JP2008068468A - Functional resin substrate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a functional resin substrate excellent in durability and having water repellency and photocatalytic activity. <P>SOLUTION: A resin substrate, which is provided with the hydrolyzable SiX<SB>4</SB>(wherein X is a hydrolyzable functional group) chemically bonded to a hydrolyzable resin layer, is installed on the surface of a resin substrate 10 having a hydrolyzable resin layer overlying its surface and a layer of a hydrolyzable TiY<SB>4</SB>or RnTiY<SB>4-n</SB>(wherein n is an integer of 1-3, R is an alkyl group or a fluoroalkyl group and Y is a hydrolyzable functional group) chemically bonded the SiX<SB>4</SB>layer is provided on the resin substrate. By this method, the hydrolyzable silane compound (wherein X is a hydrolyzable functional group) is chemically strongly bonded to a hydrolyzed (activated) resin molecule to mutually fix resin molecules through a silane compound SiX<SB>4</SB>layer to stabilize a resin surface. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a functional resin substrate provided with a hydrolyzable titanium compound layer on the surface of a hydrolyzable resin substrate and a method for producing the same.

Conventionally, a number of means have been used to provide, for example, a function on the surface of an olefin resin. For example, a method of mixing a silicone compound with polypropylene resin, a method of applying silicone or fluoroalkylalkylsilane after irradiating the polypropylene resin with UV or corona discharge, or a silica film after irradiating the polypropylene resin with UV or corona discharge There is a method of providing alkylsilane or fluoroalkylsilane. (For example, refer to Patent Document 1).
JP 2001-128891 A

  However, the method of mixing a silicone compound with a polypropylene resin has a problem that the mechanical strength of the resin is lowered. Further, in the method of applying silicone or fluoroalkylalkylsilane after irradiating UV or corona discharge to polypropylene resin, there is a problem in durability of the film, particularly abrasion resistance, because the resin surface is soft.

  In order to solve this problem, the method of providing a silica coat after irradiating the resin with UV or corona discharge and providing alkylsilane or fluoroalkylsilane has a large thermal expansion difference between the resin and the silica coat. There was a problem of (adhesion strength reduction). In addition, since the resin surface is extremely stable, even if UV or corona discharge is performed, even if the surface cannot be activated or even if activated, it takes time to cause thermal movement of the polymer chain of the resin. Since the activated surface sunk inside and the surface returned to the original state again, there was a problem in the adhesion strength and stability between the surface and the film. Furthermore, application to a resin molded product, for example, post-processing was difficult.

The present invention solves this problem. On the surface of a resin substrate having a hydrolyzable resin layer on the surface, the hydrolyzable SiX ₄ (X is hydrolyzed) by chemically bonding to the hydrolyzable resin layer. TiY ₄ or RnTiY _4-n (n is an integer of 1 to 3, where R is an integer of 1 to 3) chemically bonded to a hydrolyzable SiX ₄ layer on the resin substrate provided with a functional group). Photodegradable functional group, Y is a hydrolyzable functional group) layer.

According to the present invention, the hydrolyzable silane compound SiX ₄ (X is a hydrolyzable functional group) layer is chemically bonded to the hydrolyzed (activated) resin molecule, whereby the silane compound SiX ₄ The resin molecules are fixed to each other through the layer to stabilize the resin surface. In addition, since this layer is an ultra-thin film at the molecular level, it does not break due to a difference in thermal expansion.

Therefore, the hydrolyzable silane compound SiX ₄ layer having a very stabilized surface is obtained. Furthermore, a titanium compound TiY ₄ or R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, and Y is a hydrolyzable functional group) can be provided thereon. Thus, a durable functional resin substrate can be provided. Further, since it can be applied to resin molding using a mold, the application range is wide and the industrial utility value is large.

In the first invention, a hydrolyzable silane compound SiX ₄ (X is a hydrolyzable functional group) chemically bonded to a hydrolyzable resin layer on a resin substrate surface having a hydrolyzable resin layer on the surface. ) Layer and a hydrolyzable titanium compound TiY ₄ (Y is a hydrolyzable functional group) layer chemically bonded to the hydrolyzable SiX ₄ layer.

According to this configuration, the hydrolyzable silane compound SiX ₄ (X is a hydrolyzable functional group) layer is chemically bonded to the hydrolyzed (activated) resin molecule, thereby forming the silane compound SiX ₄ layer. The resin molecules are fixed to each other to stabilize the resin surface. In addition, since this layer is an ultra-thin film at the molecular level, it does not break due to a difference in thermal expansion.

Therefore, the surface is extremely stabilized hydrolyzable substrate with a titanium compound TiX ₄ layers. And since the hydrolyzable silane compound SiY ₄ layer is provided on this, the functional resin base | substrate excellent in durability can be provided. As a specific function, photocatalytic properties are exhibited by light irradiation.

In the first invention, a hydrolyzable silane compound SiX ₄ (X is a hydrolyzable functional group) chemically bonded to a hydrolyzable resin layer on a resin substrate surface having a hydrolyzable resin layer on the surface. ) Layer and a hydrolyzable and photodegradable titanium compound R _n TiY _4-n chemically bonded to the hydrolyzable SiX ₄ layer (n is an integer of 1 to 3, R is a photodegradable functional group) , Y is a resin substrate provided with a hydrolyzable functional group) layer.

According to this configuration, the hydrolyzable silane compound SiX ₄ (X is a hydrolyzable functional group) layer is chemically bonded to the hydrolyzed (activated) resin molecule, whereby the silane compound SiX ₄ layer The resin molecules are fixed to each other to stabilize the resin surface. In addition, since this layer is an ultra-thin film at the molecular level, it does not break due to a difference in thermal expansion. Therefore, the hydrolyzable silane compound SiX ₄ layer having a very stabilized surface is obtained.

Then, this on the silane compound R _n TiY _{4-n (n} is an integer of 1 to 3 R photodegradable functional group, Y is a hydrolyzable functional group) since provided layer, durability of the function A functional resin substrate can be provided. Specifically, it exhibits water repellency and photocatalytic properties by light irradiation.

The third invention is particularly the hydrolyzable titanium compound R _n TiY _{4-n of} the second invention (where n is an integer of 1 to 3, R is a photodegradable functional group, and Y is a hydrolyzable functional group. ) layer is characterized in that it is a hydrolyzable RTiY _3.

  With this configuration, since the titanium compound is densely immobilized on the surface, the water repellency is increased, and the titanium is fixed in a highly dispersed state by light irradiation, so that highly active photocatalytic properties are exhibited.

The fourth invention is particularly characterized in that the hydrolyzable titanium compound RTiY ₃ (R is a photodegradable functional group, Y is a hydrolyzable functional group) layer of the third invention is a monomolecular film. To do. Since the titanium compounds are densely and highly dispersed on the surface, the water repellency and photocatalytic activity by light irradiation can be further improved. Moreover, it becomes a colorless and transparent ultra-thin film, and can maintain the color of the resin.

  The fifth invention is particularly characterized in that the hydrolyzable resin of the first to fourth inventions is a thermosetting resin.

This configuration facilitates hydrolysis of the resin surface, so that a chemically bonded silane compound SiX ₄ layer can be formed.

  The sixth invention is characterized in that the pencil hardness of the surface of the hydrolyzable resin of the first to fourth inventions is H or more.

With this configuration, since the resin to which the silane compound SiX ₄ layer is bonded becomes a hard resin, durability, particularly wear resistance, is improved.

  The seventh invention is particularly characterized in that the hydrolyzable resin of the first to fourth inventions is acrylic, silicone, and a copolymer thereof, or polyimide, polyamide, and a copolymer thereof.

With this configuration, the resin surface is easily hydrolyzed, and the resin to which the silane compound SiX ₄ layer is chemically bonded becomes a hard resin, so that durability, particularly wear resistance, is greatly improved.

  The eighth invention is particularly characterized in that the resin of the first or second invention is a polyolefin resin.

  With this configuration, the conventional method has a problem in the adhesiveness between the surface and the film having a siloxane bond because the surface of the thermoplastic resin, particularly the polyolefin resin, is extremely stable, which can be solved.

The ninth invention includes a step of providing a hydrolyzable resin layer on the resin substrate surface, a step of hydrolyzing the resin layer surface, and a step of contacting at least a silane compound SiX ₄ (X is a hydrolyzable functional group). And hydrolyzing the formed SiX ₄ layer, contacting the hydrolyzed SiX ₄ layer with at least a titanium compound TiY ₄ (R is a hydrocarbon group, Y is a hydrolyzable functional group), and formation And a step of hydrolyzing the formed TiY ₄ layer.

The tenth invention is a step of providing a hydrolyzable resin layer on the resin substrate surface, a step of hydrolyzing the resin layer surface, and a step of contacting at least a silane compound SiX ₄ (X is a hydrolyzable functional group). When the step of hydrolyzing SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed _R n _{TiY 4-n} (n is an integer of 1 to 3 R photodegradable functional group, Y It is a method for producing a resin substrate having a step of contacting a hydrolyzable functional group) and a step of hydrolyzing the formed R _n TiY _4-n layer.

