury lamp through a resolution chart mask of 50 lp / mm
Irradiation for 2 minutes. Next, the waterless printing ink (Inktec Waterless S manufactured by The Inktec)
Yellow), RI tester (RI-2 manufactured by Ishikawajima Sangyo Kikai)
Using a mold) to coat the entire surface of the obtained exposed pattern formed body. 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 is applied by spin coating.
The composition was applied on a substrate having a sodium ion blocking layer having a thickness of 0.2 μm. Next, by drying at a temperature of 150 ° C. for 30 minutes, hydrolysis and polycondensation proceed, and a 0.2 μm-thick photocatalyst-containing composition layer in which a photocatalyst and a 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 change over time of the contact angle with water was measured with a contact angle measuring instrument (CA-Z type manufactured by Kyowa Interface Science). FIG. 8 shows the results. From the figure, the contact angle, which was 63 ° before irradiation, decreased with irradiation time,
° was confirmed.

Example 26 3 g of silica sol, Glasca HPC7002 (Nippon Synthetic Rubber), and HPC40, an alkylalkoxysilane
1 g of 2H (Japanese synthetic rubber) was mixed and stirred for 5 minutes.
This solution is spin-coated to a thickness of 0.15 m.
m of an aluminum base material 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 obtained printing plate precursor was used as a lithographic printing plate precursor with water at 175 lines /
The pattern was formed by exposing with a xenon lamp through a gradation positive film having 2% to 98% halftone dots in inches. Next, the obtained printing plate was attached to an offset printing machine (Alpha New Ace, manufactured by Alpha Giken), and the ink for offset printing (Across Red, manufactured by The Inktec) and fountain solution were used.
When printing was performed on coated paper at a printing speed of 5000 sheets / hour, 20,000 good printed matters were obtained.

Example 27 A photocatalyst-containing layer having a thickness of 0.4 μm was formed on a transparent substrate made of quartz glass by spin coating with the same composition as in Example 4. Then, 70 mW / m / m by a mercury lamp through a mask having a circular pattern with an opening diameter of 9 mm.
Exposure was performed for 90 seconds at an illuminance of cm ² to obtain a transparent substrate having a circular pattern with high wettability on the surface.

1000 g of a water-soluble ultraviolet-curable ester acrylate resin (AQ-7 manufactured by Arakawa Kogyo) and a curing initiator (Irgacure 18 manufactured by Ciba Specialty Chemicals)
4) 50 g 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, and the diameter was 9 mm and the focal length was 45 mm.
Was manufactured.

Example 28 A photocatalyst-containing layer having a thickness of 0.4 μm was formed on a transparent substrate made of quartz glass by spin coating with the same composition as in Example 4. Then, 70 mW /
Exposure was performed for 90 seconds at an illuminance of cm ² to obtain a transparent substrate having a circular pattern with high wettability on the surface.

1000 g of a water-soluble ultraviolet-curable ester acrylate resin (AQ-7 manufactured by Arakawa Kogyo) and a curing initiator (Irgacure 18 manufactured by Ciba Specialty Chemicals)
4) 50 g and 125 g of water were mixed and stirred for 3 minutes. The resulting mixed solution is spin-coated on a circular pattern having a different wettability formed on a transparent substrate to a thickness of 2 μm.
When the mixture was applied at a thickness of 0 μm, the mixed solution adhered only to the circular portions. Then, irradiation was performed with an illuminance of 70 mW / cm ² for 3 seconds using a mercury lamp to obtain a diameter of 1 mm and a focal length of 2.5 m.
m lenses were produced.

