WO2006137173A1

WO2006137173A1 - Antifouling base for printing, printed matter using same and printed body

Info

Publication number: WO2006137173A1
Application number: PCT/JP2005/012870
Authority: WO
Inventors: Takayoshi Nakasone; Norihiro Nakayama; Shinji Tanaka; Naoki Tanaka
Original assignee: Ube-Nitto Kasei Co., Ltd.
Priority date: 2005-06-22
Filing date: 2005-07-12
Publication date: 2006-12-28
Also published as: TW200700477A; JP2007001088A

Abstract

Disclosed is an antifouling base for printing which exhibits self-cleaning properties for a long time due to photocatalytic activity. Also disclosed are a printed matter using such an antifouling base and a printed body. Specifically disclosed is an antifouling base for printing which is characterized in that a photocatalytically active layer is arranged on one side of an organic base via an activity blocking layer and the other side of the organic base serves as a printing surface.

Description

Specification

Antifouling printing substrate and printed matter and printed matter using the same

Technical field

[0001] The present invention relates to an antifouling printing substrate having self-cleaning properties by a photocatalytic activity, a printed matter and a printed body using the same.

[0002] Since photocatalytically active materials have a surface purification action by making them superhydrophilic, a so-called antifouling effect that keeps the surface of signboards and the like beautiful and free of maintenance is expected, and various methods have been proposed. Has been tried.

[0003] For example, in a printed matter that is directly exposed to the outside air or displayed for a long period of time, it is composed of at least a printed layer, an active blocking layer made of an inorganic material that blocks photoactivity, and a photoactive antifouling layer There has been proposed a weather-resistant printed material having a laminated body strength in which protective layers are sequentially laminated. (See Patent Document 1)

This weather-resistant printed matter can decompose and wash off or wipe off oil even if dust or oily dirt adheres to the printed surface, prevent contamination by dust on the surface, and synergistic action with the UV blocking layer. Expected to prevent discoloration and fading due to light.

However, the printed matter of Patent Document 1 is printed on the surface of the base material, and the active blocking layer and the photoactive layer are applied again on the upper layer, so that the printing blots in the organic solvent used during coating and the heat drying process. In addition, there is a possibility that the clearness of printing may be impaired by the occurrence of evaporation of ink. In addition, considering continuous production in consideration of economic efficiency, it is desirable that there are a large amount of the same fixed-size printed matter, but the printed matter is often in a small amount and many varieties, and each time a coating process is required. It was necessary and very laborious.

[0004] Further, on one surface of the base material, at least an antifouling layer containing a metal oxide having a photocatalytic function is contained, and the surface force of the antifouling layer is transmitted through the sublimation transfer printing method. In this way, a printed material is proposed that is formed by transferring an image onto a base material! (See Patent Document 2)

However, since the method described in Patent Document 2 performs printing from the antifouling layer side by the sublimation transfer printing method, the sublimation ink remains on the antifouling layer, and the antifouling property is initially reduced, or There was a risk that the ink bleeded out over time and the photocatalytic activity was reduced.

In order to form a porous layer in the formation of the antifouling layer, a low temperature sol-gel method is used. There is a problem that the printing method is limited to the sublimation transfer printing method and is technically limited and cannot be applied to general printing.

[0005] As described above, a practical printed material that can be subjected to antifouling treatment without affecting the printed layer has been developed yet for a small variety of printed materials.

Furthermore, a printing substrate having an antifouling effect that can be applied to a small variety of printed materials and having a high printability capable of performing beautiful printing has not yet been obtained.

[0006] Patent Document 1: Japanese Unexamined Patent Publication No. 2000-117187

Patent Document 2: JP 2003-43960 A

Disclosure of the invention

[0007] The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide an antifouling printing substrate having a self-cleaning property due to a photocatalytic activity over a long period of time. Another object of the present invention is to provide a printed matter and a printed body using the same.

As a result of diligent research to achieve the above object, the present inventors prepared a printing substrate in which an active blocking layer and a photocatalytic active layer were previously formed on one surface of an organic substrate, and printed on the other surface. It was found that the above problems can be solved.

That is, the present invention

(1) An antifouling printing substrate characterized by having a photocatalytic active layer on one side of an organic substrate via an active blocking layer and the other side as a printing surface,

(2) An antifouling printed matter characterized by being printed on the antifouling printing substrate described in (1) above,

(3) An antifouling printed matter comprising an adhesive layer on the surface of the antifouling printed matter described in (2) above

Is to provide.

[0008] The antifouling printing substrate of the present invention (hereinafter referred to as "printing substrate") has a photocatalytic active layer on one surface of an organic substrate via an active blocking layer, and the other surface. The printing layer after printing is separated by a transparent organic substrate, so that the photocatalytic active layer does not adversely affect the printed layer after printing. The composition of the photocatalytic active layer, combined with weather resistance and crack resistance, makes the printed layer beautiful for a long time. And it can be kept clear.

According to the printing substrate of the present invention, since the photocatalytic active layer is already provided on one surface of the transparent organic substrate via the active blocking layer, depending on the size and amount of the printed matter, It is only necessary to prepare the required number of substrates and perform the required printing on the other side of the substrate for printing, so it can flexibly handle a small amount of printed content, and it can be used as an advertising medium, etc. It is possible to provide a wide variety of antifouling prints and prints for outdoor exhibitions having antifouling properties. Since the anti-fouling function is added at the beginning, each user can easily print any photo or picture on the home printing machine (printer) and post it outdoors without getting dirty. It becomes possible.

Furthermore, the printing saturation can be improved by attaching a white pigment or the like to the printing surface during printing.