The eleventh invention includes a step of providing a hydrolyzable resin layer on the resin substrate surface, a step of hydrolyzing the resin layer surface, and a step of contacting at least a silane compound SiX ₄ (X is a hydrolyzable functional group). When the formed SiX ₄ layers of hydrolyzing at least a titanium compound SiX _4-layer hydrolyzed _R n _{TiY 4-n} (n is an integer of 1 to 3, R represents photolysis functional group Y A resin substrate having a step of contacting a hydrolyzable functional group), a step of hydrolyzing the formed R _n TiY _4-n layer, and a step of photolyzing the hydrolyzed R _n TiY _4-n layer It is a manufacturing method.

The twelfth invention includes a step of hydrolyzing one surface of the hydrolyzable resin layer, a step of bringing the hydrolyzed resin layer surface into contact with at least a silane compound SiX ₄ (X is a hydrolyzable functional group), Hydrolyzing the formed SiX ₄ layer, contacting the hydrolyzed SiX ₄ layer with at least a titanium compound TiY ₄ (Y is a hydrolyzable functional group), and hydrolyzing the formed TiY ₄ layer And a step of providing a substrate resin layer so that the TiY ₄ layer is on the surface.

The thirteenth invention includes a step of hydrolyzing the hydrolyzable resin layer one side surface, a step of bringing the hydrolyzed resin layer surface into contact with at least a silane compound SiX ₄ (X is a hydrolyzable functional group), a step of hydrolyzing SiX ₄ layer formed, hydrolyzed least titanium compound SiX _{4-layer R} n _{TiY 4-n} (n is an integer of 1 to 3, R represents photolysis functional groups, Y is hydro The step of contacting the functional group), the step of hydrolyzing the formed R _n TiY _4-n layer, and the substrate resin layer so that the hydrolyzed R _n TiY _4-n layer is on the surface. And a step of providing the resin substrate.

The fourteenth invention includes a step of hydrolyzing one surface of the hydrolyzable resin layer, a step of bringing the hydrolyzed resin layer surface into contact with at least a silane compound SiX ₄ (X is a hydrolyzable functional group), a step of hydrolyzing SiX ₄ layer formed, hydrolyzed least titanium compound SiX ₄ layers were _R n _{TiY 4-n} (n is an integer of 1 to 3 R photodegradable functional group, Y is a hydrolyzable A possible functional group), a step of hydrolyzing the formed R _n TiY _4-n layer, a step of photolyzing the hydrolyzed R _n TiY _4-n layer, And a method of producing a resin substrate having a step of providing a substrate resin layer so that the R _n TiY _4-n layer is on the surface.

  By these methods, the hydrolyzable resin layer and each layer on the hydrolyzable resin layer are more firmly adhered via a covalent bond, and the hydrolyzable resin layer and the resin are excellent in adhesion because the difference in thermal expansion is small. Therefore, a functional resin substrate having excellent durability can be easily manufactured. Specifically, a substrate that exhibits water repellency and photocatalytic properties by light irradiation can be produced.

A fifteenth aspect of the invention includes a step of forming a hydrolyzable resin layer on the mold surface, a step of supplying a resin to perform molding, a step of hydrolyzing the surface of the hydrolyzable resin layer, and hydrolysis. the resin layer surface, and contacting at least a silane compound SiX 4 _(X is a hydrolyzable functional group), and hydrolyzing the SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed This is a method for producing a resin substrate having a step of contacting TiY ₄ (Y is a hydrolyzable functional group) and a step of hydrolyzing the formed TiY ₄ layer.

The sixteenth invention includes a step of forming a hydrolyzable resin layer on the mold surface, a step of supplying a resin to perform molding, a step of hydrolyzing the surface of the hydrolyzable resin layer, and hydrolysis. the resin layer surface, and contacting at least a silane compound SiX 4 _(X is a hydrolyzable functional group), and hydrolyzing the SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed A step of contacting R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group), and the formed R _n TiY _4-n layer And a step of hydrolyzing the resin substrate.

The seventeenth invention includes a step of forming a hydrolyzable resin layer on the mold surface, a step of supplying a resin for molding, a step of hydrolyzing the surface of the hydrolyzable resin layer, and hydrolysis. the resin layer surface, and contacting at least a silane compound SiX 4 _(X is a hydrolyzable functional group), and hydrolyzing the SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed A step of contacting R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group), and the formed R _n TiY _4-n layer and hydrolyzing a hydrolyzed R _n TiY _4-n layer manufacturing method of the resin substrate having the optical decomposing step a.

By these methods, the hydrolyzable resin layer and each layer on the hydrolyzable resin layer are more firmly adhered via a covalent bond, and the hydrolyzable resin layer and the resin are excellent in adhesion because the difference in thermal expansion is small. Therefore, a resin molded product having a functional surface with excellent durability can be manufactured. Specifically, a resin molded product having a surface that exhibits water repellency and photocatalytic properties by light irradiation can be produced.

The eighteenth invention includes a step of mounting a hydrolyzable resin film on the mold surface, a step of supplying a resin and performing film in-mold molding, and hydrolysis of the resin layer surface of the molded resin hydrolyzable A step of bringing the hydrolyzed resin layer surface into contact with at least a silane compound SiX ₄ (where X is a hydrolyzable functional group), a step of hydrolyzing the formed SiX ₄ layer, and hydrolysis at least a titanium compound TiY 4 to SiX _{4-layer (Y} is a hydrolyzable functional group) is a step and, formed TiY method for producing a resin substrate having a step of hydrolyzing _4-layer in contact with the.

The nineteenth invention includes a step of mounting a hydrolyzable resin film on the mold surface, a step of supplying a resin for film in-mold molding, and a hydrolysis of the hydrolyzable resin layer surface of the molded resin. A step of contacting the hydrolyzed resin layer surface with at least a silane compound SiX ₄ (X is a hydrolyzable functional group), a step of hydrolyzing the formed SiX ₄ layer, and a hydrolyzed SiX A step of contacting at least the titanium compound R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, and Y is a hydrolyzable functional group) in _four layers, and the formed R _n And a step of hydrolyzing the TiY _4-n layer.

The twentieth invention includes a step of mounting a hydrolyzable resin film on the mold surface, a step of supplying a resin and performing film in-mold molding, and hydrolysis of the hydrolyzable resin layer surface of the molded resin A step of contacting the hydrolyzed resin layer surface with at least a silane compound SiX ₄ (X is a hydrolyzable functional group), a step of hydrolyzing the formed SiX ₄ layer, and a hydrolyzed SiX A step of contacting at least the titanium compound R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, and Y is a hydrolyzable functional group) in _four layers, and the formed R _n and TiY _4-n layer hydrolyzing step is hydrolyzed _{R n TiY 4-n} layer manufacturing method of the resin substrate having the optical decomposing step a.

  Thus, a resin molded product having a functional surface having a highly durable siloxane bond can be easily produced only in the mold. Specifically, a substrate that exhibits water repellency and photocatalytic properties by light irradiation can be produced.

The twenty-first invention includes a step of hydrolyzing the hydrolyzable resin film one side surface, and a step of bringing at least the silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the hydrolyzed resin film one side surface; The step of hydrolyzing the formed SiX ₄ layer, the step of bringing the hydrolyzed SiX ₄ layer into contact with at least the compound titanium compound TiY ₄ (Y is a hydrolyzable functional group), and the formed TiY ₄ layer A resin substrate comprising: a step of hydrolyzing, a step of attaching a resin film so that the hydrolyzed TiY _4-n layer is on the surface of the mold, and a step of supplying a resin and performing film-in-mold molding It is a manufacturing method.

The twenty-second invention includes a step of hydrolyzing the hydrolyzable resin film one side surface, and a step of bringing at least the silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the hydrolyzed resin film one side surface; a step of hydrolyzing SiX ₄ layer formed, hydrolyzed least compound titanium compound SiX _{4-layer R} n _{TiY 4-n} (n is an integer of 1 to 3, R represents photolysis functional group, Y is a step of contacting a hydrolysable functional group), a step of hydrolyzed R _n TiY _4-n wears the resin film so that the surface on the mold surface, the film in-mold molding by supplying the resin A process for producing a resin substrate.

The twenty-third invention includes a step of hydrolyzing the hydrolyzable resin film one side surface, and a step of bringing at least the silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the hydrolyzed resin film one side surface; , and the formed SiX ₄ layers of hydrolyzing at least compound titanium compound _R n _{TiY 4-n} (n is an integer of 1 to 3 to SiX _{4-layer hydrolyzed,} photolysis R _{n TiY 4-n} layer Manufacturing a resin substrate having a step of attaching a resin film so that R _n TiY _{4- n} photodissolved on the mold surface becomes a surface, and a step of supplying a resin and performing film-in-mold molding Is the method.

