JP2002274077A - Pattern forming body and pattern forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming body using a photocatalyst. SOLUTION: A pattern forming body records a pattern by changing wetting properties through exposure by a method wherein a base has either a photocatalyst containing layer, which contains a substance having wetting properties changing by the action of the photocatalyst through the exposure of the pattern, a layer containing the substance having wetting properties changing by the action of the photocatalyst through the exposure of the pattern on the photocatalyst containing layer, or a base material has the photocatalyst containing layer, which has a layer dissolvingly removing by the action of the exposure of the pattern thereon, or the base material has a composition layer consisting of a photocatalyst, a substance dissolved by the action of the photocatalyst through the exposure of the pattern and a binder.

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 formed by transferring a pattern-like layer formed on the pattern-formed body in accordance with a change in wettability and transferred. Means layer.

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

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

A printing plate for offset printing is developed by exposing the printing plate precursor through a mask on which a pattern is drawn, or by directly exposing by electrophotography to form a plate on the printing plate precursor. And the like. An electrophotographic offset printing plate precursor is exposed by an electrophotographic method as a photoconductor provided with a photoconductive layer mainly composed of photoconductive particles such as zinc oxide and a binder resin on a conductive substrate, 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.

[0006] Instead of the method of forming an oleophobic site by immersing in water, instead of immersion in water or the like, a highly oleophobic site is formed, so that the ink receiving site and the ink receiving site are separated. A printing plate precursor for dry lithographic printing, which forms an unacceptable site, has also been used.

[0007] Further, a method for producing a lithographic printing plate precursor using a heat mode recording material capable of forming a portion having high ink receptivity and a portion having ink repellency by laser irradiation is proposed. Have been. Heat mode recording materials have the characteristic that printing plates can be manufactured simply by forming an image with a laser beam without the need for processes such as development, but adjustment of laser intensity and deterioration by laser There are problems in the treatment of the residue of the solid substance thus obtained, the printing durability, and the like.

As a method for forming a high-definition pattern, a photoresist layer applied on a substrate is exposed to a pattern, and after the exposed photoresist is developed, 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 for a liquid crystal display device, forming a microlens, manufacturing a fine electric circuit board, and forming a chromium mask used for pattern exposure. Although it is used in manufacturing, etc., it is necessary to use a photoresist and develop or etch with a liquid developer after exposure depending on these methods, so that it is necessary to treat a waste liquid. In addition, when a functional material is used as a photoresist, there is a problem that the material is deteriorated by an alkali solution used in the 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 provided a pattern forming body and a pattern forming method for forming a pattern using a substance whose wettability changes by the action of a photocatalyst. As proposed in Japanese Patent Application No. 9-214845, the present invention provides a pattern-formed body and a pattern-forming method having better characteristics in such a pattern-formed body and a forming method using a photocatalyst. .

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a new pattern forming body and a 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, and has excellent characteristics when used for forming various functional elements. It is an object to provide a pattern forming body and a pattern forming method capable of providing a functional element.

[0013]

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.

[0014] In the pattern-forming body for optically forming a pattern, a pattern-forming body 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. It is.

In a pattern forming body for optically forming a pattern, a photocatalyst-containing layer is provided on a substrate, and a layer containing a substance whose wettability is changed by the action of a photocatalyst upon exposure of the pattern is formed on the photocatalyst-containing layer. It is a pattern formed body having.

A pattern-forming body for optically forming a pattern is a pattern-forming 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.

In the above-mentioned pattern forming body, the layer containing a photocatalyst contains a compound having a siloxane bond.

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

[0019] The above-mentioned pattern forming body, wherein a fluoroalkyl group is bonded to a silicon atom of silicone.

The above-mentioned pattern-formed body, wherein the silicone is obtained from a composition containing an organoalkoxysilane.

The above-mentioned pattern-formed body, wherein the silicone is obtained from a composition containing a reactive silicone compound.

The above-mentioned pattern-formed body is a printing plate precursor.

Also, in the method for optically forming a pattern, a pattern formed body provided with a photocatalyst-containing layer containing a substance whose wettability changes by the action of a photocatalyst on a substrate.
A pattern formed body in which a layer containing a substance whose wettability changes by the action of a photocatalyst is formed on a photocatalyst-containing layer formed on a substrate, and a pattern is formed on the photocatalyst-containing layer by having a photocatalyst-containing layer on the substrate. 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 for the photocatalyst-containing layer is the above-described pattern forming method performed by light drawing irradiation.

The pattern exposure for the photocatalyst-containing layer is the above-described pattern forming method performed by exposure through a photomask.

The pattern exposure for the photocatalyst-containing layer is the above-described pattern forming method performed while heating the pattern formed body.

An element having the above-mentioned pattern formed body on a base material and having a functional layer disposed on a portion corresponding to the pattern of the pattern formed body obtained by the above 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. is there.