Moreover, since the printing body of this invention provides the adhesion layer on the surface of a printing layer, the sticking to the board | substrate of a signboard, the glass of a building, a wall surface, etc. becomes easy.

In the printed matter and printed matter of the present invention, since the printing layer itself does not directly contact the active blocking layer or the photocatalyst layer, various inks can be selected and used without considering the solvent used in these layers. In addition, it can be used as a display material with good color development, such as a photograph, a picture, a poster, etc., and a high advertising effect can be realized in combination with the self-cleaning effect by the photocatalytic action. In addition, if water is applied to the glass or wall of a building or building and sprayed for cleaning purposes, the water will spread over the entire surface due to the super-hydrophilic effect, and the effect of cooling the construction object due to the hammering effect is expected. .

The photocatalytic function enables self-purification by rain or water spraying, so it can be used for outdoor art exhibitions that use internal lighting similar to outdoor theaters, gardening materials (printing fences, flowerbeds, etc.), or many times according to the season Use for long-term or repetitive use with a beautiful surface, such as for outdoor bulletin board materials to be removed (for example, printed Christmas trees, printed carp streamers, printed dolls, printed stained glass, printed self-made calendars, etc.) It is out.

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view of a printing substrate according to an embodiment of the present invention. 圆 2] A graph showing the XPS measurement results of the coating for active barrier layer obtained in Example 1. 圆 3] A schematic cross-sectional view of a printed material according to an example of the present invention.

Explanation of symbols

1. Substrate for printing

2. Organic base material

2a. Finorem base material

2b. UV shielding layer

3. Active blocking layer (gradient film layer)

4. Photocatalytic active layer

5. Material ¾: Surface

6. Release film

7. Adhesive layer

8. Release film with adhesive

9. Print layer

10. Printed matter

BEST MODE FOR CARRYING OUT THE INVENTION

The organic substrate that can be used for the printing substrate of the present invention is a support for the printed layer, has a strength that does not hinder the printed material and printed matter, and can withstand the outdoors and exposure to sunlight. It is a material with a small amount of material, and at least it is selected as an organic material having transparency that allows the printed content to be viewed from the photocatalytic active layer side.

As the form of the organic base material of the present invention, a film, sheet, plate material, etc., which is transparent and has a transparency, a plastic having excellent chemical adsorption power, affinity, and compatibility with printing ink is preferably used. .

Moreover, when it is set as a self-supporting signboard etc., a transparent material with a plate-like thickness is preferable. In the case of a plate-like material, it is not always necessary to have a solid and uniform wall thickness, and a plastic corrugated cardboard with parallel ribs between the upper and lower liners, or an independent cylindrical space between the upper and lower liners. Even if it is a sheet-like material, the liner surface is Any material having flatness sufficient to form a fault can be used. If these are used, it will be possible to reduce the cost and convenience in terms of weight in installation work.

Furthermore, the organic base material that can be used in the present invention includes synthetic fibers having transparency, woven fabrics such as natural fibers and non-woven fabrics, and synthetic paper.

The fibrous organic base material may be formed into a film shape with a heat calender roller or the like as required for design and the like.

[0012] Examples of the organic base material include acrylic resins such as polymethylmethacrylate, styrene resins such as polystyrene and ABS resins, polyolefin resins such as polyethylene and polypropylene, polyethylene terephthalate and polyethylene. Polyester resin such as naphthalate, polyamide resin such as 6-nylon and 6, 6-nylon, polysalt vinyl resin, polysalt vinylidene resin, polycarbonate resin, Examples thereof include powerful base materials such as polyphenylene sulfide-based resins, polyphenylene ether-based resins, polyimide-based resins, polyetherimide-based resins, and cellulose-based resins such as cellulose acetate. Among them, acrylic resin such as polymethylmethalate, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, poly salt resin resin, poly salt vinyl-redene resin, polycarbonate resin Fat is preferred in terms of transparency.

[0013] These organic base materials can be subjected to a surface treatment by an oxidation method, a concavo-convex method or the like, if desired, in order to further improve the adhesion to the active blocking layer or the printing ink. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone 'ultraviolet irradiation treatment, and the like. Examples of the unevenness method include sand blast method, solvent Treatment methods and the like. These surface treatment methods are appropriately selected depending on the type of substrate.

The organic base material needs to be transparent so that the printed layer can be visually recognized, but it need not be colorless and transparent, and may be transparent colored to increase printing saturation. As the transparency, those having a total light transmittance of 70% or more can be used.

[0014] The active blocking layer provided on one surface of the organic base material is provided to prevent deterioration of the organic base material due to photocatalytic action and to prevent influence on the printed layer. It also has a function of improving the adhesion to it, and those usually used as a protective layer of a photocatalytic film can be used.

In general, as the protective layer, a silicone resin, such as an acrylic-modified silicone resin, having a thickness of about several tens / zm is used, and these can also be used in the present invention. However, if necessary, the surface of the organic base material may be laminated with the above-described surface treatment or modified material. As the modified material, those containing acrylic, polyester, epoxy group or urethane group are preferably used.

[0015] When higher durability and weather resistance are desired for printed materials for outdoor exhibitions, the active blocking layer includes a composite in which an organic polymer compound and a metal oxide compound are chemically bonded. And a component gradient structure in which the content of the metal component continuously changes in the thickness direction of the film, and the concentration of the metal oxide compound component is substantially high at the interface with the photocatalytic active layer. It is more desirable that the organic-inorganic composite gradient layer has a high concentration of the organic polymer compound component on the surface in contact with the organic substrate.

