JP2003048280A - Stainproof printing sheet and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stainproof printed sheet which shows high discoloration/ fading proofness and self-cleaning properties and can be used outdoors for a long time. SOLUTION: This stainproof printing sheet includes a sheet-like base material (this material may be formed of a base sheet such as a fibrous cloth and a resin-coated layer), a outermost face dirt-proof layer containing a photocatalytic substance and an intermediate protecting layer which is formed between the former two and protects the base material and a printed image against an action by a photocatalytic substance. In addition, the printing sheet has an image printed on the surface of the base material or has a transparent resin layer formed between the base material and the intermediate protecting layer or has an image printed on the transparent resin layer whose image-printed face is positioned opposite to the base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling print film material and a method for producing the same. More specifically, according to the present invention, colorful patterns, images such as characters are printed, and building members such as medium and large tents and shade tents, and advertisement sheets, billboard sheets, banners, tapestries, etc. Regarding a film material or a sheet that is preferably used as an outdoor advertising material, particularly, it has an excellent effect of preventing discoloration and fading of a printed image, and at the same time, the aesthetic appearance and appearance of the tent film material and the sheet are free from stains for a long period of time. Alternatively, the present invention relates to an antifouling print sheet that can be maintained in a small amount and a method for producing the same. In the present invention, the printed image includes all recorded images which are visible by visible light, such as characters, symbols, figures, patterns, patterns, photographs and solid printings, which are recorded by printing.

[0002]

2. Description of the Related Art A photocatalytic substance is applied to the surface of an inorganic compound product such as glass or an outer wall of a tile to oxidize and reduce oily stains on the surface of these products due to exhaust gas, smoke, etc. Cleaning technology that decomposes and removes by action has been put to practical use. In addition, recently, by applying a photocatalytic substance to the surface of daily necessities such as paper, fiber, film, plastic, etc., a odor that is in contact with or attached to the surface of these products or harmful substances floating in the atmosphere, A deodorizing technique and a cleaning technique for decomposing and removing dust and soot by a photocatalytic substance have been proposed and applied to uses such as filters, curtains and wallpapers. In the field related to hygiene, there is also proposed a product that can prevent the proliferation of fungi, molds, bacteria, etc. only by the redox action of the photocatalytic substance without using conventional antibacterial agents and antifungal agents. ing. However, in products in which these photocatalytic substances are adhered to the surface of the plastic material, due to the strong redox action of the photocatalytic substances, fields such as malodor, exhaust gas and dust in the air, fungi,
Not only the effect of killing molds, bacteria, etc., but also the decomposition and deterioration of the plastic that is the base material also progresses and is promoted at the same time, and the photocatalytic substance becomes There is a problem that it will fall out with the decomposed product of plastic, and for this reason,
The plastic material has a drawback that the photocatalytic effect cannot be maintained for a long time.

The strong redox action of the photocatalytic substance is
In addition to the decomposition and deterioration of the plastic material of the base material, various processing agents, additives, compounding agents, and other sub-components that are processed, added, and mixed into paper, fibers, films, plastics, etc. are also decomposed at the same time. At the same time, there is a problem that the product is deteriorated. An example of everyday photodegradation is the phenomenon that colorants used for coloring plastic products are discolored by exposure to sunlight, but when used in combination with a photocatalytic substance, color deterioration is further promoted and is noticeable. There are also colorants that This phenomenon of discoloration and fading can be easily discerned and recognized visually, so that it greatly affects the value and reliability of the product. For example, for shade tents and medium and large tents,
These tent film materials are composite sheet materials obtained by coating with a colored thermoplastic resin, and these tent film materials are used outdoors for a long period of 5 to 10 years. Therefore, the manufacturers of these tent film materials are continuing the research and development of the material design that enables the durability of 10 years or more. One of the targets for improving the durability is the long-term maintenance of the appearance and color of the tent film material. For example, even if the tent film material itself has a durability of 5 years or more, the weather resistance of the color of the tent film material does not reach 5 years, and the appearance of the tent structure will be extremely poor. The tent film material and its colorant need to be designed to have excellent durability and weather resistance, respectively. In particular, film materials for tents require colorful hues and abundant color variations, and the types and blending amounts of colorants used for these are hue, design, light transmission effect, cost efficiency, processing method, etc. There are various types according to.