This is a method for producing an element having the above-mentioned pattern-formed body on a substrate and forming a functional layer on a portion corresponding to the pattern of the pattern-formed body obtained by the above-mentioned pattern exposure.

The functional layer is transferred onto another substrate by transferring a functional layer onto a portion corresponding to the pattern of the pattern formed body obtained by the above-mentioned pattern exposure on the pattern formed body, thereby forming a functional layer on the base material. This is an element manufacturing method in which a layer is formed.

The step of laminating the composition for a functional layer on the entire surface of the pattern-formed body and 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 are included. The above-described method for manufacturing an element.

The above-mentioned element manufacturing method comprises a step of laminating a functional layer composition on the entire surface of the pattern formed body and a step of forming a functional layer in a pattern by removing the unexposed portion of the functional layer. is there.

The step of laminating the functional layer composition on the entire surface of the pattern-formed body and the step of forming the 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 are included. The above-described method for manufacturing an element.

The above element manufacturing method comprises the steps of laminating a functional layer composition on the entire surface of the pattern-formed body, and forming a functional layer in a pattern by removing the unexposed functional layer. is there.

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

The formation of the functional layer on the pattern formed body is the above-described method for producing an element by discharging the functional layer composition from a nozzle.

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

[0040]

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 the action of a photocatalyst capable of causing a chemical change in a nearby substance by light irradiation. In the present invention, a pattern means a portion that receives or repels ink when transferring printing ink when it is used for printing designs, images, characters, and the like. Further, the pattern formed body of the present invention can be used for purposes other than printing. In this case, the pattern 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.

Although the mechanism of action by the photocatalyst represented by the titanium oxide of the present invention is not necessarily clear, the carrier generated by light irradiation may react directly with a nearby compound or in the presence of oxygen and water. It is believed that the generated reactive oxygen species change the chemical structure of organic matter.

By using the action of the photocatalyst, oily stains are decomposed by light irradiation, and the oily stains are made hydrophilic so that they can be washed with water, or a hydrophilic film is formed on the surface of glass or the like to prevent them. A so-called antibacterial tile or the like has been proposed which imparts haze or forms a layer containing a photocatalyst on the surface of a tile or the like to reduce the number of airborne bacteria.

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 due to the action of a photocatalyst, or a layer having a composition composed of a substance decomposed by the action of a photocatalyst and a binder, etc., and accepting a printing ink or a toner in a 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.

Examples of the photocatalyst that can be used in the pattern forming body and the pattern forming method of the present invention include titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), 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 the anatase type titanium, those having a small particle size are preferable because the photocatalytic reaction occurs efficiently. The average particle size is preferably 50 nm or less, more preferably 20 nm or less. For example, anatase-type titania sol of peptized hydrochloric acid (ST manufactured by Ishihara Sangyo Co., Ltd.)
S-02, average crystallite diameter of 7 nm) and nitrate-peptized anatase titania sol (Nissan Chemical Industries, TA-15, average crystallite diameter of 12 nm).

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

Accordingly, as the binder, a silicone resin having a main skeleton having 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, the general formula Y _n Si
One or more hydrolytic condensates and cohydrolytic condensates of the silicon compound represented by X _4-n (n = 1 to 3) can be used. Y can include an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, or an epoxy group, and X can include a halogen, a methoxyl group, an ethoxyl group, or an acetyl group.

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 in a sol-gel method or the like, the crosslink density can be improved by using a trifunctional silicone precursor, such as trialkoxymethylsilane, as a main component. In the case where the wettability is made different as described above, the oil repellency can be improved when the dimethylsiloxane component is contained more than when the methylsiloxane component is contained.

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

[0055]

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 have a molar ratio of 60% or more.

The molecular weight is 500 to 1,000,000
Is preferable, and when the molecular weight is small, R ¹ ,
Since the amount of R ² is small, oil repellency and the like are hardly exhibited. On the other hand, if the molecular weight is too large, the ratio of terminal X and Y becomes relatively small, so that there is a problem that the crosslink density becomes small.

X and Y are selected from the following groups.
And Y may be the same or different, and R has 1 carbon atom.
It is a hydrocarbon chain of 0 or less.

[0059]

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 crosslinking reaction is carried out using a crosslinking agent,
Examples of the cross-linking agent include generally used isocyanates, and preferably the following compounds.

[0062]

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.

The oil repellency may be enhanced by mixing a stable organosiloxane compound such as dimethylpolysiloxane which does not undergo a cross-linking reaction with the reactive silicone compound used as the binder of the present invention.

In this case, 60% of the siloxane contained in the layer obtained from the composition containing the reactive silicone compound is used.
It is preferable that at least 60% by weight be obtained from a reactive silicone compound. If the amount is less than 60% by weight, dimethylsiloxane will decrease and water repellency will deteriorate, which is not preferable.

As the binder, an amorphous silica precursor can be used, which is 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 20% by weight to 40% by weight. Is more preferred.

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.