[0016] The active barrier layer force (A) -coating composition containing at least one hydrolysis condensate of metal alkoxide represented by the general formula (I) is formed. desirable.

MR ¹ (OR ² )--(I)

(Wherein, M is a metal of Si, Ti, Al, Zr, R ¹ is an alkyl group, an alkyl group, an alkyl group, an aryl group, an aralkyl group or an acyl group, R ² is a C 1-6 carbon atom. An alkyl group, m represents the valence of metal M, and X represents an integer of 0 to 2.)

In the general formula (I), R ¹ is a non-hydrolyzable group, and the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and the alkenyl group and the alkyl group are carbon atoms. Those having a number of 2 to 20 are preferred. The aryl group preferably has 6 to 20 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms. Further, examples of the acyl group include an aliphatic acyl group having 2 to 20 carbon atoms and an aromatic acyl group (aroyl group) having 7 to 20 carbon atoms. On the other hand, OR ² is a hydrolyzable group, and the alkyl group having 1 to 6 carbon atoms represented by R ² may be linear, branched, or cyclic. Group, ethyl group, n propyl group, isopropyl group, n butyl group, isobutyl group, sec butyl group, tert-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like. X is an integer of 0 to 2, when R ¹ are a plurality, each R ¹ to each other may be identical der connexion, when a plurality Yogumata OR ² is be different, each OR ² is another May be the same or different.

The active blocking layer formed of such an organic / inorganic composite gradient layer is formed of (B) an amorphous titanium oxide forming compound and (C) at least one titanium selected from inorganic salts, organic salts and alkoxides. It is more desirable in terms of durability, crack resistance, and weather resistance to form a coating composition containing a metal compound other than the above.

Examples of the (B) amorphous titanium oxide forming compound, that is, the component (B) include, for example, the general formula (Π)

TiR ¹ (OR ² )

Four

(In the formula, R ¹ is an alkyl group, an alkyl group, an alkyl group, an aryl group, an aralkyl group or an acyl group, R ² is an alkyl group having 1 to 6 carbon atoms, and X is an integer of 0 to 2. Show.)

It may contain the titanium alkoxide represented by the above as it is, or it may contain a hydrolysis product condensate thereof, or may contain both of them. More preferred.

In the general formula (II), R ¹ is a non-hydrolyzable group, and the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and the alkenyl group and alkynyl group are Those having 2 to 20 carbon atoms are preferred. The aryl group preferably has 6 to 20 carbon atoms, and the aralkyl group preferably has 7 to 20 carbon atoms. Furthermore, preferred examples of the acyl group include an aliphatic acyl group having 2 to 20 carbon atoms and an aromatic acyl group (aroyl group) having 7 to 20 carbon atoms.

[0018] On the other hand, OR ² is a hydrolyzable group, and the alkyl group having 1 to 6 carbon atoms represented by R ² may be linear, branched or cyclic. Are methyl, ethyl, n propyl, isopropyl, n butyl, isobutyl, sec butyl, te Examples thereof include rt-butyl group, pentyl group, hexyl group, cyclopentyl group, cyclohexyl group and the like. X is an integer of 0 to 2, when R ¹ are a plurality, each R ¹ to each other may be identical der connexion, when a plurality Yogumata OR ² is be different, each OR ² is another May be the same or different.

Among the titanium alkoxides represented by the general formula (II), titanium tetraalkoxides are preferable. Examples of the titanium tetraalkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetra- _n -propoxide, titanium tetraalkoxide. Preferable examples include isopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-sec-butoxide and titanium tetra-tert-butoxide. These may be used alone or in combination of two or more.

[0020] In the composition forming the active blocking layer of the present invention, as a solvent used for hydrolysis and condensation, alcohols having an ether type oxygen having 3 or more carbon atoms, which alcohols are preferable, hydrolysis Further preferable alcohols having ether oxygen having 3 or more carbon atoms include solvents having an interaction with titanium alkoxide, such as ethylene glycol monomethyl ether. Cellosolve solvents such as Nole, Ethylene Glyco-Nole Monoethylenoate, Ethylene Glyco-Nole Monopropenoate, Ethylene Glycol Monobutyl Ether, Diethylene Glycole Monomethinoatenore , Diethylene glycol monopropinoreate , Diethylene glycolenomonobutylenoate, propylene glycolenomonoethylenoate, propylene glycolenomonoethylenoate, propylene glycolenomonopropenoate, propylene glycolenomonobutinole ether, etc. Can be mentioned. Among these, cellosolve solvents are particularly preferable. These solvents can be used alone or in combination of two or more.

[0021] Hydrolysis of titanium tetraalkoxide When using a condensate, the hydrolysis-condensation reaction of titanium tetraalkoxide is preferably 4 to 20 times, more preferably 5 to 12 times that of titanium tetraalkoxide. Using an alcohol catalyst such as hydrochloric acid, sulfuric acid, nitric acid, etc., using 0.5 mole of the alcohol and preferably 0.5 to 4 moles of water, more preferably 1 to 3.0 moles of water. Is usually carried out at a temperature in the range of 0 to 70 ° C, preferably 20 to 50 ° C. The acidic catalyst is used in an amount of usually 0.1 to 1.0 times mol, preferably 0.2 to 0.7 times mol, with respect to titanium tetraalkoxide.