Further, among these tent film materials, there is a print tent film material whose surface is printed. The print tent film material is a part of the surface of the sunshade tent, medium and large tents, or the whole surface, with a pattern or characters,
It is obtained by printing by a known technique such as gravure printing and silk printing. As a film material for a tent used for this printing, when a hue base material based on white is used like drawing paper, the contrast and outline of the printing become clear, and it is most preferred. However, the category of printing technology is not limited to those centered on white in particular. On the other hand, recently, inkjet printing capable of performing precise color printing directly on an output medium of a digital image captured by a digital camera or a computer has been rapidly developed. Ink jet printing is performed by various operating principles, for example, an electrostatic suction method, a method of applying mechanical vibration or displacement to ink by using a piezoelectric element, a method of heating and foaming the ink, and a method of utilizing the pressure of the ink. The small droplets of the ink jet are ejected toward the output medium such as the paper surface to attach and fix them to print and record images and characters. Recently, high quality full color printing compatible with inkjet printing printers and large size With progress in printing support and high-speed printing support, not only conventional output media such as paper and film, but also industrial fabric sheets such as fiber fabrics and composite sheets of fiber base fabric and thermoplastic resin Direct and precise printing becomes easier, and demand for printing on film materials for tents, advertising signboard sheets, building construction curing sheets, internally illuminated tents, roll screens, etc. is also increasing. That.

Specifically, for the above-mentioned applications, a soft polyvinyl chloride resin-coated sheet and a mesh containing a fiber cloth as a base material are used for reasons such as film material strength, outdoor durability, flame resistance, and versatility. Suitable for inkjet printing sheets. By using a solvent-based ink discharge type printer, it is possible to directly perform precise full-color printing on this soft polyvinyl chloride resin-coated sheet base material and mesh base material. For type printers, soft polyvinyl chloride resin coated sheets and those having an ink receiving layer formed on the surface of a fiber cloth are gradually becoming popular. Sheets printed on the surface of these base materials, especially those with limited application for advertising purposes, are intended for relatively short-term use of 1 to 3 months, and therefore have resistance to print weather resistance and stains. No special consideration has been given to it. However, it is used indoors and outdoors for a long period of 1 to 5 years in applications such as print tent film materials, print advertising signboard sheets, print building architectural curing sheets, print interior lighting tents, and print roll screens. Regarding the material, as described above,
Since it is used outdoors for 10 years, it is necessary to have weather resistance and stain resistance of the print corresponding to it. However, as a technique for improving the durability of these print film materials, there is no effective means other than a method of separately forming an antifouling film layer on the surface, and in this method, the resulting composite laminated sheet,
The interface adhesion durability between the printed surface and the film layer was insufficient.

Recently, in the field of these tent film materials, functional tent film materials utilizing the redox reaction of the photocatalytic substance as an antifouling function have been investigated. Only the technical measures for protection are enforced, and regarding the color maintenance of the colored substrate,
No special improvement has been made as to the problem of weather resistance of the colorant. Further, regarding the maintenance of the color of the coloring, no particular improvement has been made on the maintenance of the color of the printing layer formed on the surface of the sheet base material as the problem of the weather resistance of the printing ink in the print tent film material as well. It was In particular, for the print film material obtained by inkjet printing, it is difficult to define the photocatalytic substance, and at the same time, the print pattern is faded in the image within a short period due to the redox reaction of the photocatalytic substance. Not in practical use. Therefore, it is a composite sheet that can be used outdoors for a long time, such as medium- and large-sized tents and shade tents, and that is colorful and has excellent color retention, and that can maintain a beautiful printed pattern for a long time. An antifouling print sheet having the function of decomposing dirt by means of has not yet been put into practical use.

[0007]

DISCLOSURE OF THE INVENTION The present invention can be used outdoors for a long period of time and is printed with an image excellent in discoloration prevention property, and at the same time has a self-cleaning antifouling property. It is intended to provide a print sheet. The present invention also has an industrial material sheet having the above-mentioned performance and suitable for decorative applications such as tent film materials for medium and large-sized tents, shade tents, etc. It is intended to provide an antifouling print sheet suitable as an advertising material and a method for producing the same.

[0008]

The present invention has been studied and studied in view of the above-mentioned circumstances, and as a result, a specific print layer is provided on the surface of a substrate, and the print layer and the photocatalytic substance-containing layer are provided. By providing a specific resin layer in the middle of
Alternatively, by arranging a specific resin layer on which a specific printed layer is formed, between the base material and the photocatalytic substance-containing layer, a specific intermediate protective layer is provided to solve the problems that were difficult in the above-mentioned conventional techniques. The inventors have found that it is possible and completed the present invention.