Further, a titanium-based, aluminum-based, zirconium-based, or chromium-based coupling agent 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, and bead coating. Further, when an ultraviolet-curable component is contained as a binder, a layer of the composition containing the photocatalyst can be formed on the substrate by irradiating ultraviolet rays and performing a curing treatment.

The 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 with a fine beam such as a laser, a desired pattern can be drawn directly 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.

The pattern forming body of the present invention can be made sensitive to visible and other wavelengths by doping metal ions such as chromium, platinum and palladium, adding a fluorescent substance, and adding a photosensitive dye. . For example, cyanine dyes such as cyanine dyes, carbocyanine dyes, dicarbocyanine dyes, hemicyanine dyes, and the like; other useful dyes include crystal violet, and diphenylmethane dyes such as triphenylmethane dyes such as basic fuchsin. And xanthene dyes such as rhodamine B, Victoria blue, brilliant green, malachite green, methylene blue, pyrylium salts, benzopyrylium salts, trimethine benzopyrylium salts, triallylcarbonium salts and the like.

When a mask is used 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 significantly reduced. Exposure is preferably performed at intervals.

Further, by exposing the space between the mask and the pattern forming body while blowing air, the reaction is promoted and the sensitivity is improved, and the non-uniformity due to the difference in the position between the central part and the peripheral part is prevented. Can be. 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.

The substrate which can be used for the pattern-formed body of the present invention includes 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 for improving adhesion, improving surface roughness, preventing deterioration of a substrate due to the action of a photocatalyst, preventing a decrease in photocatalytic activity, and the like, before applying the photocatalyst-containing layer composition. 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 the alkyl chain of the silicone compound is converted to an OH group by the action of a photocatalyst 7 as shown in FIG. 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 forming 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 on the photocatalyst-containing composition layer, a wettability changing substance layer 10 whose wettability changes by the action of a photocatalyst when irradiated with light is formed.
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 the 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 weight compound, a high molecular weight compound, a surfactant or the like, whose wettability is changed by a photocatalyst, can be used.

Specifically, a silane compound in which an organic group is changed to a hydroxyl group by the action of a photocatalyst, such as a silane coupling agent, chlorosilane, alkoxysilane, or a hydrolyzed condensate or a cohydrolyzed condensate of two or more of these. Things can be mentioned.

Further, as a third embodiment, FIG.
As shown in (A), a photocatalyst-containing composition layer 43 is formed on a substrate 2, and on the photocatalyst-containing composition layer, a material layer 12 that is decomposed and removed by the action of a photocatalyst when irradiated with light. Then, as shown in FIG. 3 (B), exposure 6 is performed using the pattern 5, and as shown in FIG. 3 (C), a portion 13 having different wettability according to the pattern is formed 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, hydrocarbons such as NIKKOL BL, BC, BO, and BB series manufactured by Nippon Surfactant Industry; 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. 4 (A), 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.

As the substance that changes the wettability of the surface,
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 BL, BC, BO, manufactured by Nippon Surfactant Industries, Ltd.
Hydrocarbons such as BB series, DuPont: ZON
YL FSN, FSO, Asahi Glass: Surflon S-14
1, 145, Dainippon Ink: Megafac F-141,
144, Neos: Futuregent F-200, F25
1, Daikin Industries Unidyne DS-401, 402,
3M: Fluorine-based or silicone-based nonionic surfactants such as Florade FC-170 and 176 can be used, 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. .

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

The pattern-formed body of the present invention is used as a printing plate since the surface energy is changed by the action of the photocatalyst in the composition and the wettability is changed at the site where the acceptability of the printing ink is changed. be able to.

When the pattern-formed body of the present invention is used as a printing plate precursor, there is no need for wet development or the like, and it is characterized in 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 preparing a printing plate precursor, a base material 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. In addition, if there is a fear that the base material is deteriorated by the photooxidation action of the photocatalyst such as plastic, a protective layer may be formed by coating the base material with silicone or a fluororesin in advance. Any shape such as a sheet shape, a ribbon shape, and a roll shape can be used.

Further, 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,
The formed pattern may be visualized.

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

When the pattern formed body of the present invention is used for an element having a pattern laminated thereon, 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 is defined as 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, magnetically permeable, etc., electric and 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, heat insulation properties, infrared radiation properties, etc.), biological functions (biocompatibility, (Eg, antithrombotic properties).

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

In this case, examples of the composition for the functional layer include a liquid composition which is not diluted with a solvent represented by an ultraviolet curable monomer and the like, and a liquid composition which is diluted with a solvent. 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 solvent evaporates during the pattern formation, causing an increase in viscosity and a change in surface tension.

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 or the like, and a means such as electroless plating. In addition, when the composition for a functional layer contains a component curable by ultraviolet light, heat, electron beam, or the like as a binder, by performing a 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, the peeling is performed by peeling off the adhesive tape, for example, by using the adhesive force difference between the exposed or unexposed part and the interface of the functional layer, by adhering the adhesive tape. The functional layer on the unexposed area 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 vacuum film forming means such as PVD and 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 only by forming a layer on a pattern forming body but also those which show the properties as a functional layer only by forming a layer do not show the properties as a functional layer. Treated with chemicals after layer formation,
Also includes those that require treatment with ultraviolet light, heat, or the like.