Example 29 A degreased aluminum plate having a thickness of 0.23 mm was coated with a 20% by weight dimethylformamide solution of primer (Kansai Paint 90T-25-3094, a primer paint for metal manufactured by Kansai Paint), and dried at 200 ° C. for 1 minute. A primer layer of 3 μm was formed. Next, on this primer layer, both ends OH-modified polydimethylsiloxane (X-22-160AS, functional group equivalent 112, manufactured by Shin-Etsu Chemical) 9
g, crosslinking agent (polyisocyanate, Coronate L, manufactured by Nippon Polyurethane), 1 g, butyltin dilaurate 0.05
g, titanium oxide powder (Ishihara Sangyo ST-01 particle size 7n)
m) A composition comprising 1 g, 5 g of 1,4-dioxane, and 5 g of isopropanol was applied and dried at 120 ° 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 = 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 with 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 mounted on an offset printing press (Komori Sprint 4-color press) and printed on coated paper using printing ink (Dryo Color Indigo Ink manufactured by Dainippon Ink and Chemicals, Inc.). And a good 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 (Shin-Etsu) 8 g of chemical X-22-160AS), 1 g of polydimethylsiloxane (KF96 by Shin-Etsu Chemical),
1 g of crosslinking agent (polyisocyanate, Coronate L, manufactured by Nippon Polyurethane), 0.05 g of dibutyltin dilaurate
g, titanium oxide powder (Ishihara Sangyo ST-01 particle size 7n)
m) A composition consisting of 1 g, 5 g of toluene and 5 g of isopropanol was applied, dried at 150 ° C. for 2 minutes, and dried to a thickness of 1 μm.
m of the photocatalyst-containing layer 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, 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. A contact angle measuring device (Kyowa Interface Science Co., Ltd.)
(AZ type), 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 Silica sol (Nippon Synthetic Rubber Glasca HPC700)
2) 3 g and 1 g of alkylalkoxysilane (Nippon Synthetic Rubber, HPC402H) were mixed and stirred for 5 minutes. The area of this solution is 7.5 cm by spin coating.
^It was applied to the glass substrate of No. 2 to form a sodium ion blocking layer having a thickness of 2 μm. Next, 3 g of isopropyl alcohol and silica sol (Glaska HP made by Nippon Synthetic Rubber)
C7002) 0.75 g, Alkylalkoxysilane (Nippon Synthetic Rubber Glasca HPC402H) 0.25
g, fluoroalkoxysilane (MF-160E manufactured by Tochem Products: N- [3- (trimethoxysilyl))
Propyl] -N-ethyl perfluorooctanesulfonamide in 50% by weight isopropyl ether) 0.1
5 g were mixed. The obtained dispersion is kept at 100 ° C. for 20 minutes.
And stirred. 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 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, polydimethylsiloxane modified at both ends with OH (X-22-1 manufactured by Shin-Etsu Chemical Co., Ltd.)
60 g), 2 g of silica sol (Glaska HPC7002, manufactured by Nippon Synthetic Rubber) and 1 g of alkylalkoxysilane (HPC402H, manufactured by Nippon Synthetic Rubber), and agitated for 5 minutes to apply a dispersion liquid.
After drying for 0 minute, a pattern formed body having a dry film thickness of 0.5 μm was obtained. When the average roughness of the surface of the obtained pattern formed body was measured by a stylus method, Ra was 2 nm. Then, a 365 nm YAG laser was irradiated at 200 mJ / cm ^2.
Irradiation was performed at an intensity of 5 to form a pattern and a photocatalytic reaction occurred. Contact angles of water and n-octane of the light irradiation section were 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, as in the case of Example 27, the printing original plate was transferred to an offset printing machine (Komori Sprint 4).
Color machine) and printing on coated paper using a printing ink (Dryocolor Indigo Ink manufactured by Dainippon Ink and Chemicals, Incorporated) resulted in good printed matter.

Example 33 In the same manner as in Example 29, a primer layer was formed on a 0.23 mm-thick aluminum substrate, and an emulsion-type addition-reaction-type polydimethylsiloxane (Shin-Etsu) was formed on the primer layer. Chemicals KM-768 Active ingredient 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) 0 .012 g and mixed after application.
It dried at 1 degreeC for 1 minute, and obtained the 1 micrometer-thick photocatalyst containing layer.
In addition, a mask is brought into close contact with a high-pressure mercury lamp of 70 mw / cm ²
Table 7 shows the results of measuring the contact angle with water and n-octane using a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science) after irradiating ultraviolet rays for 10 minutes at an illuminance of 10 to cause a photocatalytic reaction.