[0022] On the other hand, the metal compound other than titanium as component (C) functions as a crystallization inhibitory compound for amorphous titanium oxide. From the viewpoint of effects, inorganic salts, organic salts and alkoxides are used. A compound selected from the group consisting of nitric acid, acetic acid, sulfuric acid, aluminum chloride and zirconium salts, and hydrates of these inorganic salts, aluminum chelates such as aluminum triacetylacetonate And metal alkoxides such as tetra-n-propoxydylconium, tetraethoxysilane, and phenoltrimethoxysilane, and hydrolysates or condensates of these compounds. Among these, it is preferable that the metal other than titanium is aluminum and Z or zirconium. In particular, aluminum nitrate and hydrates thereof are more preferable. The metal compounds may be used alone or in combination of two or more.

The order of addition of the metal compound other than titanium as the component (C) is not particularly limited as long as it is added as it is to the liquid containing the component (B).

In the formation of the active blocking layer of the present invention, the amount of the metal compound other than titanium as component (C) is usually selected in the range of 5 to 50 mol% with respect to the titanium atom. When the amount used is at least mol%, a good crystallization inhibiting effect is obtained, and at 50 mol% or less, the physical properties inherent to amorphous titanium oxide are exhibited well. When aluminum nitrate is used as the dissimilar metal compound, the use amount is particularly preferably in the range of 10 to 30 mol%.

[0024] The thus obtained coating composition for forming an active blocking layer of the present invention has the properties described above, and the solid content concentration thereof is usually about 0.1 to 30% by mass, preferably Is about 0.5 to 20% by mass. This coating composition is applied on a desired substrate so as to have a dry thickness force of about SO.01 to 2111, preferably 0.02 to 0.7 m, for example, by drying at room temperature, or If desired, by further heat treatment, it is colorless and excellent in transparency, and it is difficult to newly generate fine cracks of about 50 nm to 5 m in length. V, forming an amorphous titanium oxide composite coating film be able to. [0025] The coating composition for forming an active barrier layer of the present invention further comprises (D) an organic component that can be chemically bonded to amorphous titanium oxide, thereby providing a coating film on an organic substrate. In addition, it is possible to obtain a coating film having a self-gradient composition force in which the content of the amorphous titanium oxide component is inclined toward the substrate from the surface of the coating film.

[0026] Examples of the organic component that can be chemically bonded to (D) amorphous acid titanium include, for example, (a) an ethylenically unsaturated monomer containing no metal, and (b) a coupling cage Preferable examples include organic polymer compounds obtained by copolymerizing an ethylenically unsaturated monomer having a containing group.

[0027] Examples of the (a) ethylenically unsaturated monomer containing no metal include, for example, the general formula (III) [0028] [Chemical Formula 1]

R ³

I

H ₂ C = C— X (III)

(Wherein R ³ is a hydrogen atom or a methyl group, and X is a monovalent organic group.)

An ethylenically unsaturated monomer represented by general formula (IIIa)

[0029] [Chemical 2]

R ³

H ₂ C = C-COOR ⁴ (II 卜 a)

(Wherein R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a monovalent hydrocarbon group, an epoxy group, a halogen atom or a hydrocarbon group having an ether bond.)

One or a mixture of two or more ethylenically unsaturated monomers represented by

[0030] In the ethylenically unsaturated monomer represented by the above general formula (III a), represented by R ⁴ Charcoal

Examples of the hydride group include linear or branched alkyl groups having 1 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 10 carbon atoms. Preferable examples can be given. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, and various butyl group, pentyl group, hexyl group, octyl group, decyl group and the like. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, and cyclooctyl group. Examples of aryl groups having 6 to 10 carbon atoms include phenol group, Group, xylyl group, naphthyl group, methylnaphthyl group and the like, and examples of the aralkyl group having 7 to 7 carbon atoms include benzyl group, methylbenzyl group, phenethyl group, naphthylmethyl group and the like. Examples of the hydrocarbon group having an epoxy group, a halogen atom or an ether bond include a linear or branched alkyl group having 1 to 10 carbon atoms having these groups, atoms or bonds, or a carbon group having 3 to 10 carbon atoms. Preferred examples include cycloalkyl groups, aryl groups having 6 to 10 carbon atoms, and 7 to carbon atoms: aralkyl groups having L0. A chlorine atom etc. are mentioned as a halogen atom of the said substituent.

[0031] Examples of the ethylenically unsaturated monomer represented by the general formula (IIIa) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Atarylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenol (meth) acrylate, benzyl (meth) acrylate, glycidyl (Meth) Atalylate, 3—Glycidoxypropyl (Meth) Atalylate, 2— (3, 4—Epoxycyclohexyl) ethyl (Meth) Atylate, 2 — Black-Ethoxyl (Meth) Atalylate, 2— Brogetyl (meth) acrylate. These can be used alone! Two or more kinds may be used in combination.

In addition to these, the ethylenically unsaturated monomer represented by the general formula (III) may be styrene, α-methylolstyrene, α-acetoxystyrene, m—, ο or ρ. Stabilizers for polymerizable polymers having ethylenically unsaturated groups such as bromostyrene, m-, o or p-chlorostyrene, m-, o or p vinylphenol, 1 or 2-burnaphthalene, etc. Unsaturated, antioxidant, UV absorption A collecting agent, a light stabilizer and the like can also be used. These may be used alone or in combination of two or more.

[0033] On the other hand, examples of the (b) ethylenically unsaturated monomer having a coupling group-containing group include, for example, the general formula (IV)

[0034] [Chemical 3]

(Wherein R ⁵ represents a hydrogen atom or a methyl group, A represents an alkylene group having 1 to 4 carbon atoms, and R ⁶ represents a methyl group or an ethyl group.)

Preferred examples include compounds represented by: In the general formula (III), the three R ⁶ are the same or different from each other! /, May! /.