Next, an element which can be manufactured using the pattern formed body of the present invention will be described.

A color filter used in a liquid crystal display device or the like has a high-definition pattern in which a plurality of colored pixels such as red, green, and blue are formed. Thus, a high-definition color filter can be manufactured. For example, when a colorant-containing composition for forming a color filter is applied on a photocatalyst-containing layer formed on a transparent glass substrate after pattern exposure, a change in wettability of an exposed portion causes a change in the colorant-containing composition only in the exposed portion. Since the object is applied, the amount of the colorant-containing composition used can be reduced. In addition, since the colorant-containing composition layer is formed only on the pattern, if a photosensitive resin composition is used as the colorant-containing composition, only the photocuring treatment after application can be performed without performing development or the like. Resolution color filters are possible.

Further, the pattern forming body of the present invention can be used for producing microlenses. For example, circular exposure is performed on the photocatalyst-containing layer laminated on the transparent substrate to form a circular pattern having changed wettability. Next, when the lens-forming composition is dropped on the portion where the wettability has changed, the lens-forming composition wets and spreads 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, a predetermined hydrophilicized pattern is formed on the pattern-formed body of the present invention by light irradiation, and then, a part which has been rendered hydrophilic by a pretreatment liquid for chemical plating is subjected to a treatment. The desired metal can be immersed to form a pattern. 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 in a method of forming a pattern of a metal or the like using a vacuum film forming technique.

For example, a pattern having a large adhesiveness is formed 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. To form 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, so a patterned metal thin film is formed by a method of peeling by pressing an adhesive on the thin film surface, a method of peeling with a chemical, etc. can do.

In the case of peeling using an adhesive, the adhesive-coated sheet is brought into contact with the surface of the thin film, and then the adhesive-coated sheet 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, a metal pattern can be formed without forming a resist pattern, and a printed circuit board, an electronic circuit element, or the like having a finer pattern than by a printing method can be manufactured. it can.

The method of manufacturing the device of the present invention will be described below with reference to the drawings.

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

In the pattern exposure step of FIG.
As shown in A1, a pattern forming body 1 having a photocatalyst containing layer 4 provided on a substrate 2 is exposed using a photomask 20 according to a pattern of an element to be formed, or a pattern is formed as shown in A2. Laser 2 with wavelength in the ultraviolet region
By drawing directly using 1 or the like, a portion 13 having different wettability is formed on the surface of the pattern forming body.

Next, in the entire film forming step shown in FIG.
Coating using a blade coater 22 as shown in 1 or coating using a spin coater 23 as shown in B2;
Film forming means 2 utilizing vacuum such as vapor deposition and CVD shown by B3
4, a functional layer 25 is formed on the entire surface of the pattern formed body.

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 the difference in surface energy caused by exposure of the pattern formed body.

Next, in the peeling step shown in FIG. 9C, a method of peeling the functional layer formed on the unexposed portion by peeling the adhesive surface of the adhesive tape 26 and then peeling it off from the end portion, The functional layer 28 is formed by removing the functional layer from a portion having a small adhesive force by a method of injecting air 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 is a view for explaining a cross section.

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

Next, as shown in FIG. 10 (C), the functional layer 25 was transferred onto the
8 is formed.

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 pattern forming body 1 in which the photocatalyst containing layer 4 is provided on the base material 2 is exposed using a photomask 20 in accordance with the pattern of the element to be formed. A portion 13 having changed wettability is formed.

Next, as shown in FIG. 11 (B), a thermal transfer member 3 having a heat-fusible composition layer 31 formed on a sheet 30 was used.
The surface on which the heat-fusible composition layer 2 is formed is brought into 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 the 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 to form an unexposed portion and a portion 13 having changed wettability by the exposure.

As shown in FIG. 12B, the discharge nozzle 3
From 5, the ultraviolet curable resin composition 36 is discharged toward a circular pattern.

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

Next, as shown in FIG. 12D, the microlenses 3 are irradiated with ultraviolet rays for curing 37.
8 can be formed.

[0135]

The present invention will be described below with reference to examples.

Example 1 30 g of Glasca 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. The solution was applied to a glass substrate having an area of 7.5 cm ² by spin coating, and dried at a temperature of 150 ° C. for 10 minutes to form a sodium ion block layer having a thickness of 2 μm.

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

The obtained pattern-formed body was irradiated with ultraviolet light at an illuminance of 6.6 mW / cm ^{2 using} a xenon lamp, and the change over time in 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. Further, by irradiating ultraviolet rays through a lattice-like mask, irradiation is performed at an illuminance of 6.6 mW / cm ² for 6 hours using a xenon lamp 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.