Example 34 A 20% by weight dimethylformamide solution of a primer (Kansai Paint Prime Coat 90T-25-3094) was applied on a degreased aluminum plate having a thickness of 0.23 mm and dried at 200 ° C. for 1 minute. And 3 μm
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 coated on the previously formed primer layer with a blade coater,
Drying was performed at 00 ° C. for 10 minutes.

Next, 3 g of isopropyl alcohol, 0.75 g of silica sol (Glaska HPC7002, solid content 12%, manufactured by Nippon Synthetic Rubber) and 0.2 of alkylalkoxysilane (HPC402H, solid content of 50%, manufactured by Nippon Synthetic Rubber)
5 g, fluoroalkoxysilane (MF-160E manufactured by Tochem Products: 50% by weight solution of N- [3- (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in isopropyl ether)
0.15 g and 0.15 g of dimethoxydimethylsilane (TSL8112 manufactured by Toshiba Silicone) were mixed. This solution was stirred for 20 minutes while maintaining the temperature at 100 ° C. afterwards,
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 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%. The surface roughness Ra of the obtained pattern formed body measured by the stylus method was 2 nm.

Next, this pattern-formed body was irradiated with 70 mW / cm ² illuminance by a high-pressure mercury lamp through a grid-like mask.
Table 1 shows the results of measuring the contact angle 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 35 A pattern formed body manufactured in the same manner as in Example 34
A photocatalytic reaction was performed by irradiating a 355 nm YAG laser at an intensity of 200 mJ / cm ^{2 in} a pattern. 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 measurement 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%. Was prepared and evaluated in the same manner as in Example 31, and the results are shown in Table 7. Also,
When printing was performed on the coated paper in the same manner as in Example 31, a favorable printed matter without background smear was obtained.

Example 37 A 20% by weight dimethylformamide solution of a primer (Kansai Paint Metal Coat 90T-25-3094) was applied on a degreased aluminum plate having a thickness of 0.23 mm and dried at 200 ° C. for 1 minute. And 3 μm
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 coated on the previously formed primer layer with a blade coater,
Drying was performed at 00 ° C. for 10 minutes.

Next, 3 g of isopropyl alcohol and silica sol (Glaska HPC7002 manufactured by Nippon Synthetic Rubber) were added.
75g, Alkylalkoxysilane (made by Nippon Synthetic Rubber)
HPC402H) 0.25 g, fluoroalkoxysilane (manufactured by Tochem Products, MF-160E: N- [3-
(Trimethoxysilyl) propyl] -N-ethyl perfluorooctanesulfonamide in 50% by weight of isopropyl ether) and 0.15 g of dimethoxydimethylsilane. The solution is added for 20 minutes to 100
The mixture was stirred while maintaining the temperature at ° 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 give 0.2
A μm coating layer was formed to obtain a pattern formed body.

Next, the obtained pattern formed body was irradiated with YAG laser at 200 mJ / cm ² through a lattice-like mask.
Exposure was performed at an energy density of 1 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 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.

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.
When the photocatalyst-containing layer was attached to a printing press in the same manner as in Example No. 0, the photocatalyst-containing layer was partially peeled off from the aluminum base material, 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 having a primer layer did not peel, but those without a primer layer did peel. .

Comparative Example 6 A commercially available original plate for offset printing was applied to a thermal plate Pea.
Example 2 using rl dry (manufactured by Presstek)
The characteristics were evaluated in the same manner as in Example 9, and the results are shown in Table 7.

Comparative Example 7 Offset plate H without water using a commercially available original plate for offset printing
The properties were evaluated using GII (manufactured by Toray Industries Inc.) in the same manner as in Example 29, and the results are shown in Table 7.

Comparative Example 8 A pattern formed 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%. Was prepared, and the surface of the photocatalyst-containing layer was measured by a stylus method. The surface roughness Ra was 500 nm. The surface of the photocatalyst-containing layer was disturbed, and a printing plate could not be prepared.