Examples of the ethylenically unsaturated monomer represented by the general formula (IV) include 2- (meth) atari-mouthed _{kichetiltrimethoxysilane} , 2- (meth) _{atarilochhetyltriethoxysilane} , _Ύ -(Meth) _{Atalyloxypropyltrimethoxysilane} , _Ύ — (Meth) Atalyloxypropyltriethoxysilane.

This ethylenically unsaturated monomer having a coupling-caine-containing group as component (D) may be used alone or in combination of two or more.

[0035] Initiating radical polymerization of the (a) component-free ethylenically unsaturated monomer and the component (b) the ethylenically-unsaturated monomer having a coupling-caine-containing group By carrying out radical polymerization in the presence of the agent, a compound having a self-gradient composed of an organic polymer compound having a coupling group-containing group used as a component of the component (D) can be obtained.

[0036] In the active barrier layer of the present invention, the organic polymer compound having a coupling-caine-containing group as component (D) thus obtained is mixed with an appropriate solvent such as alcohol, ketone, or ether. Solution of titanium alkoxide, which is the component (B) described above, Decomposition 'condensate is mixed with a metal compound other than titanium as component (c) and a solution obtained by diluting Z or a reaction solution containing it as necessary, thereby coupling the coupling agent in the organic polymer compound. The element-containing group is hydrolyzed, and selectively reacts with the hydrolysis condensate of titanium alkoxide in the reaction solution of component (B) to form a coating composition for forming an organic-inorganic composite gradient film, that is, the printing substrate in the present invention. A composition for an active barrier layer is obtained.

In this case, it is desirable to use a solvent containing an alcohol having an ether oxygen having 3 or more carbon atoms as the diluting solvent for the reaction solution containing the hydrolysis condensate of titanium alkoxide to be used.

[0037] By using such a coating composition, when applied to an organic base material and dried, the organic base material side is substantially the organic polymer compound component and the opposite side is the amorphous oxide titanium component. Thus, it is possible to stably form an organic-inorganic composite gradient film having a good component gradient structure in which the content ratios of both components continuously change in the film thickness direction. The organic-inorganic composite gradient film can be used as an active blocking layer.

[0038] Since this composite gradient active barrier layer contains an amorphous titanium oxide component as an inorganic component, crystallization of the inorganic component is suppressed even when exposed to the accelerated weathering test. Deterioration of mechanical properties, cracks, and transparency are suppressed.

[0039] In order to form a composite gradient film as an active blocking layer on an organic substrate, the coating composition of the present invention thus obtained is used with a dry film thickness force of usually 5 m or less, Desirably ί0. 01 ~: L 0 m, more preferably 0.02 ~ 0.7 m, date coat method, spin coat method, spray coat method, bar coat method, knife coat. The film is applied by a known method such as a coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method, and the solvent is evaporated to form a coating film.

The organic substrate in the present invention includes materials having an organic coating film on the surface of a material other than the organic materials exemplified above, for example, a substrate made of glass or a transparent ceramic material.

[0040] In addition, the tilt structure of the active blocking layer can be confirmed by, for example, sputtering the surface of the coating to scrape the film, and over time, the content of carbon atoms and titanium atoms on the surface of the film is determined by X-ray photoelectron. It can be performed by measuring by spectroscopic method or the like.

The content of the metal component in the composite gradient film as the active blocking layer is not particularly limited, but is usually 5 to 98 mass%, preferably 20 to 98 mass%, particularly preferably 50 in terms of metal oxide. It is the range of -95 mass%. The degree of polymerization and the molecular weight of the organic polymer compound are not particularly limited as long as they can be formed into a film, and may be appropriately selected depending on the type of polymer compound and the physical properties of the desired gradient membrane material. Oh ,.

[0041] The photocatalytic active layer of the present invention may be a layer obtained by solidifying an anatase-type titanium oxide generally used as a photocatalytic layer with a binder. However, in consideration of durability and weather resistance, It is desirable to comprise with the following composition.

That is, the improved photocatalytically active layer coating composition of the present invention may further include (E) fine particles having a photocatalytic function and Z or silica fine particles in addition to (A) and (C).

As the fine particles having a photocatalytic function, titanium oxide particles mainly composed of anatase type crystals can be used.

The titanium oxide fine particles containing the anatase type crystal as a main component (hereinafter sometimes referred to as anatase crystal oxide titanium particles) are photocatalyst particles and may contain a small amount of rutile type crystals. Visible light-responsive photocatalyst particles partially containing titanium nitride, low-order titanium oxide, and the like can also be used. The average particle diameter of the anatase crystalline titanium oxide particles is preferably in the range of 1 to 500 nm, more preferably in the range of 1 to 100 nm, and the most preferable range is in the range of 1 to 50 nm because of having an excellent photocatalytic function. The average particle diameter can be measured by a scattering method using laser light.

[0042] Further, in the inside of the titanium oxide particle and Z or the surface thereof, as a second component, among V, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Pt and Au, It is preferable to contain at least one metal selected from the group consisting of Z and a metal compound because it has a higher photocatalytic function. Examples of the metal compound include metal oxides, hydroxides, oxyhydroxides, sulfates, halides, nitrates, and metal ions.

The content of the second component is appropriately selected according to the type of the substance. [0043] The anatase crystalline acid titanium particles can be produced by a conventionally known method, but it is advantageous to use them in the form of an acid titanium sol for homogeneous dispersion in the coating liquid. is there.

To produce the acid titanium sol, for example, powdered anatase crystalline acid titanium may be dissolved in the presence of an acid or alkali, and the particle size may be controlled by grinding! /ヽ. Further, hydrous or neutralized decomposition of titanium sulfate or titanium chloride may be used to control the crystallite size and particle size by physical and chemical methods. Furthermore, a dispersion stabilizer can be used in order to impart dispersion stability in the sol solution.