Next, an Nd: YAG laser (355n)
The pattern was formed using a recording energy of 300 mJ / cm < ² > using a 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 Indigo, manufactured by The Inktec), 20,000 sheets of good printed matter were obtained.

In addition, the printing was performed in the same manner except that the laser was exposed to a xenon lamp at 175 lines / inch through a gradation negative film having 2% to 98% of halftone dots instead of the laser. Prints were 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: 10% by weight, manufactured by Ishihara Sangyo)
Was added and stirred for another 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. The average roughness of the surface of the obtained photocatalyst-containing layer was measured by a stylus method.
a = 2 nm.

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

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 /
UV irradiation for 2 minutes at an illuminance of cm ² , 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 photocatalyst-containing layer having a thickness of 0.3 μm 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. Was irradiated with ultraviolet light at 70 mW / cm ² for 2 minutes using a high-pressure mercury lamp.

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 device (CA-Z type, manufactured by Kyowa Interface Science Co., Ltd.).
When the critical surface tension was determined by an plot, the critical surface tension of the unexposed portion was 14.6 mN / m, and that of the exposed portion was 72.3 mN / m.

Next, a lithographic ink without water (Inktec Waterless S Indigo, manufactured by The Inktech) 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 area, and is selectively applied only to the exposed area, and is applied to the transparent polycarbonate substrate 2 via the photocatalytic layer 4 at a blue color of 50 lp / mm. A striped pattern 18 was obtained.

Example 6 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 on a degreased aluminum plate to obtain a primer layer having a thickness of 2 μm.

Next, the primer layer of Example 3
And the photocatalyst containing layer described in 4 was formed to obtain a waterless printing plate precursor.

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 base (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 Indigo, manufactured by The Inktec), 20,000 sheets of good printed matter were obtained.

In addition, instead of using a laser, a high-pressure mercury lamp was irradiated with ultraviolet light at a luminance of 70 mW / cm ² for 2 minutes at 175 lines / inch through a gradation negative pattern having halftone dots of 2% to 98%. When the printing characteristics were evaluated, good printed matter was obtained.

Example 7 A sodium ion blocking layer was formed 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 irradiated with ultraviolet light at an illuminance of 70 mW / cm ² for 5 minutes through a lattice-shaped mask on the photocatalyst-containing layer,
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 a light-shielding layer having a size of 150 × 300 μm.
A high-pressure mercury lamp was passed through a mask arranged at 0 μm intervals.
Ultraviolet irradiation was performed at an illuminance of 0 mW / cm ² for 5 minutes.

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 device (CA-Z type, manufactured by Kyowa Interface Science).
When the critical interfacial tension was determined by an plot, the critical surface tension of the unexposed portion was 15.4 mN / m, and that of the exposed portion was 73.3 mN / m.

Next, carbon black (manufactured by Mitsubishi Chemical Corporation)
# 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 to the entire surface of the exposed photocatalyst layer by a blade coater at a blade gap of 40 μm and a speed of 0.6 m / min. As shown in FIG. 7, the unexposed portion repels the light-shielding composition, and is selectively applied only to the exposed portion.
By heating at 00 ° C. for 30 minutes, a grid-like light-shielding pattern 19 was obtained on the substrate 2 made of glass via the photocatalyst layer 4.

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 manufactured by Ishihara Sangyo) Average particle size 2
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 ^TwoFor 5 minutes
UV irradiation and contact with water and n-octane
The angle is measured with a contact angle measuring instrument (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 were subjected to X-ray photoelectron spectroscopy (ESCALAB22, manufactured by VG Sientific).
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.

[0163]

[Table 1]

[0164] Exposure shows that the proportions of carbon and fluorine are reduced and the proportion of oxygen is increased. From the results of Example 9, considering that the contact angle 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 irradiated on the photocatalyst-containing layer with a high-pressure mercury lamp at an illuminance of 70 mW / cm ² for 10 minutes through a lattice-shaped mask, and the contact angle with water and n-octane was measured with a contact angle measuring device (CA manufactured by Kyowa Interface Science Co., Ltd.
-Z type) are shown in Table 4.

Example 12 A photocatalyst-containing layer having a thickness of 0.3 μm was formed in the same manner as in Example 4. Ultraviolet irradiation was performed with a high-pressure mercury lamp at an illuminance of 70 mW / cm ² for 2 minutes through a mask having a light-shielding layer having a pitch of 100 μm. Dispenser (EFD)
(1500XL) manufactured by the company, and spread over the exposed area to form a pixel.

Example 13 3 g of isopropyl alcohol, 0.3 g of organosilane (TSL8113 manufactured by Toshiba Silicone), and fluoroalkoxysilane (MF-160E manufactured by Tochem Products):
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.

With the obtained pattern formed body heated to various temperatures on a hot plate, an ultra-high pressure mercury lamp (Ushio Inc.)
UXM-3500, ML-40D type lamp house), removing the heat rays, irradiating only ultraviolet light of 241 nm to 271 nm at an intensity of 8.1 mW / cm ² for 300 seconds, and measuring a contact angle with water with a contact angle measuring instrument. (CA-Z type manufactured by Kyowa Interface Science) as shown in Table 2,
This shows that heating promotes the photocatalytic reaction.