The antifouling print sheet (1) of the present invention comprises
Of the sheet-like base material and the front and back surfaces of this sheet-like base material,
At least a photocatalytic substance formed on its surface
And an outermost surface antifouling layer containing, on the surface of the sheet-shaped substrate
The image is printed on the
Between the coated surface and the outermost antifouling layer.
The photo-catalytic substance is used to display the sheet-shaped substrate and the printed image.
Has an intermediate protective layer formed to protect it from the effects of quality.
It is characterized by Antifouling pretreatment of the present invention
The sheet (2) comprises a sheet-like base material and this sheet-like substrate.
Formed on at least the surface of both sides of the material
And an outermost surface antifouling layer containing a photocatalytic substance,
An image is printed on the surface of the sheet-shaped substrate,
The printed surface of the sheet-shaped substrate and the outermost surface
In the middle of the antifouling layer, contains a thermoplastic resin and is transparent.
A clear transparent resin layer was printed on the sheet-like substrate.
The transparent resin layer formed on the surface and the outermost surface
Between the antifouling layer, the transparent resin layer of the photocatalytic substance
That an intermediate protective layer is formed to protect it from action.
It is a feature. Antifouling print sheet of the present invention
(3) is a sheet-shaped substrate and both front and back sides of this sheet-shaped substrate
Surface, at least on the surface, and
The outermost surface antifouling layer containing a medium substance, and the sheet-shaped substrate
The sheet-like material between the material and the outermost antifouling layer.
A transparent transparent resin containing a thermoplastic resin on the surface of the substrate.
An oil layer is formed, and the transparent resin layer and the outermost surface are antifouling.
Between the layer and the transparent resin layer, the action of the photocatalytic substance
An intermediate protective layer for protection from the transparent tree is formed.
An image is pre-printed on the surface of the oil layer that is to be joined to the sheet-shaped substrate.
It is characterized by being installed. The present invention
Antifouling print sheet (1), (2) or (3)
The sheet-shaped base material is a fiber cloth or a plastic cloth.
It may be selected from film and synthetic paper. Antifouling property of the present invention
In the print sheet (1) or (2), the above-mentioned sheet
Substrate is formed on a base sheet and at least one surface thereof
And at least one layer of resin containing a thermoplastic resin
A coating layer and at least one of the resin coating layers
The image may be printed on the surface of the layer. The present invention
In the antifouling print sheet (3),
A substrate is formed on the base sheet and at least one side thereof.
And at least one layer of resin containing a thermoplastic resin.
It may be composed of a cover layer. Antifouling pretreatment of the present invention
In the front sheet (1), (2) or (3), the sheet
The base sheet of the sheet-shaped substrate is made of fiber cloth or plastic fabric.
It is preferably selected from film and synthetic paper. Starting
Akira antifouling print sheet (1), (2) or (3)
In the above, the sheet-shaped substrate may be colorless or
It may be colored. Antifouling print sheet of the present invention
In (1), (2) or (3), the colorless or
The colored sheet-shaped substrate may be transparent, or
It may be opaque. Antifouling print sheet of the present invention
In (1), (2) or (3), the image is
It has been printed by the Cudget printing method.
Is preferred. The antifouling print sheet (1) of the present invention,
In (2) or (3), the image is a gravure mark.
Printing, screen printing, offset printing, and transfer printing
Printed by at least one printing method selected from
It may be Antifouling print sheet of the present invention
In (1), (2) or (3), the printed
Image is an ink containing 20% by weight or more of inorganic pigment
It is preferable that it is more formed. Prevention of the present invention
Smell print sheet (1), (2) or (3) odor
The intermediate protective layer is made of a silicone resin or a fluorine resin.
Fat, melamine resin, epoxy resin, phosphase
Containing at least one selected from
Preferably there is. Antifouling print sheet of the present invention
In (1), (2) or (3), the intermediate protective layer
However, it is preferable to further contain a silicon compound. Book
Inventive antifouling print sheet (1), (2) or (3)
In the above, the silicon compound for the intermediate protective layer is polysiloxane.
Selected from xane, colloidal silica, and silica
And are preferred. The antifouling print sheet (1) of the present invention,
In (2) or (3), the intermediate protective layer is 10 or more.
Lower haze value (ASTM D1003) and / or 80
It is preferable to have a light transmittance of at least%. Of the present invention
In the antifouling print sheet (2) or (3), the above
The transparent resin layer has a haze value of 10 or less (ASTM D10
03) and / or having a light transmittance of 80% or more
Is preferred. The antifouling print sheet (1) of the present invention,
In (2) or (3), the transparent resin layer and the transparent resin layer
The formed composite layer consisting of the intermediate protective layer is
As a body, haze value of 10 or less (ASTM D100
3) and / or having a light transmittance of 80% or more
preferable. The antifouling print sheet (1) of the present invention,
In (2) or (3), the outermost surface antifouling layer is 9 to
70% by weight of the photocatalytic substance and 25-90% by weight
, Selected from metal oxide gel and metal hydroxide gel
At least one and 1 to 20% by weight of a silicon compound
It is preferable to contain. Antifouling print sheet of the present invention
(1), (2) or (3), the outermost surface is antifouling
The photocatalytic material of the layer is titanium oxide (TiO 2₂ ), Peroxide
Titanium (peroxotitanic acid), zinc oxide (ZnO),
Tin oxide (SnO₂ ), Strontium titanate (SrT
iO₃ ), Tungsten oxide (WO₃ ), Bismuth oxide
(Bi₂ O ₃ ), And iron oxide (Fe₂ O₃ ), Fine particles of
And one or more of the above compounds in a porous carrier.
At least one selected from the porous fine particles
Preferably. Antifouling print sheet of the present invention
The manufacturing method of (1) is
Printing an image on at least the surface of the sheet
On the printed surface of the sheet-shaped substrate,
Protect printed images from the action of photocatalytic substances
An intermediate protective layer for forming a light protective film on the intermediate protective layer.
Forming an outermost surface antifouling layer containing a medium substance,
To do. Antifouling print sheet (2) of the present invention
The manufacturing method for the
Also print an image on the surface of the sheet-shaped substrate
The printed surface contains thermoplastic resin and is transparent
Transparent resin layer is formed on the transparent resin layer.
An intermediate protective layer for protecting the resin layer from the action of photocatalytic substances.
A protective layer is formed, and a photocatalytic substance is contained on the intermediate protective layer.
The outermost surface antifouling layer is formed.
It Manufacturing method of antifouling print sheet (3) of the present invention
Method (1) uses a transparent film containing a thermoplastic resin.
Print the image on one side, and
Among them, at least the surface of the transparent film
Laminated surfaces are laminated, and the transparent film is laminated
Of the transparent resin layer on the non-printed side of
Forming an intermediate protective layer to protect against the action of catalytic substances
The outermost surface protective layer containing a photocatalytic substance is formed on the intermediate protective layer.
It is characterized by forming a dirty layer. The present invention
The method (2) for producing the antifouling print sheet (3) is
An image is displayed on one side of a transparent film that contains a plastic resin.
Print and light it on the other side of the transparent film.
Forming an intermediate protective layer to protect against the action of catalytic substances
However, at least the front and back sides of the sheet-shaped substrate
Stick the printed side of the transparent film on the surface
The outermost surface protective layer containing a photocatalytic substance is formed on the intermediate protective layer.
It is characterized by forming a dirty layer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION An antifouling print sheet (1) of the present invention comprises a sheet-like base material, and a photocatalytic substance formed on at least the surface of the front and back surfaces of the sheet-like base material. Having an outermost surface antifouling layer containing, an image is printed on the surface of the sheet-shaped substrate, between the printed surface of the sheet-shaped substrate, and the outermost surface antifouling layer, An intermediate protective layer for protecting the sheet-shaped substrate and the printed image from the action of the photocatalytic substance is formed. Further, the antifouling print sheet (2) of the present invention comprises a sheet-like base material,
Of the front and back surfaces of this sheet-like substrate, it has an outermost surface antifouling layer which is formed on at least the surface thereof and contains a photocatalytic substance, and an image is printed on the surface of the sheet-like substrate. , A printed surface of the sheet-shaped substrate, and a transparent transparent resin layer containing a thermoplastic resin in the middle of the outermost surface antifouling layer, on the printed surface of the sheet-shaped substrate. An intermediate protective layer that is formed and protects the transparent resin layer from the action of the photocatalytic substance is formed between the transparent resin layer and the outermost surface antifouling layer. is there. Furthermore, the antifouling print sheet (3) of the present invention comprises a sheet-like substrate and the outermost surface of the sheet-like substrate, which is formed on at least the surface of the sheet and has a photocatalytic substance. A layer, in the middle of the sheet-shaped substrate and the outermost surface antifouling layer, on the surface of the sheet-shaped substrate, containing a thermoplastic resin, and a transparent transparent resin layer is formed, and Between the transparent resin layer and the outermost surface antifouling layer, an intermediate protective layer for protecting the transparent resin layer from the action of the photocatalytic substance is formed, and the transparent resin layer, in the sheet-shaped substrate. An image is printed on the surfaces to be joined. The sheet-shaped substrate may be selected from a fiber cloth, a plastic film and a synthetic paper, or a base sheet and at least one resin coating formed on at least one surface thereof and containing a thermoplastic resin. It may be composed of layers.