  By these methods, for example, a roll coater can be used to easily produce a functional resin film having a siloxane bond with excellent durability by roll-to-roll, and the film is simply used for film-in-mold molding. It is very convenient. In addition, it is possible to easily manufacture a resin molded product having a functional surface with excellent durability in mass production. Specifically, a substrate that exhibits water repellency and photocatalytic properties by light irradiation can be produced.

  According to a twenty-fourth aspect of the invention, in any one of the ninth to twenty-third aspects, the step of hydrolyzing the surface of the hydrolyzable resin layer is at least UV irradiation or corona ray irradiation. It is a manufacturing method.

  According to this method, only the surface of the hydrolyzable resin layer can be irradiated with UV or corona rays, so that the hydrolyzable resin layer surface can be hydrolyzed without affecting other parts of the resin.

  In a twenty-fifth aspect of the invention, in particular, in any one of the ninth to twenty-third aspects, the step of hydrolyzing the surface of the hydrolyzable resin layer includes at least ozone or oxygen plasma between the mold surface and the hydrolyzable resin layer. It is a manufacturing method of the resin base | substrate characterized by these contact.

  According to this method, ozone or oxygen plasma can be brought into contact with only the surface of the hydrolyzable resin layer regardless of the shape to be molded, so that the hydrolyzable resin layer surface is hydrolyzed without affecting other parts of the resin. Can be disassembled.

  In a twenty-sixth aspect of the invention, in particular, in any one of the fifteenth to twentieth aspects, the step of hydrolyzing the surface of the hydrolyzable resin layer is between the mold surface and the hydrolyzable resin layer, and at least ozone or oxygen A method for producing a resin substrate, characterized by being in contact with plasma.

  According to this method, since the surface of the hydrolyzable resin layer can be hydrolyzed inside the mold in the resin molding step, the resin substrate of the present invention can be produced more easily.

  A twenty-seventh aspect of the invention is a method for producing a resin substrate according to any one of the twenty-fourth to twenty-sixth aspects, characterized in that the atmosphere for hydrolyzing the surface of the hydrolyzable resin layer is 10% or more of humidity. is there.

  According to this method, according to this method, hydrolysis of the hydrolyzable resin layer by the UV irradiation, corona discharge irradiation, ozone or oxygen plasma contact can be accelerated.

  A twenty-eighth aspect of the invention is a method for producing a resin substrate, in particular, in any one of the ninth to twenty-third aspects, wherein the hydrolyzable functional group X or Y is a halogen group, an alkoxy group or an isocyanate group. .

  According to this method, a hydrolyzable resin layer and a film having a silane compound or a titanium compound are strongly covalently bonded, and the hydrolyzable resin layer and the resin are excellent in adhesion because the difference in thermal expansion is small. A resin substrate with excellent durability can be produced.

According to a twenty-ninth aspect of the invention, in particular, in the twenty-eighth aspect of the invention, there is provided a method for producing a resin substrate, which is a chloro halide group.

  According to this method, since the reactivity of chlorosilane or chlorotitanium is high, the hydrolyzable resin layer and the film having a silane compound or titanium compound can be more strongly and quickly covalently bonded, so that the durability and mass productivity are excellent. A resin substrate provided with a film having a siloxane bond can be produced.

  A thirtieth aspect of the invention is a method for producing a resin substrate according to any one of the ninth to twenty-third aspects, wherein the step of contacting the silane compound or the titanium compound is an anhydrous atmosphere having a humidity of 35% or less.

  According to this method, since the hydrolyzable resin layer and the film having the silane compound or titanium compound can be strongly covalently bonded without reacting the silane compound or titanium compound with water vapor in the air, the siloxane has excellent durability. A resin substrate provided with a film having bonds can be manufactured.

  A thirty-first invention is a method for producing a resin substrate according to any one of the ninth to twenty-third inventions, characterized in that the step of bringing the silane compound or titanium compound into contact is contact with a solution of the silane compound.

  According to this method, a film having a silane compound or a titanium compound can be formed on the surface of the hydrolyzed resin layer regardless of the shape to be molded.

  According to a thirty-second invention, in particular, in any one of the ninth to twenty-third inventions, the step of bringing the silane compound or the titanium compound into contact is at least contact of the vapor of the silane compound between the mold surface and the hydrolyzable resin layer. A method for producing a resin substrate characterized by the following.

  According to this method, a film having a silane compound or a titanium compound can be formed only on the surface of the hydrolyzed resin layer regardless of the shape to be molded, and other parts of the resin are not affected.

The thirty-third invention is characterized in that, in the eleventh, fourteenth, seventeenth and twentieth inventions, the step of photolyzing the hydrolyzed R _n TiY _4-n layer is irradiation with UV light of 300 nm or less. It is the manufacturing method of the resin gas to do.

  According to this method, in a state where the titanium compound is immobilized, titanium is immobilized with high efficiency and high dispersion by both photolysis of the functional group R and the photocatalytic action of the titanium compound. A resin substrate having the same can be manufactured.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments.

(Embodiment 1)
In FIG. 1, an acrylic resin solution is applied to a mold surface 1 and dried to form 50 μm of an acrylic resin (polymethyl methacrylate) 2, and a polypropylene resin 3 is supplied. Thereafter, molding is performed on the surface. A polypropylene resin substrate 4 having an acrylic resin layer is manufactured.

By irradiating the surface of the resin substrate 4 with excimer UV light 5 having a wavelength of 172 nm, the surface is hydrolyzed by water vapor in the atmosphere, and the resin substrate 6 in which a hydroxyl group is formed is manufactured.

  Under a nitrogen atmosphere (anhydrous), the resin substrate 6 is immersed in a fluorolinate (manufactured by 3M) solution containing tetrachlorosilane 7 and dried in a normal atmosphere, whereby hydroxyl groups and chlorosilyl groups on the resin surface undergo a dehydrochlorination reaction. The resin and tetrachlorosilane are chemically bonded through a siloxane bond, and the resins are fixed through the tetrachlorosilane.

  As a result, the resin substrate 8 on which the hydrolyzed layer of tetrachlorosilane firmly fixed on the resin surface is formed is manufactured.

  The hydroxyl group of the tetrachlorosilane hydrolysis layer and the chloro group of tetrachlorochlorotitanium undergo a dehydrochlorination reaction by immersing in a fluorolinate (manufactured by 3M) solution containing tetrachlorotitanium 9 on the resin substrate 8 and drying in a normal atmosphere. As a result, tetrachlorotitanium is immobilized on the tetrachlorosilane hydrolyzed layer via a covalent bond, and the functional resin substrate 10 having photocatalytic ability having excellent durability is produced.

(Embodiment 2)
In FIG. 2, an acrylic resin solution is applied to the mold surface 11 and dried to form 50 μm of an acrylic resin (polymethyl methacrylate) 12, and a polypropylene resin 13 is supplied. Thereafter, molding is performed on the surface. A polypropylene resin substrate 14 having an acrylic resin layer is manufactured.

  By irradiating the surface of this resin substrate 14 with excimer UV light 15 having a wavelength of 172 nm, the surface is hydrolyzed by water vapor in the atmosphere to produce a resin substrate 16 in which hydroxyl groups are formed.

  Under a nitrogen atmosphere (anhydrous), the resin substrate 16 is immersed in a fluorolinate (manufactured by 3M) solution containing tetrachlorosilane 17 and dried in a normal atmosphere, so that hydroxyl groups and chlorosilyl groups on the resin surface undergo a dehydrochlorination reaction. The resin and tetrachlorosilane are chemically bonded through a siloxane bond, and the resins are fixed through the tetrachlorosilane.

  As a result, a resin substrate 18 having a tetrachlorosilane hydrolyzed layer firmly fixed on the resin surface is manufactured.

  The resin substrate 18 is immersed in a fluorinate (manufactured by 3M) solution containing decyltrichlorotitanium 19 and dried in a normal atmosphere, whereby the hydroxyl group of the tetrachlorosilane hydrolyzed layer and the chloro group of decyltrichlorotitanium undergo a dehydrochlorination reaction. Thus, decyltrichlorotitanium is immobilized on the tetrachlorosilane hydrolyzed layer via a covalent bond, and the functional resin substrate 20 having excellent durability and water repellency is produced.

  Further, by irradiating the functional resin substrate 21 with UV, the decyl group undergoes photodegradation by the photocatalytic action of the immobilized decyltrichlorotitanium, thereby producing a functional resin substrate 22 having a photocatalytic ability having excellent durability. Is done.

Silane compound SiX ₄ (X is a hydrolyzable functional group) and titanium compound TiY ₄ , R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is hydrolyzable) As the functional groups X and Y that can be hydrolyzed, halogenated silyl groups such as chlorosilyl groups, alkoxysilyl groups, and isocyanatesilyl groups are effective, but chlorosilyl groups are hydrolyzable resin layer surfaces. In particular, in the case of this embodiment, it is particularly effective in view of the fact that the resin substrate is difficult to be heat-treated at high temperature.