[0169]

[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.

[0171]

[Table 3]

Example 15 A gap of 100 μm was provided in the same manner as in Example 14, and exposure was performed in a state where air was blown onto the exposed surface of the pattern-formed body. It was less than 5 cm.

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.

Next, on a polyester film having a thickness of 10 μm, as a hot-melt ink layer, the following composition: carbon black (# 25, manufactured by Mitsubishi Chemical Corporation): 20 parts by weight ethylene-vinyl acetate copolymer (Dupont Mitsui Polychemicals) ): 10 parts by weight Carnauba wax: 10 parts by weight Paraffin wax (HNP-11, manufactured by Nippon Seiro): 60 parts by weight An ink ribbon formed with a heat-fusible ink composition layer consisting of Adhere, 9
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 high-pressure mercury lamp was used to form a line having a width of 5 μm on the obtained pattern formed body through a photomask formed at the same interval as the line width.
0 to 390 nm ultraviolet light at 70 mW / cm ² illuminance
Irradiated for minutes.

Next, the pattern-formed body irradiated with light was shaken at 25 ° C. for 20 seconds at a concentration of 12.5 ml / l obtained by diluting a sensitizer solution for chemical plating (S-10X for glass and ceramic manufactured by Uemura Kogyo). After immersion while moving, after washing with water, 12.5 m diluted with a reducing catalyst-applied liquid (Palladium colloid catalyst A-10X manufactured by Uemura Kogyo)
After being immersed in a solution having a concentration of 1 / l while rocking at 25 ° C. for 20 seconds, it is rocked and immersed in an electroless nickel plating solution (Nimden LPX manufactured by Uemura Kogyo) at 80 ° C. for 1 hour to give an exposed portion. A nickel layer having a thickness of 0.5 μm was formed.

Further, it was immersed in a 90 ° C. electroless gold plating bath (ELGB511 manufactured by Uemura Kogyo) while rocking for 5 minutes to form a 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 The same composition as in Example 4 was spin-coated on a quartz glass substrate having a length of 10 cm, a width of 10 cm and a thickness of 0.1 cm to form a photocatalyst layer having a thickness of 0.4 μm. Next, 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.

[0181]

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 base material 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 in adhesiveness between the exposed and unexposed portions of the aluminum thin film, the adhesiveness between the exposed and unexposed portions of the aluminum thin film and the transparent base material was reduced. 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 device (CA-Z type, manufactured by Kyowa Interface Science Co., Ltd.).
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.

Then, 100 parts by weight of an ultraviolet curable monomer (Beam Set 770 manufactured by Arakawa Kogyo) and a curing initiator (Irgacure 170 manufactured by Ciba Specialty Chemicals)
0) A composition was prepared by mixing 5 parts by weight.

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. Then
When irradiated with ultraviolet light at 70 mW / cm ² for 3 minutes using a high-pressure mercury lamp, the resin cured with the ultraviolet light had a diameter of 5 mm.
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 Offset plate H without water using a commercially available original plate for offset printing
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 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-41 manufactured by Ishihara Sangyo) Average particle size 5
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 the stylus method in the same manner as in Example 1, Ra = 30
m. A high pressure mercury lamp was irradiated on the photocatalyst-containing layer with a high-pressure mercury lamp at 70 mW / cm ² for 5 minutes through a lattice-shaped mask for 5 minutes to measure the contact angle with water and n-octane with a contact angle measuring device (CA manufactured by Kyowa Interface Science Co., Ltd.) -Z type) are shown in Table 4.

[0193]

[Table 4]

Example 21 A composition for forming a primer layer (Kancoat 9 manufactured by Kansai Paint Co., Ltd.) was formed 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.

Next, 3 g of isopropyl alcohol and organosilane (TSL8113 manufactured by Toshiba Silicone)
2 g and 0.2 g of titanium oxide powder (ST-01, average particle size 7 nm, manufactured by Ishihara Sangyo) were mixed. The resulting dispersion was treated with 6
The mixture was stirred for 0 minute while maintaining the temperature at 100 ° C. This dispersion was applied on a substrate on which a primer layer had been formed by a spin coating method. This was dried at a temperature of 150 ° C. for 5 minutes to allow hydrolysis and polycondensation reactions to proceed, thereby forming a film.

Next, a high-pressure mercury lamp was irradiated with ultraviolet light at an illuminance of 70 mW / cm ² for 10 minutes, and the contact angle with water and n-octane was measured with a contact angle measuring device (C Kyowa Interface Science Co., Ltd.).
Table 5 shows the results of measurement by A-Z type).