Comparative Example 9 A pattern-formed 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%. Example 3
Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 7. The surface roughness Ra measured by the stylus method was 50 nm. In addition, when printing was performed on coated paper in the same manner as in Example 34, background smearing occurred.

[0149]

Table 7 Exposed part Unexposed part Water n-octane Water n-octane Example 29 5 ° or less 5 ° or less 113 ° 16 ° Example 31 5 ° or less 5 ° or less 113 ° 16 ° Example 32 5 ° or less 5 115 ° 15 ° or less Example 33 5 ° or less 5 ° or less 107 ° 15 ° Example 34 5 ° or less 5 ° or less 113 ° 16 ° Example 35 80 ° or less 5 ° or less 113 ° 16 ° Example 36 70 ° 5 ° or less 113 ° 16 ° Example 37 80 ° or less 5 ° or less 115 ° 15 ° Comparative Example 6 84 ° 5 ° or less 105 ° 11 ° Comparative Example 7 104 ° 5 ° or less 116 ° 13 ° Comparative Example 9 80 ° 5 ° or less 115 ° 20 °

[0150]

According to the pattern forming body of the present invention, since the photocatalyst-containing composition layer is formed on the substrate, the pattern is formed by changing the wettability of the surface by the action of the photocatalyst upon irradiation with light. Therefore, a pattern can be formed without a step of development or the like, and can be used for many applications including a printing plate precursor and a functional element.

[Brief description of the drawings]

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

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

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

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

FIG. 5 is a diagram illustrating the relationship between light irradiation time and 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 diagram illustrating another embodiment of the method for manufacturing an element of the present invention.

FIG. 11 is a diagram illustrating another embodiment of the method for manufacturing an element of the present invention.

FIG. 12 is a diagram illustrating another embodiment of the method for manufacturing an element of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Pattern forming body, 2 ... Base material, 3 ... Primer layer,
4, 41, 42, 43, 44: photocatalyst containing layer, 5: pattern, 6: exposure, 7: photocatalyst, 8: hydrophilic site, 9: hydrophobic site, 10: wettability changing material layer, 11: wettability Are different, 12 is a material layer to be decomposed and removed, 13 is a portion having different wettability, 14 is a hydrophobic portion, 15 is a hydrophilic portion,
16 photocatalytic decomposable substance, 17 part changed according to pattern, 18 stripe pattern, 19 lattice light-shielding pattern, 20 photomask, 21 laser, 22 blade coater, 23 spin coater , 24
... film forming means utilizing vacuum, 25 ... functional layer, 26 ... adhesive tape, 27 ... air jet nozzle, 28 ... functional layer, 2
9: element forming substrate, 30: sheet, 31: heat-fusible composition layer, 32: thermal transfer member, 34: heating plate, 35: discharge nozzle, 36: ultraviolet curable resin composition, 38: ultraviolet ray for curing , 38 ... micro lens

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 10-85955 (32) Priority date Hei 10 (1998) March 31 (33) Priority claim country Japan (JP) (31) Priority Claim Number Japanese Patent Application No. 10-86293 (32) Priority Date Hei 10 (1998) March 31 (33) Priority Country Japan (JP) (72) Inventor Manabu Yamamoto 1-chome, Ichigaya-Kagacho, Shinjuku-ku, Tokyo No. 1 Inside Dai Nippon Printing Co., Ltd.

Claims (27)