  In addition, by using a siloxane bond, the resin bonds more firmly to the substrate than a conventional covalent bond (for example, sulfide bond -S-), so that the heat resistance, water resistance, electric resistance, etc. are excellent. . As R for imparting water repellency, an alkyl group is preferable, and in the case of imparting oil repellency and enhancing antifouling property, a fluoroalkyl group is excellent.

  Furthermore, these functional groups are preferably linear or n = 1 in order to increase the ratio (coverage) of the compound to be immobilized.

As a result, R _n TiY _4-n (where n is an integer of 1 to 3 R is a photodegradable functional group, Y is a hydrolyzable functional group) becomes a monomolecular film, and CH ₃ groups and the like are exposed on the surface. In addition, the water repellency is further increased. Furthermore, since this is irradiated with UV to hydrolyze R, titanium is highly dispersed, so that the photocatalytic activity is further increased.

From the above, as a specific example of the compound used in the present embodiment, in the case of the silane compound SiX ₄ (X is a hydrolyzable functional group), the following can be exemplified.

(1) SiCl ₄
(2) Si (OC ₂ H ₅ ) ₄
(3) Si (NCO) ₄
In general _{formula, X 3 SiO- (SiX 2 O} ) m -X ( where, n is a natural number of 1 or more, m, 1 is a natural number, k is X is 0 or 1 halogen group, an alkoxy group, isocyanate group) The following compounds corresponding to are also applicable.

(4) SiCl ₃ —O—SiCl _{3
(5) SiCl 3 -O-SiCl} 2 -O-SiCl 3
(6) Si (OCH ₃ ) ₃ —O—Si (OCH ₃ ) ₃
(7) Si (OC ₂ H ₅ ) ₃ —O—Si (OCH ₃ ) _{3
(8) Si (OC 2 H} 5) 3 -O-Si (OC 2 H 5) 3
(9) Si (NCO) ₃ —O—Si (NCO) ₃
In the case of the titanium compound TiY ₄ (Y is a hydrolyzable functional group), the following can be exemplified.

(10) TiCl ₄
(11) Ti (OC ₂ H ₅ ) ₄
(12) Ti (NCO) ₄
The general formula Y ₃ TiO— (TiX ₂ O) _m —X (where n is a natural number of 1 or more, m, 1 is a natural number, k is 0 or 1, and X is a halogen group, an alkoxy group, or an isocyanate group) The following compounds corresponding to are also applicable.

(13) TiCl ₃ —O—TiCl ₃
(14) TiCl ₃ —O—TiCl ₂ —O—TiCl ₃
(15) Ti (OCH ₃ ) ₃ —O—Ti (OCH ₃ ) ₃
(16) Ti (OC ₂ H ₅ ) ₃ —O—Ti (OCH ₃ ) ₃
(17) Ti (OC ₂ H ₅ ) ₃ —O—Ti (OC ₂ H ₅ ) ₃
(18) Ti (NCO) ₃ —O—Ti (NCO) ₃
In the case of a titanium compound R _n TiY _4-n that imparts water repellency (where n is an integer of 1 to 3, R is a photodegradable functional group, and Y is a hydrolyzable functional group), the following can be exemplified.

_{(19) CH 3 - (CH} 2) r TiZ p Cl 3-p
_{(20) CH 3 (CH 2} ) s O (CH 2) t TiZ q Cl 3-q
_{(21) CH 3 (CH 2} ) u -Si (CH 3) 2 (CH 2) v -TiZ q Cl 3-q
_{(22) CF 3 COO (CH} 2) w TiZ q Cl 3-q
However, p is an integer of 1-3, q is an integer of 0-2, r is an integer of 1-25, s is an integer of 0-12, t is an integer of 1-20, u is an integer of 0-12, v represents an integer of 1 to 20, and w represents an integer of 1 to 25. Z is hydrogen, an alkyl group, an alkoxyl group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

  Further, specific titanium compounds include (23)-(32) shown below.

(23) CH ₃ (CH ₂ ) ₉ TiCl ₃
(24) CH ₃ CH ₂ O (CH ₂ ) ₁₅ TiCl _{3
(25) CH 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 TiCl 3
(26) CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ TiCl ₃
(27) CH ₃ COO (CH ₂ ) ₁₅ TiCl _{3
(28) CF 3 (CF 2} ) 7 - (CH 2) 2 -TiCl 3
_{(29) CF 3 (CF 2} ) 5 - (CH 2) 2 -TiCl 3
_{(30) CF 3 (CF 2} ) 7 -C 6 H 4 -TiCl 3
(31) (CF ₃ ) ₂ —TiCl _{2
(32) (CF 3) 3} -TiCl
Further, instead of the chlorotitanium compound, an isocyanate compound in which all chloro groups are handled as isocyanate groups, for example, (33) to (36) shown below may be used.

_{(33) CH 3 - (CH} 2) r TiZ p (NCO) 3-p
_{(34) CH 3 (CH 2} ) s O (CH 2) t TiZ q (NCO) q-P
_{(35) CH 3 (CH 2} ) u -Si (CH 3) 2 (CH 2) v -TiZ q (NCO) 3-q
_{(36) CF 3 COO (CH} 2) v TiZ q (NCO) 3-q
However, p, q, r, s, t, u, v, w, and X are the same as described above.

  In place of the titanium compound, titanium compounds specifically exemplified in the following (37) to (46) may be used.

(37) CH ₃ (CH ₂ ) ₉ Ti (NCO) ₃
(38) CH ₃ CH ₂ O (CH ₂ ) ₁₅ Ti (NCO) _{3
(39) CH 3 (CH 2} ) 2 Si (CH 3) 2 (CH2) 15 Ti (NCO) 3
_{(40) CH 3 (CH 2} ) 6 Si (CH 3) 2 (CH2) 9 Ti (NCO) 3
(41) CH ₃ COO (CH ₂ ) ₁₅ Ti (NCO) _{3
(42) CF 3 (CF 2} ) 7 - (CH 2) 2 -Ti (NCO) 3
_{(43) CF 3 (CF 2} ) 5 - (CH 2) 2 -Ti (NCO) 3
_{(44) CF 3 (CF 2} ) 7 -C 6 H 4 -Ti (NCO) 3
_{(45) (CF 3) 2} -Ti (NCO) 2
_{(46) (CF 3) 3} -TiNCO
In addition, as a titanium-based compound, it is generally possible to use a material represented by TiZ _k (OA) _4-k (where Z is the same as described above, A is an alkyl group, and k is 0, 1, 2, or 3). It is. Among _{these, CF 3 - (CF 2)} n - (R) l -TiY q (OA) 3-q (n is an integer of 1 or more, preferably 1 to 22 integer, R represents an alkyl group, a vinyl group, an ethynyl group , An aryl group, a silicon or a substituent containing an oxygen atom, l is 0 or 1, and Z, A and q are the same as described above), a more water-repellent film can be formed. is not limited to this, other than _{this, CH 3 - (CH 2)} r -TiZ q (OA) 3-q and _{CH 3 - (CH 2) s} -0- (CH 2) t -TiZ _{q (OA) 3-q,} CH 3 - (CH 2) u -Ti (CH 3) 2 - (CH 2) v -TiZ q (OA) 3-q, CF 3 COO- (CH 2) v -TiZ _{q (OA) 3-q} (However, q, r, s, t , u, v, , Y and A are same as defined above), or the like can be used.

  Furthermore, as a more specific silane compound, the following (34)-(57) can be mentioned.

(47) CH ₃ (CH ₂ ) ₉ Ti (OCH ₃ ) _{3
(48) CH 3 CH 2 O} (CH 2) 15 Ti (OCH 3) 3
(49) CF ₃ CH ₂ O (CH ₂ ) ₁₅ Ti (OCH ₃ ) ₃
(50) CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Ti (OCH ₃ ) _{3
(51) CH 3 (CH 2} ) 6 Si (CH 3) 2 (CH 2) 9 Ti (OCH3) 3
(52) CH ₃ COO (CH ₂ ) ₁₅ Ti (OCH ₃ ) ₃
(53) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Ti (OCH ₃ ) _{3
(54) CF 3 (CF 2} ) 7 -C 6 H 4 -Ti (OCH 3) 3
_{(55) CH 3 CH 2 O} (CH 2) 15 Ti (OC 2 H 5) 3
_{(56) CH 3 (CH 2} ) 2 Si (CH 3) 2 (CH 2) 15 Ti (OC 2 H 5) 3
_{(57) CH 3 (CH 2} ) 6 Si (CH 3) 2 (CH 2) 9 Ti (OC 2 H 5) 3
_{(58) CF 3 (CH 2} ) 6 Si (CH 3) 2 (CH 2) 9 Ti (OC 2 H 5) 3
_{(59) CH 3 COO (CH} 2) 15 Ti (OC 2 H 5) 3
(60) CF ₃ COO (CH ₂ ) ₁₅ Ti (OC ₂ H ₅ ) ₃
(61) CF ₃ COO (CH ₂ ) ₁₅ Ti (OCH ₃ ) ₃
(62) CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Ti (OC ₂ H ₅ ) ₃
(63) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Ti (OC ₂ H ₅ ) ₃
(64) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Ti (OC ₂ H ₅ ) ₃
(65) CF ₃ (CF ₂ ) ₇ C ₆ H ₄ Ti (OC ₂ H ₅ ) ₃
(66) CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Ti (OCH ₃ ) ₃
(67) CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Ti (OCH ₃ ) ₃
(68) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ TiCH ₃ (OC ₂ H ₅ ) ₂
(69) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ TiCH ₃ (OCH ₃ ) ₂
(70) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Ti (CH ₃ ) ₂ OC ₂ H ₅
(71) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Ti (CH ₃ ) ₂ OCH ₃
When the compounds (2)-(3), (6)-(9), (11)-(12), (15)-(18), (33)-(71) are used, Since hydrochloric acid is not generated, there are also merit in equipment maintenance and work.