[0197]

[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 attached to an offset printing press (Alpha New Ace, manufactured by Alpha Giken), and a printing ink (Across Red, manufactured by The Inktec) and a fountain solution (Clean etchant 20 manufactured by Niken Chemical Co., Ltd.)
When printing was performed on coated paper at a printing speed of 5,000 sheets / hour using doubling water dilution, 20,000 sheets of good printed matter 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-1 manufactured by Nissan Chemical Co., Ltd.)
5) 0.96 g, ethanol 26.89 g, pure water 0.3
2 g 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. At a temperature of 150 ° C,
By drying for 0 minutes, hydrolysis and polycondensation reactions proceed to produce a 0.2 μm thick photocatalyst-containing composition layer having a high surface energy and a photocatalyst firmly fixed in silica. And

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 spin coating at a coating amount of 1 g / vol.
m ^2, and dried at a temperature of 80 ° C. for 10 minutes to form 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 device (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.

[0204]

[Table 6]

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 with a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science).
゜, 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.

Next, when irradiation was performed for 1 minute with an illuminance of 50 mW / cm ^{2 using} a mercury lamp, the wettability changed from 130 ° to 5 ° or less in terms of 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 Inktech), 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.

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

Next, the waterless printing ink (Inktec Waterless S Yellow manufactured by The Inktec) was added to RI
Using a tester (RI-2 type manufactured by Ishikawajima Industrial Machinery)
The whole surface was coated on the obtained exposed pattern formed body. As a result, the unexposed areas repelled the ink due to oil repellency, and a yellow pattern selectively applied only to the exposed areas was obtained.

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

Next, by drying at a temperature of 150 ° C. for 30 minutes, hydrolysis and polycondensation proceed, and a photocatalyst-containing composition having a thickness of 0.2 μm in which a photocatalyst and a surfactant are firmly fixed in silica. A material layer was 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 device (CA-Z type manufactured by Kyowa Interface Science).
FIG. 8 shows the results. From the figure, it was confirmed that the contact angle, which was 63 ° before irradiation, decreased with irradiation time, and dropped to 6 ° in about 80 minutes.

Example 26 3 g of 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 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 resulting printing plate precursor was exposed as a lithographic printing plate precursor with water at 175 lines / inch through a gradation positive film having 2 to 98% halftone dots by the above-described xenon lamp to form a pattern. did.

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

Next, 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 m.
m lenses were produced.

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 / m2 was applied by a mercury lamp through a mask having a circular pattern having an opening diameter of 1 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 125 g of water were mixed and stirred for 3 minutes. The resulting mixture was applied onto a circular pattern having different wettability formed on a transparent substrate by spin coating 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 a mercury lamp at an illuminance of 70 mW / cm ² for 3 seconds, and the diameter was 1 mm and the focal length was 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, polydimethylsiloxane modified at both ends with OH (X-2 manufactured by Shin-Etsu Chemical Co., Ltd.)
9 g of 2-160AS functional group equivalent 112), 1 g of crosslinking agent (Coronate L, manufactured by Polyisocyanate Nippon Polyurethane), 0.05 g of butyltin dilaurate, 1 g of titanium oxide powder (Ishihara Sangyo ST-01, particle size 7 nm),
A composition consisting of 5 g of 1,4-dioxane and 5 g of isopropanol is applied, dried at 120 ° C. for 2 minutes, and has 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 = 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 by a contact angle measuring device (CA-Z type, manufactured by Kyowa Interface Science), a difference in wettability could be confirmed. Table 7 shows the measurement results.

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, a polydimethylsiloxane modified with OH-terminated 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.

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

In the same manner as in Example 30, the printing plate was mounted on an offset printing press (Komori Sprint 4-color press), and printing was performed 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 32 Silica sol (Glaska HPC700 manufactured by Nippon Synthetic Rubber Co., Ltd.)
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.
^This 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 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 resulting 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 10% by weight, manufactured by Ishihara Sangyo)
Was added and stirred for another 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.

The average roughness of the surface of the obtained pattern-formed body was measured by a stylus method, and it was Ra = 2 nm.

Next, a 365 nm YAG laser was
Irradiation was performed at an intensity of 0 mJ / cm ² to form a pattern and a photocatalytic reaction was caused.

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

Further, in the same manner as in Example 27, the printing original plate was mounted on an offset printing machine (Komori Sprint 4-color machine), and coated with printing ink (Dryo Color Indigo Ink manufactured by Dainippon Ink and Chemicals, Incorporated). When printing was performed, a good printed matter was obtained.

Example 33 A primer layer was formed on an aluminum substrate having a thickness of 0.23 mm in the same manner as in Example 29, and an emulsion-type addition-reaction-type polydimethylsiloxane (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 photocatalyst containing layer of 1 micrometer in thickness.

Further, a mask is brought into close contact with a high-pressure mercury lamp
Irradiate with UV light for 10 minutes at illuminance of mw / cm ² ,
After the photocatalytic reaction, the contact angle with water and n-octane was measured with a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science).
Table 7 shows the results of the measurement.