[0044] On the other hand, colloidal silica has the effect of allowing the photocatalyst film to exhibit superhydrophilicity maintaining performance even in the dark! / Speak.

Photocatalysts exhibit the property of decomposing organic substances present on the surface by irradiation with light such as ultraviolet rays and superhydrophilicity, but such photocatalytic functions are generally not exhibited in the dark.

However, when colloidal silica is contained in the photocatalyst film, the photocatalyst film exhibits super hydrophilicity maintaining performance even in the dark.

This colloidal silica is a high purity silicon dioxide (SiO 2) solution in water or alcohol.

2

The product is a colloidal product dispersed in an agent, and the average particle size is usually in the range of 1 to 200 nm, preferably 5 to 50 nm. Hydrolysis of silicon alkoxides In the condensate, the reaction is not terminated, so the photocatalytic film that is eluted with water and immediately contains it is inferior in water resistance.

On the other hand, since colloidal silica is a reaction-terminated fine particle, a photocatalyst film that is difficult to be eluted with water has excellent water resistance.

This colloidal silica may exhibit an effect of making the surface uneven as well as an effect of improving the strength and hardness of the coating film.

[0045] A coating composition having a photocatalytic function used for the photocatalytic active layer of the present invention includes, as an example, a hydrolysis product of the titanium alkoxide as component (B) and a condensate (C) as a component. In a liquid containing a simple substance other than the above and Z or its reaction liquid, a certain amount of anatase crystalline acid-titanium sol and, optionally, colloidal silica may be added to make it homogeneous. It can be prepared by dispersing it.

[0046] The thus prepared coating composition having a photocatalytic function is applied to a known method such as a dip coating method, a spin coating method, a spray coating method, a bar on an organic substrate on which an active blocking layer is formed. A desired photocatalyst film, that is, a photocatalytic active layer, is formed by coating by a coating method, knife coating method, roll coating method, blade coating method, dying coating method, gravure coating method, etc., and then drying naturally or by heating. can get. When drying by heating, temperatures below 200 ° C can be used.

Thus, after the film formation, the formed photocatalyst film can exhibit a sufficient photocatalytic function by holding treatment at a low temperature. Therefore, it can be suitably used as the antifouling printing substrate of the present invention. it can.

[0047] The organic substrate of the present invention may be a transparent plastic film or plastic sheet having a thickness of 50 µm or more.

If the thickness is less than 50 m, it is difficult to handle in the printing process and the photocatalyst coating process, and because it is thin, deformation, elongation, damage, etc. are likely to occur due to external forces.

The thickness of the organic base material of the present invention is appropriately determined according to the purpose of use and application, such as handling after printing, followability to a sticking object, and self-supporting property as a signboard.

In addition, the form of the organic substrate of the present invention is convenient for continuous formation of a long roll-like active blocking layer, photocatalytic active layer, printing layer, etc., as long as it can be removed with a film, sheet or the like. It is.

If it is a plate-shaped object with thickness, what was cut to a fixed scale is used.

Further, the printing substrate may be formed into a continuous roll shape or a sheet-like sheet shape depending on a printing method or the like.

On the other hand, the width of the organic base material of the present invention can be 2000 mm or less, preferably 30 Omm to 1600 mm from the viewpoint of printability. If it exceeds 2000 mm, handling during printing becomes difficult.

[0048] In the present invention, an ultraviolet ray blocking layer is provided in the surface layer of one surface of the organic base material to provide an ultraviolet ray blocking layer, thereby preventing deterioration due to ultraviolet rays, surface cracks, and breakage due to brittleness, etc. can do. As the weather resistance improver that can be used in the present invention, for example, Benzofenau Examples include organic ultraviolet absorbers such as benzene, benzotriazole, oxalic acid, cyanoacrylate, and triazine, hindered amine light stabilizers, excitation energy absorbers, and radical scavengers. However, it is not limited to these. The weather resistance improver may be provided as a weather resistance improvement layer on the organic base material instead of being contained in the organic base material. In this case, the amount of the weather resistance improvement agent used can be reduced, Cost can be reduced.

[0049] An ink receiving layer can be provided on the surface of the printing substrate of the present invention. The ink receiving layer whose surface has simply been modified is for improving the adhesion with the printing ink, and can be provided by subjecting it to a surface treatment by an oxidation method or an unevenness method. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone 'ultraviolet irradiation treatment and the like. Examples of the unevenness method include sand blast method and solvent treatment. Law. These surface treatment methods are appropriately selected according to the type of organic substrate and the type of printing ink. Ink-receptive layer for inkjet requires porous hybrid film containing silica and alumina, and special hydrophilic resin similar to the hot-melt inkjet media “Pre-Make HL” manufactured by Mitsubishi Sewa Co., Ltd. It can be selected appropriately according to the situation.

[0050] The printing method for producing the antifouling printed material of the present invention is not particularly limited, but a printing method suitable for the printing medium can be employed. For example, it can be performed by any printing means such as lithographic offset printing, intaglio gravure printing, relief printing, silk screen printing, ink jet printer, electrostatic printer, sublimation ink transfer, laser printing, etc. it can.

Printing is visible in the normal state when viewed from the photocatalytic active layer side by performing so-called reversal printing in which the printed image has a mirror image relationship with the normal visual state when viewed from the printing surface side.

On the other hand, if the printed matter of the present invention is attached to the outside of the window glass and the purpose is to visually observe mainly from the room, normal printing may be performed without inversion.

In addition, the printed content can be made to stand out by printing a colored background such as white on the target printed matter.