  Moreover, the first reaction step (dehydrochlorination reaction) shown in the process of immersing the silane compound or titanium compound in FIGS. 1 and 2 is generally called a chemisorption reaction.

  Further, when the titanium compound of (19)-(72) that can impart water repellency is chemically adsorbed and then irradiated with UV, the photocatalytic action of the chemically adsorbed titanium compound causes photodegradation and imparts photocatalytic activity. it can.

  In addition, as an atmosphere in which the silane compound and the titanium compound are brought into contact with each other, in order to suppress the reaction between the silane compound or the titanium compound and water vapor in the atmosphere, the atmospheric humidity is 35% or less, and more desirably, an inert gas atmosphere and an anhydrous atmosphere Lower is desirable.

Next, as the solvent, it is preferable to use a non-aqueous solvent that does not contain water, and it is possible to use a hydrocarbon solvent that does not contain water, a fluorocarbon solvent, a silicone solvent, an alcohol solvent, or the like.

  In addition to petroleum-based solvents, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin, dimethyl millicorn, phenyl silicone , Alkyl-modified silicone, polyester silicone and the like.

  However, since these solvents may attack the resin, a fluorocarbon solvent is most preferable. Fluorocarbon solvents include chlorofluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). In addition, these may be used individually by 1 type and may mix 2 or more types as long as it mixes well.

  Further, as a method of contacting the silane compound or the titanium compound, in addition to a method of contacting the vapor or dipping in the solution, a spray or the like is effective because it does not depend on the shape. Moreover, when apply | coating to a film-form thing, a spinner, a roll coater, etc. are especially excellent from a viewpoint of the use efficiency of a chemical | medical solution.

  In addition, as a hydrolyzable resin, polyethylene terephthalate resin (PET), polybutylene terephthalate (PBT), epoxy resin, and the like can be generally used. However, a resin having a harder surface resin layer to which a film having a siloxane bond is bonded is more durable. Acrylic resin (for example, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, etc.), silicone resins, copolymers thereof, or polyimide Resins, polyamide resins, and copolymers thereof are preferred.

  Further, in the case of the above-mentioned resins similar to thermosetting resins and these modified resins, the heat resistance is improved.

  In addition, as the resin of the substrate, polyethylene resin (PE), polypropylene resin (PP), polystyrene resin (PP), acrylonitrile styrene copolymer (AS), acrylonitrile butadiene styrene copolymer (ABS), polyacetal resin (POM) Further, thermoplastic resins such as polyvinyl chloride resin, the above thermosetting resins and modified resins thereof can be applied, but are not limited thereto.

  In particular, in the present embodiment, it is possible to form a film having a siloxane bond on a polyolefin resin, which has been extremely difficult by the conventional method.

  Although these forms are not particularly limited to a planar shape, a curved surface form such as a resin molded product may be used as long as it can be processed.

  Further, as a means for hydrolysis of the resin surface, a WET process using acid or alkali may be used, but considering the deformation of the resin due to water absorption, the DRY process is preferable. When the resin surface is a flat plate, UV treatment or corona discharge treatment is excellent.

  In this UV treatment, UV light having a wavelength of 400 nm or less is effective, but particularly in the vacuum ultraviolet region of 200 nm or less, strong ozone is generated, and UV does not reach the inside of the resin, so that the resin can be photodegraded. Absent. When the resin is a shape product, ozone treatment or oxygen plasma treatment is effective.

  In addition, UV light having an absorption region of 300 nm or less, which is an absorption region of the titanium compound, is effective as a UV light capable of imparting a photocatalytic ability due to the photocatalytic action of the chemically adsorbed titanium compound. In particular, when the functional group has a photosensitive group such as a carnconyl group or a cinnamoyl group, UV light of 400 nm or less is also effective.

(Example 1)
An acrylic resin solution is applied to the mold surface and dried to form 50 μm of acrylic resin (polymethyl methacrylate). Then, a polypropylene resin is supplied, molded, and a polypropylene resin substrate having an acrylic resin layer on the surface is formed. Manufactured.

  By irradiating the surface of this resin substrate with excimer UV light having a wavelength of 172 nm, the surface is hydrolyzed by water vapor in the atmosphere to produce a resin substrate on which hydroxyl groups are formed.

  Under a nitrogen atmosphere (anhydrous), the resin substrate is immersed in a fluorolinate (manufactured by 3M) solution containing tetrachlorosilane and dried in a normal atmosphere, so that the hydroxyl group and chlorosilyl group on the resin surface undergo a dehydrochlorination reaction to produce siloxane. The resin and tetrachlorosilane are chemically bonded through the bond, and the resins are fixed through the tetrachlorosilane.

  As a result, a resin substrate having a tetrachlorosilane hydrolyzed layer firmly fixed on the resin surface is produced.

  The resin substrate is immersed in a fluorolinate (manufactured by 3M) solution containing tetrachlorotitanium and dried in a normal atmosphere, whereby the hydroxyl group of the tetrachlorosilane hydrolyzed layer and the chloro group of tetrachlorotitanium undergo a dehydrochlorination reaction, Tetrachlorotitanium is immobilized by a chemical bond of the tetrachlorosilane hydrolysis layer via a covalent bond, and a functional resin substrate A having excellent durability is produced.

(Comparative Example 1)
A resin substrate R1 was produced in the same manner as in Example 1 except that 50 μm of the acrylic resin (polymethyl methacrylate) in Example 1 was not formed.

(Comparative Example 2)
A resin substrate R2 was prepared in the same manner as in Example 1 except that polyethylene terephthalate resin was used instead of the polypropylene resin of Example 1 and 50 μm of acrylic resin (polymethyl methacrylate) was not formed.

(Comparison of photocatalytic activity)
When writing with oily magic on resin bases A, R1 and R2 and irradiating with UV light of 300 nm or less for 24 hours, A disappeared, R1 did not disappear at all, and R2 disappeared slightly. Although A and R2 have a hydrolyzed film of tetrachlorotitanium having covalent bonds formed through hydroxyl groups on the resin substrate surface, R1 does not have hydroxyl groups formed on the resin surface. It can be seen that no film was formed. Therefore, the effect of the present invention has been demonstrated, and it can be seen that polyolefin fin resin including polypropylene is particularly effective.

(Comparative Example 3)
A resin substrate R3 was produced in the same manner as in Example 1 except that the excimer UV light having a wavelength of 172 nm in Example 1 was not irradiated.

(Comparison of photocatalytic activity)
When characters were written with oil-based ink on the resin substrates A and R3 and irradiated with UV light of 300 nm or less for 24 hours, A disappeared and R3 did not disappear at all. It can be seen that the resin substrate A was formed while R3 did not form this film. This is because a hydrolyzed film of tetrachlorotitanium having a covalent bond formed via a hydroxyl group on the surface of the resin substrate was formed, whereas R3 formed this film because no hydroxyl group was formed on the resin surface. It was because there was not.

  In the present invention, an effect similar to that of the resin substrate A was also observed in the case of UV other than excimer UV and corona discharge irradiation.

(Comparative Example 4)
A resin substrate R4 was prepared in the same manner as in Example 1 by using a commercially available silica sol solution instead of the fluorolinate (manufactured by 3M) solution containing tetrachlorosilane in Example 1.

(Comparative Example 5)
A resin substrate R5 was prepared in the same manner as in Example 1 except that it was not immersed in a fluorinate (manufactured by 3M) solution containing tetrachlorosilane in Example 1.

(Comparison of photocatalytic activity and durability)
When letters were written on the resin substrates A, R4, and R5 with oil-based ink and irradiated with UV light of 300 nm or less for 24 hours, A and R4 disappeared and R5 remained thin. This is presumably because R5 has few small acid groups on the resin surface, and it is difficult to form a hydrolyzed film of tetrachlorotitanium having covalent bonds formed therethrough.