The antifouling print sheet (1) of the present invention comprises
An image is printed on at least the surface of the front and back surfaces of the sheet-shaped substrate, and the sheet-shaped substrate and the printed image are formed on the printed surface of the sheet-shaped substrate from the action of the photocatalytic substance. It is manufactured by forming an intermediate protective layer for protection and forming an outermost surface antifouling layer containing a photocatalytic substance on the intermediate protective layer. The antifouling print sheet (2) of the present invention has an image printed on at least the front surface and the back surface of a sheet-like substrate, and contains a thermoplastic resin on the printed surface of the sheet-like substrate. , And a transparent transparent resin layer is formed, and an intermediate protective layer for protecting the transparent resin layer from the action of the photocatalytic substance is formed on the transparent resin layer, and the photocatalytic substance is formed on the intermediate protective layer. It is manufactured by forming an outermost surface antifouling layer containing. The antifouling print sheet (3) of the present invention contains a thermoplastic resin and has an image printed on one surface of a transparent film, and the transparent film is formed on at least the surface of both sides of the sheet-like substrate. Laminating the printed surface of the film, the transparent film laminated, on the non-printed surface, to form an intermediate protective layer for protecting the transparent resin layer from the action of the photocatalytic substance, It is manufactured by forming an outermost surface antifouling layer containing a photocatalytic substance on the intermediate protective layer.