As the printing ink, various inks can be used in addition to inks based on solvent-based pigments. [0051] In the present invention, a printed body in which an adhesive layer is directly formed on the printing surface may be used. This adhesive layer is a case where re-peeling after sticking is predicted, but in the case where re-peeling is not planned, it may be an adhesive layer.

The pressure-sensitive adhesive of the pressure-sensitive adhesive layer is selected in consideration of the pressure-sensitive adhesiveness with the organic substrate, the degree of influence on the printed layer, the pressure-sensitive adhesive force with the object to be bonded, and the like. Examples of the adhesive that can be used include acrylic, urethane, silicone rubber, and rubber adhesives that have been conventionally used, and are not particularly limited. Easy to design re-peelability V, acrylic adhesive is more preferred.

It is desirable that a separator (release paper) is laminated on the surface of the adhesive layer, and it is also desirable to interpose a separator even when a protective layer is provided.

Example

[0052] Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

The total light transmittance and haze shown in each example were determined according to the following procedure. (Total light transmittance of coating film)

In accordance with JIS K7361-1, the total light transmittance and haze were measured using the following apparatus and measurement sample.

Device name: Nippon Denshoku Co., Ltd. Haze Mater NDH2000

(X-ray photoelectron spectroscopy)

Using an XPS device “PHI-5600” [manufactured by ULVAC-FAI Co., Ltd.], argon sputtering (4 kV) was applied at an interval of 3 minutes to scrape the film, and the content of carbon atoms and metal atoms on the film surface was measured. The inclination was examined.

[0053] Example 1

(Production of film with photocatalyst layer)

(1) Formation of active blocking layer

In a 1 L separable flask under a nitrogen atmosphere, methyl isobutyl ketone 424. Og, methanolic acid methanolic acid 200. . In this mixed solution, methyl isoform in which 1.9 g of azobisisobutyric-tolyl was dissolved A butyl ketone solution was added dropwise to initiate the polymerization reaction, and the mixture was stirred for 30 hours to obtain an organic component solution (a).

To a solution of titanium tetraisopropoxide 35. 55 g to E Chino receptacle Honoré Seo Norev 70. 02G, 60 mass ^_0/0確酸5. 94 g, mixture of water 2. 14 g and E Chino receptacle nitroso Norev 27. 39g The solution was slowly added dropwise with stirring, and then stirred at 30 ° C for 4 hours to obtain a mixed solution (b).

Next, using the above mixed solution (b), ethyl cellsolve, and aluminum nitrate as the foreign metal compound, the amount of added aluminum nitrate is 15 mol% with respect to Ti atoms, and the solid content concentration of the entire solution is 5 mass%. Thus, a composite metal compound solution (c) was obtained.

Next, 1.46 g of the above solution (a), 47.15 g of methyl isobutyl ketone, 19.01 g of ethyl cellosolve, 29.60 g of the solution (c) and 2.78 g of colloidal silica dispersion were mixed and stirred for 15 minutes. Thereafter, it was stored overnight at 5 to 10 ° C. to obtain an organic one-inorganic component gradient solution (e). Next, as the organic substrate 2 shown in FIG. 1, a polyethylene terephthalate (PET) film substrate (Toray, T-60, thickness 100 m, width 1600 mm) HALS (manufactured by Adeka Gas, Adeka Stub LA-68, An active shielding fault 3 was formed by forming a film having a total thickness of 105 μm on a 105 μm PET film provided with an ultraviolet shielding layer 2b by MW = 1900) by gravure coating.

When the component gradient of the active blocking layer 3 was examined by the XPS measurement method, the component gradient of the organic component and the inorganic component was confirmed. Figure 2 shows the XPS measurement results.

(2) Fabrication of photocatalytically active layer and production of printing substrate by adhesion treatment

E Chino receptacle Honoré Seo Norev 40.63g, 1 Purono Nonore mixed solvent [this 44.50g, 60 mass ^_0/0 probability acid 0.34 g, water 6.84 g, photocatalyst dispersion liquid (Titanium Kogyo "PC- 201, solid concentration 20.7 wt% ”) and 0.483 g colloidal silica dispersion (Nissan Chemical“ Snowtex IP A-ST, solid content concentration 30 wt% ”) 2.167 g are added, and the above solution (b) 5.00 g is added. The photocatalyst liquid (f) was prepared by adjusting the total solid content concentration to 1% by mass. The photocatalytic active layer 4 was formed by depositing this photocatalytic solution on a PET film provided with the active blocking layer 3 by gravure coating so as to have a film thickness of 40 nm. Furthermore, a PET release film (not shown) with a thickness of 30 μm was cold laminated on the photocatalytic active layer. A photocatalytic film as a printing substrate 1 was obtained.

[0055] (3) Evaluation of printing substrate

When the photocatalytic film as the printing substrate 1 was measured for total light transmittance and haze in the above-described measurement procedure, the total light transmittance was 91% and haze was 1.0%.

When this printed substrate was subjected to an accelerated weathering test for 2000 hours using a carbon arc sunshine weather meter (SWM) (S300, S300), the total light transmittance was 90% and the haze was 1.5%. Thus, it was confirmed that the substrate was a printing substrate with a reduced total light transmittance and a small increase in haze.