[Claims] 1. A pattern forming body for optically forming a pattern, comprising a photocatalyst-containing layer on a substrate, wherein the photocatalyst-containing layer contains a substance whose wettability changes by the action of a photocatalyst upon exposure of the pattern. A pattern forming body, characterized in that: 2. A pattern forming body for optically forming a pattern, having a photocatalyst-containing layer on a base material, and having a layer on the photocatalyst-containing layer which is decomposed and removed by the action of a photocatalyst upon exposure of the pattern. A pattern formed body characterized by the above. 3. A pattern-forming body for optically forming a pattern, comprising a photocatalyst-containing layer on a base material, and containing on the photocatalyst-containing layer a substance whose wettability is changed by the action of a photocatalyst upon exposure of the pattern. A pattern formed body having a layer. 4. A pattern forming body for optically forming a pattern, comprising: a composition layer comprising a photocatalyst, a substance decomposed by the action of the photocatalyst upon exposure of the pattern, and a binder. body. 5. The pattern forming body according to claim 1, wherein the layer containing a photocatalyst contains a compound having a siloxane bond. 6. The pattern forming body according to claim 1, wherein the layer containing the photocatalyst contains silicone. 7. The pattern forming body according to claim 6, wherein a fluoroalkyl group is bonded to a silicon atom of the silicone. 8. The pattern forming body according to claim 6, wherein the silicone is obtained from a composition containing an organoalkoxysilane. 9. The pattern forming body according to claim 6, wherein the silicone is obtained from a composition containing a reactive silicone compound. 10. The pattern forming body according to claim 1, wherein the pattern forming body is a printing plate precursor. 11. A method for optically forming a pattern, comprising: 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; A pattern-formed body in which a layer containing a substance whose wettability changes by the action of a photocatalyst is formed on the layer. On a pattern formed body having a layer, or on a substrate, a photocatalyst, a substance that is decomposed by the action of the photocatalyst by exposure of the pattern, and a pattern formed body formed with a composition layer composed of a binder are exposed to a pattern, A pattern forming method characterized by changing the wettability of the surface by the action of a photocatalyst. 12. The method according to claim 11, wherein the pattern exposure on the photocatalyst-containing layer is performed by light drawing irradiation.
The pattern forming method described in the above. 13. The pattern forming method according to claim 11, wherein pattern exposure of the photocatalyst-containing layer is performed by exposure through a photomask. 14. The pattern forming method according to claim 11, wherein the pattern exposure of the photocatalyst-containing layer is performed while heating the pattern forming body. 15. A pattern forming body according to any one of claims 1 to 9 on a base material, wherein the pattern forming body is provided.
An element, wherein a functional layer is disposed on a portion corresponding to the pattern of the pattern formed body obtained by the pattern exposure of any one of the above. 16. A functional layer formed on a portion corresponding to the pattern of the pattern formed body obtained by the pattern exposure according to any one of claims 11 to 14 on another patterned substrate. An element characterized by being formed by being transferred to a substrate. 17. A pattern forming body according to claim 1 on a base material, wherein the pattern forming body is provided on a substrate.
Forming a functional layer on a portion corresponding to the pattern of the pattern formed body obtained by the pattern exposure of any one of the above. 18. A functional layer is transferred onto a portion corresponding to a pattern of the pattern formed body obtained by the pattern exposure according to any one of claims 11 to 14 onto another patterned substrate. A method for producing an element, comprising forming a functional layer on a substrate by performing the method. 19. A step of laminating a composition for a functional layer on the entire surface of a pattern-formed body, wherein a functional layer is formed in a pattern only on a portion where the wettability of an exposed portion has changed due to the repulsion of an unexposed portion. The method according to claim 17, further comprising a step.
An element manufacturing method according to the above. 20. A method of forming a functional layer in a pattern by removing a functional layer in an unexposed portion by laminating a functional layer composition on the entire surface of a pattern formed body. The method for producing an element according to claim 17, wherein 21. A step of laminating a composition for a functional layer over the entire surface of a pattern-formed body, wherein a functional layer is formed in a pattern only on a portion where the wettability of an exposed portion has changed due to the repulsion of an unexposed portion. 19. The method according to claim 18, further comprising a step.
An element manufacturing method according to the above. 22. A method comprising the steps of: laminating a functional layer composition on the entire surface of a pattern-formed body; and forming a functional layer in a pattern by removing unexposed portions of the functional layer. The method for manufacturing an element according to claim 18, wherein 23. The method according to claim 19, wherein the formation of the functional layer on the pattern forming body is performed by applying a functional layer composition. 24. The method according to claim 19, wherein the formation of the functional layer on the pattern forming body is performed by discharging a functional layer composition from a nozzle. 25. 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.
3. The element manufacturing method according to 2. 26. The element 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. 27. 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 electroless plating.