1 to 4 are cross-sectional explanatory views showing a laminated structure of various aspects of an antifouling print sheet of the present invention. In the antifouling print sheet shown in FIG. 1,
The ink image 2 is printed on the surface of the sheet-shaped substrate 1, the intermediate protective layer 3 is formed on the image-printed surface of the substrate 1, and the intermediate protective layer 3 is formed on the entire surface of the intermediate protective layer 3. The outer surface antifouling layer 4 (containing a photocatalytic substance) is formed. In the antifouling print sheet shown in FIG. 2,
The transparent resin layer 5 is formed on the surface of the sheet-shaped substrate 1 on which the ink image 2 is printed, and the intermediate protective layer 3 and the outermost surface antifouling layer 4 are sequentially formed on the transparent resin layer 5.

The antifouling print sheet shown in FIG.
It has a layered structure similar to that shown in FIG.
The sheet-shaped substrate 1 is composed of a substrate sheet 1a (fiber cloth or film) and resin coating layers 1b and 1c covering both front and back surfaces thereof, and an ink image 2
Is printed on the surface resin coating layer 1b. Figure 4
The antifouling print sheet shown in FIG. 2 has a laminated structure similar to that shown in FIG.
Is composed of a base sheet 1a and resin coating layers 1b and 1c covering both front and back surfaces thereof, and an ink image is printed on one surface of the transparent resin layer 5, The surface of the transparent resin layer 5 on which the ink image 2 is printed is the surface resin coating layer 1 of the sheet-shaped substrate 1.
It is joined to b.

The sheet-like substrate used in the present invention includes a colorless or colored opaque plastic film, a colorless or colored transparent plastic film,
It may be made of fiber cloth or synthetic paper, or
It may be composed of a base sheet and a resin coating layer formed on at least one surface thereof and containing a thermoplastic resin, and the base sheet can be selected from fiber cloth, plastic film and synthetic paper. In particular, it is preferable that the base sheet made of fiber cloth is coated with a thermoplastic resin.