Example 34 A 20% by weight dimethylformamide solution of primer (Kansai Paint 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.

Silica sol (Glaska H made by Japan Synthetic Rubber)
3 g of PC7002) and 1 g of alkylalkoxysilane (HPC402H manufactured by Nippon Synthetic Rubber) were mixed and stirred by a stirrer for 5 minutes. This solution was applied on the previously formed primer layer with a blade coater and dried at 100 ° C. for 10 minutes.

Next, 3 g of isopropyl alcohol, 0.75 g of silica sol (Glaska HPC7002, solid content 12%, manufactured by Nippon Synthetic Rubber) and 0.2 of alkylalkoxysilane (HPC402H, solid content 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 proceed to form a 3 μm-thick layer in which the photocatalyst is firmly immobilized with organopolysiloxane to form a pattern-formed body. Obtained.

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, the pattern formed body was irradiated with 70 mW / cm ² illuminance by a high-pressure mercury lamp through a grid-shaped 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).

Further, the pattern-formed body on which the pattern was formed was attached to an offset printing machine (Komori Sprint 4-color machine), and the coated paper was coated with waterless printing ink (Dryo Color Indigo Ink manufactured by Dainippon Ink and Chemicals, Inc.). When printing was performed, 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.

Further, when printing was performed on coated paper in the same manner as in Example 31, a good printed matter free of background smear was obtained.

Example 37 A 20% by weight dimethylformamide solution of a primer (Kansai Paint 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.

Silica sol (Glaska H made by Japan Synthetic Rubber)
3 g of PC7002) and 1 g of alkylalkoxysilane (HPC402H manufactured by Nippon Synthetic Rubber) were mixed and stirred by a stirrer for 5 minutes. This solution was applied on the previously formed primer layer with a blade coater and dried at 100 ° C. for 10 minutes.

Next, 3 g of isopropyl alcohol 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-
0.15 g of (trimethoxysilyl) propyl] -N-ethylperfluorooctanesulfonamide in 50% by weight of isopropyl ether) and 0.30 g of dimethoxydimethylsilane were mixed. 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.

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 resulting dispersion was applied to form a 0.2 μm coating layer to obtain a patterned product.

Next, the obtained pattern formed body was irradiated with 200 mJ / cm ² with a YAG laser 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).

Further, the pattern-formed body on which the pattern was formed was mounted on an offset printing machine (Komori Sprint 4-color printing machine), and coated with waterless printing ink (Dryo Color Indigo Ink manufactured by Dainippon Ink and Chemicals, Inc.). When printing was performed, 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 machine 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 with 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 used with 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 A commercially available offset printing plate precursor, waterless offset plate H
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 forming body was prepared in the same manner as in Example 34 except that the amount of dimethoxydimethylsilane (TSL8112 manufactured by Toshiba Silicone) used in the photocatalyst-containing layer was 0.2 g and the dimethylsiloxane unit was 50%. 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 forming body was prepared in the same manner as in Example 31 except that the amount of dimethoxydimethylsilane (TSL8112 manufactured by Toshiba Silicone) used in the photocatalyst-containing layer was 0.01 g and the dimethylsiloxane unit was 5%. 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.

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

[0268]

[Table 7]

[0269]

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 illustrating 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 illustrating 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 a device 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 substance layer to be decomposed and removed, 13 is a part having different wettability, 14 is a hydrophobic part, 15 is a hydrophilic part,
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 using vacuum, 25 ... functional layer, 26 ... adhesive tape, 27 ... air jet nozzle, 28 ... functional layer, 2
Reference numeral 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 Continuation of the front page (31) Priority claim number Japanese Patent Application No. Hei 10-85955 (32) Priority date March 31, 1998 (March 31, 1998) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 10-86293 (32) Priority date March 31, 1998 (March 31, 1998) (33) Country claiming priority Japan (JP) (72) Inventor Shinichi Hikosaka 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Manabu Yamamoto 1-1-1-1 Ichigaya Kaga-cho, Shinjuku-ku, Tokyo F term (reference) 2H025 AB03 AC01 AD01 AD03 BB00 BH03 CB32 CB41 2H084 AA30 AA40 AE03 BB02 CC05 2H096 AA06 BA13 HA07 LA30 2H114 AA05 AA11 AA14 AA22 BA01 DA08 DA15 DA23 DA38 DA39 DA52 DA57 DA72 DA73 EA03 EA06 FA16

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, wherein the wettability of a surface is changed 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 according to 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 wettability of an exposed portion has changed due to a repelling action of an unexposed portion. 18. The method according to claim 17, further comprising a step.
The method for producing an element described in the above. 20. A method comprising: 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 method for manufacturing an element according to claim 17, wherein 21. A step of laminating a composition for a functional layer on the entire surface of a pattern-formed body, wherein a functional layer is formed in a pattern only on a portion where wettability of an exposed portion has changed due to repulsion of an unexposed portion. 19. The method according to claim 18, further comprising a step.
The method for producing an element described in 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 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.