[0056] (4) Printing

On the surface 5 opposite to the photocatalytic active layer 4 of the printing substrate 1 obtained in (2) above, an ink jet printer (trade name 64S) manufactured by Seiko Instruments Inc. (SII) was used to prepare a solvent-based pigment (IP 6 A printed layer 9 on which an image of an arbitrary pattern is printed is formed using a series), and a release film 8 with an adhesive having an adhesive layer 7 is laminated on a 38 μm PET release film 6 from above. A 30 μm-thick PET release film (not shown) on the photocatalytic active layer was peeled off to obtain a printed product 10 shown in FIG. This printed matter 10 was placed on a power pole signboard along the national highway, and the change in the appearance of the stain and the design were confirmed one year later. The printing layer 9 was clear with little stains, and the design was maintained.

[0057] Comparative Example 1

Polyethylene terephthalate (PET) film substrate 2a with a thickness of 38 μm in advance on a 100 m PET film (Toray, TP-60) with a UV shielding layer 2b of HAL S, the same as in Example 1, on the top surface A comparative sample was prepared by laminating PET release film 8

(Evaluation as a printing substrate)

For this film, the total light transmittance and haze were measured in the same manner as in Example 1. The total light transmittance was 91% and haze was 1.0%.

This comparative sample was subjected to an accelerated weathering test for 2000 hours using a carbon arc sunshine weathermeter (SW M) (S300, S300), and the total light transmittance was 90%. 3. 0%. (printing)

On this PET film, an image of the same pattern as in Example 1 was printed using a solvent-based pigment (IP6 series) with an SII inkjet printer (trade name: 64S) as in Example 1. Later, the upper film was also applied with the release film. This was pasted on a power pole signboard along the national highway, and the change in the appearance of the dirt and the design was confirmed one year later. Dirt adhered and the designability was reduced.

Industrial applicability

The antifouling printing substrate of the present invention has an active blocking layer and a photocatalytic active layer with improved weather resistance and crack resistance formed on one surface of an organic substrate, and the other surface of the organic substrate is a printed surface. Since this is printed, the photocatalytic layer can be used as a printing substrate having an antifouling effect due to the self-cleaning action of the photocatalytic active layer without adverse effects on the printed layer.

In addition, the antifouling printed matter and the antifouling printed material of the present invention can maintain the design properties of the printed layer for a long period of time, so that it is possible to display outdoor art exhibitions, information on outdoor exhibits, advertising billboards, gardening Materials (print fences, flower beds, etc.), outdoor art display applications that use internal lighting similar to outdoor theaters, outdoor signage (for example, printing Christmas trees, printing banners, printing dolls, printing stained glass, self-made printing) It can be used effectively as a calendar, etc.) and decorative prints for pasting windows.

Claims

The scope of the claims

[1] An antifouling printing substrate characterized by having a photocatalytic active layer on one surface of an organic substrate through an active blocking layer and the other surface as a printing surface.

[2] The antifouling printing substrate according to claim 1, wherein the organic substrate is a transparent plastic film or plastic sheet having a thickness of 50 μm or more.

[3] The antifouling printing substrate according to claim 1 or 2, wherein an ultraviolet shielding layer is provided on a surface layer on one surface of the organic substrate.

[4] The active blocking layer includes a composite in which an organic polymer compound and a metal oxide compound are chemically bonded, and the content of the metal component continuously changes in the thickness direction of the layer. It has an inclined structure, and the concentration of the metal oxide compound component is substantially high at the interface with the photocatalytic active layer and the concentration of the organic polymer compound component on the surface in contact with the organic substrate. The substrate for antifouling printing according to any one of claims 1 to 3, wherein the substrate is a high organic-inorganic composite gradient layer.

[5] The active blocking layer is formed from a coating composition containing at least one hydrolysis condensate of (A) -metal alkoxide represented by the general formula (I). Nozzle force The antifouling printing substrate according to item 1.

MR ¹ (OR ² )--(I)

[6] The active blocking layer comprises (B) an amorphous acid / titanium-forming compound and (C) at least one selected from inorganic salts, organic salts, inorganic acid salts, and alkoxides. 6. The antifouling printing substrate according to claim 1, wherein the coating composition contains a compound of a metal other than titanium.

[7] The amorphous acid / titanium-forming compound as the component (B) has the general formula (II)

TiR ¹ (OR ² )

Four

(In the formula, R ¹ is an alkyl group, an alkyl group, an alkyl group, an aryl group, an aralkyl group or an acyl group, R ² is an alkyl group having 1 to 6 carbon atoms, and X is an integer of 0 to 2. Show.) 7. The antifouling printing substrate according to claim 6, which is formed by forming a coating composition for forming an amorphous acid / titanium coating film, which is represented by the following formula:

8. The antifouling printing substrate according to claim 6 or 7, wherein the metal other than titanium as the component (C) is aluminum and Z or zirconium.

[9] The antifouling printing substrate according to any one of [6] to [8], wherein the metal compound of component (C) is aluminum nitrate.

[10] When the active barrier layer includes, further, (D) an organic component capable of chemically bonding with a hydrolysis condensate of metal alkoxide, and a coating film is provided on the substrate, the metal alkoxide The antifouling property according to any one of claims 5 to 9, wherein the content of the hydrolysis condensate is formed from a self-gradient composition that is inclined from the surface of the coating film toward the substrate. Substrate for printing

[11] The photocatalytically active layer comprises (A), (C), (E) fine particles having a photocatalytic function, and

The antifouling printing substrate according to any one of claims 5 to 10, wherein the antifouling printing substrate is formed from a composition containing Z or silica fine particles.

12. The antifouling printing substrate according to any one of claims 1 to 11, wherein an ink receiving layer is provided on the other surface of the antifouling printing substrate.

[13] An antifouling printed matter obtained by printing on the antifouling printing substrate according to any one of claims 1 to 12.

[14] An antifouling printed matter comprising an adhesive layer on the surface of the printed matter for outdoor display according to claim 13.