  Further, when R5 is observed in detail, oxidative degradation of the resin is observed, which is considered to be due to the photocatalytic action of the titanium compound. On the other hand, as for A and R4, the blocking effect of the photocatalytic action of the titanium compound by the hydrolyzed film or silica film of tetrachlorosilane was recognized.

  When these resin substrates were left in an 80 ° C. atmosphere for 10 hours and the surface was observed, no cracks were observed in the resin substrate R4, although no abnormalities were observed in the resin substrates A and R5.

  In this state, characters were written using oil-based ink and irradiated with UV light of 300 nm or less for 24 hours. As a result, although A disappeared, R4 and R5 did not disappear, and R4 had a formed silica film peeled off. This is because A is strongly crosslinked (chemical bond) between the tetrachlorosilane and the resin surface via hydroxyl groups on the resin surface to stabilize the resin surface, and this tetrachlorosilane having many hydroxyl groups by hydrolysis is tetrachlorotitanium. This is because both are strongly chemically bonded.

  On the other hand, R4 is because the resin surface and the silica film are not firmly bonded, and the silica film peels off due to the internal stress of the silica film due to the thermal expansion coefficient. In addition, R5 is considered to be because the resin surface caused molecular motion by heat to make the surface unstable, and the tetrachlorotitanium immobilized on the surface was destroyed. Therefore, it can be seen that the resin substrate of the present invention is extremely excellent in photocatalytic properties and durability.

(Example 2)
A functional resin substrate B of the present invention was produced in the same manner as in Example 1 except that decyltrichlorotitanium was used instead of tetrachlorotitanium in Example 1. Furthermore, by irradiating UV light of 300 nm or less for 1 hour, the decyl group was photolyzed to prepare a functional resin substrate B ′.

(Comparison of water repellency and photocatalytic properties)
The contact angle between the resin substrates A and B was 5 ° 107 °. This is because a monomolecular film of siltrichlorotitanium in which the decyl group is exposed on the B surface is formed and water repellency is imparted.

  In addition, letters were written on the surfaces of A and B ′ using oily magic and irradiated with UV light of 300 nm or less for 12 hours, but B ′ disappeared, but A remained thin. This is presumably because the film formed by photodegrading the film formed on the B ′ surface is more highly dispersed in titanium and has higher photocatalytic activity.

(Example 3)
Resin substrates C and C ′ of the present invention were prepared in the same manner as in Example 2 except that didecyldichlorosilane was used instead of decyltrichlorosilane in Example 2.

(Comparison of water repellency and photocatalytic activity)
The contact angle between the resin substrates B and C was 107 ° 92 °. When irradiated with UV light of 300 nm or less for 12 hours, B ′ disappeared, but C ′ remained thin. This is thought to be because didecyldichlorosilane does not cover the surface due to its bulky molecules, and it can control water and oil repellency and photocatalytic activity by the means of Example 3 as well as impart more water repellency and photocatalytic activity. If so, it can be seen that the means of Example 2 of the present invention is superior.

Example 4
Functionality similar to that of Example 2 except that the substrate was washed with fluorinate after immersion in the fluorinate (made by 3M) solution containing decyltrichlorosilane of Example 1 to remove excess heptadecafluorodecyltrichlorosilane. Resin substrates D and D ′ were produced.

(Comparison of water repellency and photocatalyst)
The contact angles of the resin substrates B and D were 108 ° and 112 °. This is presumably because the decyltrichlorosilane of D is a monomolecular film and the CH ₃ group is exposed on the surface. When irradiated with UV light of 300 nm or less for 12 hours, B ′ disappeared but D ′ remained thin. This is presumably because D's decyltrichlorosilane is a monomolecular film, and therefore D 'is super-dispersed in titanium.

(Example 5)
A resin substrate E was produced in the same manner as in Example 2 except that an acrylic resin having a surface pencil hardness of H was used instead of the acrylic resin having a surface pencil hardness of 3H in Example 2.

(Comparative Example 6)
A resin substrate R6 was produced in the same manner as in Example 2 except that an acrylic resin having a surface pencil hardness of B was used instead of the acrylic resin having a surface pencil hardness of 3H in Example 2.

(Water repellency and durability)
The contact angles of water of the resin substrates B, E, and R6 were 105 °, 103 °, and 104 °. Thereafter, when a load of 10 g / cm <2> was applied and 1000 reciprocations were carried out with a wipe soaked in water, the water contact angles of the resin substrates B, E, and R6 were 104 [deg.] 102 [deg.] And 53 [deg.]. When the surface was observed, scratches were found on the surface of R6.

  This shows that the harder the resin surface is, the harder the surface is to be scraped, and thus the superior durability of the film on it, which is practical when the pencil hardness is H or higher.

(Example 6)
A resin substrate F was produced in the same manner as in Example 2 except that PET (polyethylene terephthalate) resin was used instead of the acrylic resin of Example 2.

(Comparative Example 7)
A resin substrate R7 was produced in the same manner as in Example 2 except that a polypropylene resin was used instead of the acrylic resin in Example 2.

(Water repellency and durability)
The contact angles of water of the resin substrates B, F, and R7 were 105 °, 112 °, and 91 °. After leaving the resin substrate in a 50 ° C. atmosphere for 100 hours, the contact angles of B, F, and RD water were measured and found to be 102 °, 111 °, and 75 °. Compared with acrylic and PET resins, the polypropylene resin does not hydrolyze and therefore hardly generates hydroxyl groups. Therefore, it does not crosslink (chemically bond) with tetrachlorosilane and does not stabilize the surface. It is also considered that decyltrichlorosilane does not chemically bond. Moreover, it can be considered that F has better heat resistance than B because F is a thermosetting resin.

  The inventor examined the resin layer of the present invention for various other resins, and found that polyolefin resins such as polyethylene, AS (acrylonitrile / styrene copolymer) and ABS (acrylonitrile / butadiene / styrene copolymer) which are difficult to hydrolyze. As is the case with polypropylene, it has been found that the performance of water repellency maintenance is not good for polystyrene resins such as polymers. On the other hand, it was found that even in the case of a hydrolyzable resin, silicone, acrylic silicon copolymer, polyimide, polyamide, and polystyrene show extremely excellent water repellency maintaining performance in the same manner as acrylic resin. It was also found that heat resistance is excellent when a thermosetting resin is used. Other hydrolyzable resins such as PC (polycarbonate) exhibited water and oil repellency maintenance performance between acrylic and polypropylene.

(Example 7)
A resin substrate G was prepared in the same manner as B in Example 2 except that tetraethoxysilane was used instead of tetrachlorosilane in Example 2.

(Example 8)
Resin substrate H was produced in the same manner as B of Example 2 except that decyltriethoxysilane was used instead of decyltrichlorosilane of Example 2.

(Comparison of water repellency and its durability)
The contact angles of water of the resin substrates B, G, and H were 108 °, 101 °, and 94 °. Thereafter, when a load of 10 g / cm <2> was applied and 1000 reciprocations were carried out with a wipe soaked in water, the contact angles of water of the resin substrate, G and H were 105 [deg.] 97 [deg.] And 79 [deg.]. From this, it can be seen that chlorosilane can form a chemical bond on the surface more strongly than alkoxysilane, thereby improving the durability of the resin substrate of the present invention.

(Comparative Example 8)
Instead of immersing the resin substrate of Example 1 in a fluorolinate (manufactured by 3M) solution containing tetrachlorotitanium under a nitrogen atmosphere (anhydrous), the humidity is 20, 35, and 40%. R8 (20), R8 (35), and R8 (40) were produced.

(Comparison of photocatalytic activity)
When characters were written on the resin bases A, R8 (20), R8 (35), R8 (40) with oily magic and irradiated with UV light of 300 nm or less for 24 hours, A, R8 (20), R8 (35) Disappeared and R8 (40) did not disappear at all, so A, R8 (20), R8 (35
) Formed a hydrolyzed film of tetrachlorotitanium with a covalent bond formed via a hydroxyl group on the surface of the resin substrate, whereas R8 (40) reacted with atmospheric water vapor and tetrachlorotitanium. It can be seen that it was not formed.

(Embodiment 3)
In FIG. 3, an acrylic resin sheet (100 μm) 22 is set on the mold surface 21, and this is press-molded with a mold 23 that is molded into a sheet on the mold surface 21. Thereafter, the mold is changed from 23 to 24, polypropylene resin 25 is supplied, film-in-molding is performed to obtain a polypropylene resin substrate 26 having an acrylic resin layer on the surface, and then the surface of this resin substrate 26 is 172 nm. Excimer UV light 27 having the following wavelength is irradiated to produce a resin substrate 28 on which surface hydroxyl groups are formed.

  Furthermore, this resin substrate 28 is immersed in a fluorinate (manufactured by 3M) solution containing tetrachlorosilane 29 under a nitrogen atmosphere (anhydrous) and dried in a normal atmosphere, whereby the resin substrate 30 is produced. Subsequently, this resin substrate 30 was immersed in a fluorinate (manufactured by 3M) solution containing tetrachlorotitanium 31 under a nitrogen atmosphere (anhydrous), and dried in a normal atmosphere, thereby producing a resin substrate I.

Example 9
Instead of irradiating the excimer UV light having a wavelength of 172 nm in Example 1, an oxygen plasma treatment was performed to prepare a resin substrate J.

(Easy manufacturing)
Since letters were written on the resin substrates A, I, and J with oil-based ink and irradiated with UV light of 300 nm or less for 24 hours, both A, I, and J disappeared. Therefore, this method is simpler than the resin substrate A. Resin substrates I and J having similar performance are produced by the method.

(Embodiment 4)
In FIG. 4, an acrylic resin sheet (100 μm) 42 is set on a mold surface 41, and this is press-molded with a mold 43 that is molded into a sheet on the mold surface 41. Thereafter, the mold is changed from 43 to 44, polypropylene resin 45 is supplied, film in-mold molding is performed to form a polypropylene resin substrate 46 having an acrylic resin layer on the surface, and further, an introduction hole on the mold surface 41 is provided. Ozone and water vapor 48 are introduced from 47 and brought into contact with the resin substrate surface to produce a resin substrate 49 having surface hydroxyl groups formed thereon.

  Furthermore, this resin substrate 49 is immersed in a fluorinate (manufactured by 3M) solution containing tetrachlorosilane 50 under a nitrogen atmosphere (anhydrous) and dried in a normal atmosphere, whereby the resin substrate 51 is produced. Furthermore, this resin substrate 51 is immersed in a fluorinate (manufactured by 3M) solution containing tetrachlorotitanium 52 under a nitrogen atmosphere (anhydrous), and dried in a normal atmosphere, whereby a resin substrate K is produced.

(Easy manufacturing)
Since letters I and J disappeared when letters were written on the resin substrates I and K with oil-based ink and irradiated with UV light of 300 nm or less for 24 hours, this method was a simpler method than the resin substrate I of the present invention. A resin substrate K having similar performance is produced.

(Embodiment 5)
In FIG. 5, an acrylic resin sheet (100 μm) 62 is set on a mold surface 61, and this is press-molded by a mold 63 that is molded into a sheet on the mold surface 61. Thereafter, the mold is changed from 63 to 64, polypropylene resin 65 is supplied, and film in-mold molding is performed.
After forming a polypropylene resin substrate 66 having an acrylic resin layer on the surface, ozone and water vapor 68 are further introduced from the introduction hole 67 of the mold surface 61 and brought into contact with the surface of the resin substrate 66 to form a surface hydroxyl group-formed resin substrate. 69 is manufactured.

  Further, the tetrachlorotitanium vapor 70 is introduced from the introduction hole 67, and the resin substrate 71 is produced. Next, after once drying in a normal atmosphere, a tetrachlorotitanium vapor 72 was introduced from the introduction hole 67 to produce a resin substrate L.

(Easy manufacturing)
Resin having the same performance by a simpler method than the resin substrate K since the characters K and L disappeared when written on the resin substrates K and L with oil-based ink and irradiated with UV light of 300 nm or less for 24 hours. A substrate L is produced.

(Embodiment 6)
Referring to FIG. 6, an acrylic resin sheet 83 (100 μm) 81 is irradiated with excimer UV light 82 having a wavelength of 172 nm to produce an acrylic resin sheet 83 in which surface hydroxyl groups are formed. The acrylic resin sheet 83 is formed by immersing this acrylic resin sheet 83 in a fluorinate (manufactured by 3M) solution containing tetrachlorosilane 84 under a nitrogen atmosphere (anhydrous) and drying in a normal atmosphere. The acrylic resin sheet 87 is formed by immersing this acrylic resin sheet 85 in a fluorinate (manufactured by 3M) solution containing tetrachlorotitanium 86 under a nitrogen atmosphere (anhydrous) and drying in a normal atmosphere.

  Further, the acrylic resin sheet 87 is set on the mold surface 88, and this is press-molded by the mold 89. Thereafter, the mold is changed from 89 to 90, the polypropylene resin 91 is supplied, and film in-mold molding is performed to produce the resin substrate M.

(Easy manufacturing)
Since letters I and M disappeared when written with oil-based ink on resin bases I and ML and irradiated with UV light of 300 nm or less for 24 hours, similar performance was achieved by a simpler method than the resin base I of the present invention. A resin substrate M having the above is produced.

Example 9
Resin substrates I ′ to M ′ were produced in the same manner using decyltetrachlorotitanium instead of tetrachlorotitanium up to resin substrates I to M, and showed good water repellency (100 to 105 °). After that, UV light of 300 nm or less was irradiated to produce resin substrates I to M in the same manner. Characters were written with oil-based magic, and when irradiated with UV light of 300 nm or less for 12 hours, all of the resin substrates disappeared. . This is because the resin substrate by this method has photocatalytic performance superior to that of the resin substrates I to M because the highly dispersed titanium is immobilized.

  In the present invention, the hydrolyzable resin layer, the film having a siloxane bond, and the titanium compound are firmly bonded, and the hydrolyzable resin layer and the resin substrate have excellent adhesion because the difference in thermal expansion is small. A resin substrate having excellent durability and water repellency and photocatalytic activity can be provided. Moreover, since it is applicable also to resin molding using a metal mold | die, an application range is very wide.

Manufacturing process diagram of functional resin substrate in Embodiment 1 of the present invention Manufacturing process diagram of functional resin substrate in embodiment 2 of the present invention Manufacturing process diagram of functional resin substrate in Embodiment 3 of the present invention Manufacturing process diagram of functional resin substrate in embodiment 4 of the present invention Manufacturing process diagram of functional resin substrate in embodiment 5 of the present invention Manufacturing process diagram of functional resin substrate in embodiment 6 of the present invention

Explanation of symbols

2,12 Acrylic resin 3,13,25,45,65,91 Polypropylene resin 7,17,29,50,76,84 Tetrachlorosilane 9,31,52,72,86 Tetrachlorotitanium 10,20,22, I , K, L, M Resin base 19 Decyltrichlorotitanium 22, 42, 62, 71 Acrylic resin sheet

Claims (33)

On a resin substrate surface having a hydrolyzable resin layer on the surface, a hydrolyzable silane compound SiX ₄ (X is a hydrolyzable functional group) layer chemically bonded to the hydrolyzable resin layer, and hydrolysis A resin substrate provided with a possible SiX ₄ layer and a hydrolyzable titanium compound TiY ₄ (Y is a hydrolyzable functional group) layer chemically bonded. On a resin substrate surface having a hydrolyzable resin layer on the surface, a hydrolyzable silane compound SiX ₄ (X is a hydrolyzable functional group) layer chemically bonded to the hydrolyzable resin layer, and hydrolysis Hydrolyzable and photodegradable titanium compound R _n TiY _4-n chemically bonded to the possible SiX ₄ layer (n is an integer of 1 to 3, R is a photodegradable functional group, Y is hydrolyzed Resin substrate provided with a possible functional group) layer. The hydrolyzable titanium compound R _n TiY _4-n layer is hydrolysable RTiY ₃ (R is a photodegradable functional group, Y is a hydrolyzable functional group), 3. Resin substrate. The resin substrate according to claim 3, wherein the hydrolyzable titanium compound RTiY ₃ layer is a monomolecular film. The resin substrate according to any one of claims 1 to 4, wherein the hydrolyzable resin layer is a thermosetting resin. The resin substrate according to claim 1, wherein the surface of the hydrolyzable resin layer has a pencil hardness of H or more. The resin substrate according to any one of claims 1 to 4, wherein the hydrolyzable resin layer is acrylic, silicone, and a copolymer thereof, or polyimide, polyamide, and a copolymer thereof. 3. The resin substrate according to claim 1, wherein the resin substrate is a polyolefin resin. A step of providing a hydrolyzable resin layer on the resin substrate surface, a step of hydrolyzing the resin layer surface, a step of contacting at least a silane compound SiX ₄ (X is a hydrolyzable functional group), and the formed SiX _The step of hydrolyzing the _four layers, the step of contacting the hydrolyzed SiX ₄ layer with at least a titanium compound TiY ₄ (R is a hydrocarbon group, Y is a hydrolyzable functional group), and the formed TiY ₄ layer A method for producing a resin substrate, comprising a step of hydrolyzing. A step of providing a hydrolyzable resin layer on the resin substrate surface, a step of hydrolyzing the resin layer surface, a step of contacting at least a silane compound SiX ₄ (X is a hydrolyzable functional group), and the formed SiX _The step of hydrolyzing the _four layers, and at least the titanium compound R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group) Group) and a step of hydrolyzing the formed R _n TiY _4-n layer. A step of providing a hydrolyzable resin layer on the resin substrate surface, a step of hydrolyzing the resin layer surface, a step of contacting at least a silane compound SiX ₄ (X is a hydrolyzable functional group), and the formed SiX ₄ layer and hydrolyzing the at least titanium compound SiX _4-layer hydrolyzed _R n _{TiY 4-n} (n is an integer of 1 to 3 R photodegradable functional group, Y is a hydrolyzable functional group ), A step of hydrolyzing the formed R _n TiY _4-n layer, and a step of photolyzing the hydrolyzed R _n TiY _4-n layer. A step of hydrolyzing one surface of the hydrolyzable resin layer, a step of bringing at least a silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the surface of the hydrolyzed resin layer, and the formed SiX ₄ layer A step of contacting at least a titanium compound TiY ₄ (Y is a hydrolyzable functional group) with the hydrolyzed SiX ₄ layer, a step of hydrolyzing the formed TiY ₄ layer, and this TiY And a step of providing a substrate resin layer so that the _four layers are on the surface. A step of hydrolyzing one surface of the hydrolyzable resin layer, a step of bringing at least a silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the surface of the hydrolyzed resin layer, and the formed SiX ₄ layer a step of hydrolyzing at least a titanium compound SiX _4-layer hydrolyzed _R n _{TiY 4-n} (n is an integer of 1 to 3, R represents photolysis functional groups, Y is a hydrolyzable functional group) A step of hydrolyzing the formed R _n TiY _4-n layer, and a step of providing a substrate resin layer so that the hydrolyzed R _n TiY _4-n layer is on the surface A method for manufacturing a substrate. A step of hydrolyzing one surface of the hydrolyzable resin layer, a step of bringing at least a silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the surface of the hydrolyzed resin layer, and the formed SiX ₄ layer a step of hydrolyzing at least a titanium compound SiX _4-layer hydrolyzed _R n _{TiY 4-n} (n is an integer of 1 to 3, R represents photolysis functional groups, Y is a hydrolyzable functional group) The step of hydrolyzing the formed R _n TiY _4-n layer, the step of photolyzing the hydrolyzed R _n TiY _4-n layer, and the photo-decomposed R _n TiY _{4 A} method for producing a resin substrate, comprising: a step of providing a substrate resin layer so that the _n layer is on the surface. A step of forming a hydrolyzable resin layer on the mold surface, a step of supplying a resin for molding, a step of hydrolyzing the hydrolyzable resin layer surface, and a hydrolyzed resin layer surface, (the X hydrolyzable functional group) at least a silane compound _SiX 4 contacting a, a step of hydrolyzing SiX ₄ layer formed, at least a titanium compound _TiY 4 to SiX _4-layer hydrolyzed (Y is hydro A method for producing a resin substrate, comprising a step of contacting a decomposable functional group) and a step of hydrolyzing the formed TiY ₄ layer. A step of forming a hydrolyzable resin layer on the mold surface, a step of supplying a resin for molding, a step of hydrolyzing the hydrolyzable resin layer surface, and a hydrolyzed resin layer surface, (the X hydrolyzable functional group) at least a silane compound _SiX 4 contacting a, a step of hydrolyzing SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed _{R n TiY 4-n} (N is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group) and a step of hydrolyzing the formed R _n TiY _4-n layer The manufacturing method of the resin base | substrate which has. A step of forming a hydrolyzable resin layer on the mold surface, a step of supplying a resin for molding, a step of hydrolyzing the hydrolyzable resin layer surface, and a hydrolyzed resin layer surface, (the X hydrolyzable functional group) at least a silane compound _SiX 4 contacting a, a step of hydrolyzing SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed _{R n TiY 4-n} (N is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group), a step of hydrolyzing the formed R _n TiY _4-n layer, And a step of photolyzing the hydrolyzed R _n TiY _4-n layer. A step of attaching a hydrolyzable resin film to the mold surface, a step of supplying a resin for film in-mold molding, a step of hydrolyzing the hydrolyzable resin layer surface of the molded resin, at least titanium decomposed resin layer surface, and contacting at least a silane compound SiX 4 _(X is a hydrolyzable functional group), the SiX ₄ layer formed hydrolyzing step, the SiX _4-layer hydrolyzed A method for producing a resin substrate, comprising: contacting a compound TiY ₄ (Y is a hydrolyzable functional group); and hydrolyzing the formed TiY ₄ layer. A process of attaching a hydrolyzable resin film to the mold surface, a process of supplying a resin for film in-mold molding, a process of hydrolyzing the surface of the resin layer that can be hydrolyzed of the molded resin, and hydrolysis the resin layer surface, and contacting at least a silane compound SiX 4 _(X is a hydrolyzable functional group), and hydrolyzing the SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed A step of contacting R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group), and the formed R _n TiY _4-n layer A method for producing a resin substrate, comprising a step of hydrolyzing. A process of attaching a hydrolyzable resin film to the mold surface, a process of supplying a resin for film in-mold molding, a process of hydrolyzing the surface of the resin layer that can be hydrolyzed of the molded resin, and hydrolysis the resin layer surface, and contacting at least a silane compound SiX 4 _(X is a hydrolyzable functional group), and hydrolyzing the SiX ₄ layer formed, at least a titanium compound SiX _4-layer hydrolyzed A step of contacting R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group), and the formed R _n TiY _4-n layer and hydrolyzing, hydrolyzed R _n TiY method for producing a resin substrate having a light decomposing step the _4-n layer. The step of hydrolyzing the hydrolyzable resin film one side surface, the step of bringing at least the silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the hydrolyzed resin film one side surface, and the formed SiX ₄ Hydrolyzing the layer, contacting the hydrolyzed SiX ₄ layer with at least the compound titanium compound TiY ₄ (Y is a hydrolyzable functional group), hydrolyzing the formed TiY ₄ layer, A method for producing a resin substrate, comprising: a step of attaching a resin film so that a hydrolyzed TiY _4-n layer is on the surface of the mold surface; and a step of supplying a resin and performing film-in-mold molding. The step of hydrolyzing the hydrolyzable resin film one side surface, the step of bringing at least the silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the hydrolyzed resin film one side surface, and the formed SiX ₄ A step of hydrolyzing the layer, and at least the compound titanium compound R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group) in the hydrolyzed SiX ₄ layer Base), a step of attaching a resin film so that R _n TiY _4-n hydrolyzed on the mold surface becomes the surface, and a step of supplying a resin and performing film-in-mold molding A method for producing a resin substrate. The step of hydrolyzing the hydrolyzable resin film one side surface, the step of bringing at least the silane compound SiX ₄ (X is a hydrolyzable functional group) into contact with the hydrolyzed resin film one side surface, and the formed SiX ₄ A step of hydrolyzing the layer, and at least the compound titanium compound R _n TiY _4-n (n is an integer of 1 to 3, R is a photodegradable functional group, Y is a hydrolyzable functional group) in the hydrolyzed SiX ₄ layer Base)), photolyzing the hydrolyzed R _n TiY _4-n layer, and mounting the resin film on the mold surface so that the photo-decomposed R _n TiY _4-n is on the surface. The manufacturing method of the resin base | substrate which has a process and the process of supplying a resin and performing film in-mold shaping | molding. The method for producing a resin substrate according to any one of claims 9 to 23, wherein the step of hydrolyzing the surface of the hydrolyzable resin layer is at least UV irradiation or corona ray irradiation. The method for producing a resin substrate according to any one of claims 9 to 23, wherein the step of hydrolyzing the hydrolyzable resin layer surface is at least ozone or oxygen plasma contact. The step of hydrolyzing the surface of the hydrolyzable resin layer is between the mold surface and the hydrolyzable resin layer, and is at least contact with ozone or oxygen plasma. The manufacturing method of the resin base | substrate of description. The method for producing a resin substrate according to any one of claims 24 to 26, wherein an atmosphere for hydrolyzing the surface of the hydrolyzable resin layer is 10% or more of humidity. The method for producing a resin substrate according to any one of claims 9 to 23, wherein the hydrolyzable functional group X or Y is a halogen group, an alkoxy group or an isocyanate group. The method for producing a resin substrate according to claim 28, wherein the halogen group is a chloro group. The method for producing a resin substrate according to any one of claims 9 to 23, wherein the step of contacting the silane compound or the titanium compound is an anhydrous atmosphere having a humidity of 35% or less. The method for producing a resin substrate according to any one of claims 9 to 23, wherein the step of bringing the silane compound or the titanium compound into contact is contact with a solution of the silane compound. 21. The process according to any one of claims 15 to 20, wherein the step of bringing the silane compound or the titanium compound into contact is between the mold surface and the hydrolyzable resin layer and is at least the contact of the vapor of the silane compound or the titanium compound. A method for producing a resin substrate. Hydrolyzed _{R n TiY 4-n} layer light decomposing step is preparation of claim 11,14,17,20 or 23, wherein the resin gas, characterized in that it is a radiation of the following UV light 300nm Method.