Examples of the colored opaque film and transparent (colored) film are polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene resin, polypropylene resin, polymethylpentene resin, ionomer resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer. Molded from thermoplastic resin such as resin, polystyrene resin, polymethylmethacrylate resin, nylon resin, polyester resin, polyethylene terephthalate resin, amorphous polyethylene terephthalate resin, polycarbonate resin, polyurethane resin, silicone resin, fluorine-based copolymer resin Films and sheets, and these films and sheets may be films or sheets having a multilayer structure composed of two or more types of thermoplastic resin layers described above. These film / sheets can be produced by a known film / sheet production method, for example, T-die extrusion method, T-die coextrusion method, calender method, inflation method, casting method and the like. Further, as the synthetic paper, a film obtained by adding a foaming agent to a thermoplastic resin such as polystyrene resin, polyethylene resin, polypropylene resin, polyester resin, polyethylene terephthalate resin, or polyamide resin to contain fine bubbles, or the thermoplastic resin 3 white pigment fillers on resin
A sheet produced by an internal paper-making method such as stretching a film added with 0 to 40% by weight or a film added with 30 to 40% by weight of a white pigment filler to generate microvoids, or an adhesive on the surface of the film A sheet coated with a white pigment using, or a sheet produced by a surface paper-making method such as roughening the film surface by sandblasting can be used. The weight per unit area of these synthetic papers is not limited, but those of 50 to 450 g / m ² are suitable for the present invention.

During the production of these colored opaque films, transparent (colored) films, and synthetic paper, pigments such as organic pigments, inorganic pigments, and metal powder pigments are added to the raw material thermoplastic resin for coloring. You can also In particular, the pigment is preferably selected from only inorganic pigments and colored. Alternatively, the total content of the inorganic pigment is preferably 70% by weight or more based on 100 parts by weight of the total amount of the pigment used. If the total content of the organic pigments exceeds 30% by weight with respect to 100 parts by weight of the total amount of pigments used for coloring the plastic film or sheet, the decomposition resistance to the photocatalytic substance becomes insufficient and the film or sheet changes. May cause fading. Further, the transparent (colorless or colored) film is a film that is not colored by any of an inorganic pigment and an organic pigment, or only the above inorganic pigment, or an inorganic pigment and an organic pigment within the above blending ratio range. A haze value (ASTM D1003) of 10 is obtained by coloring with a small amount of a mixture with a base pigment.
It has transparency below or below 80% of light transmittance. The thickness of these films or sheets includes
There is no particular limitation, but it is generally preferably 100 to 1000 μm, and particularly preferably 200 to 500 μm.

As the fiber cloth, any of woven cloth, knitted cloth and non-woven cloth can be used. Woven fabrics include plain weave (having a minimum constitutional unit of at least two warps and wefts) and twill weave (having a minimum constitutional unit of at least three warps and wefts: 3 sheets, diagonal 4 1 sheet italic, 5 sheet italic, 6 sheet italic,
8-slanted pattern), satin fabric (having a minimum constitutional unit using a minimum of 5 warp yarns and 5 weft yarns: regular skipping of 2 jumps, 3 jumps, 4 jumps, 5 jumps, etc.) and the like can be preferably used.
In addition to the above, the woven fabric may be a modified plain woven fabric, a modified twill woven fabric, a modified satin woven fabric, etc. obtained by an expansion method, an exchange method, an arrangement method, a placement method, a splicing method, and / or a cutting method, and the like. Furthermore, honeycomb fabrics, pear fabrics, torn diagonal fabrics, day and night satin fabrics, woven fabrics (sachet fabrics, gauze fabrics), sewn fabrics, double fabrics and the like can be mentioned. Among these, plain weave fabrics are particularly preferably used because they have excellent balance of physical properties in the weft direction. Russell knitting is preferred as the knitted fabric, and spunbonded nonwoven fabric using long fibers can be used as the nonwoven fabric.

The warp and weft of the fiber cloth are synthetic fibers,
The fibers may be woven by any of natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these, but when a fiber cloth is directly printed, natural fibers such as cotton, hemp, Regenerated fibers such as silk, for example,
Fiber cloths made of rayon and synthetic fibers such as polyvinyl alcohol fibers, polyamide fibers and polyester fibers are preferred. When a fiber cloth is used as the base sheet and is surface-coated with a thermoplastic resin, the fibers for the base sheet include polypropylene fiber, polyethylene fiber, polyvinyl alcohol fiber, polyester fiber, nylon fiber, polyamide. Fibers, acrylic fibers, polyurethane fibers, or mixed fibers thereof can be used. It is used for a sheet-shaped base material or a base sheet. The fiber yarn may be a monofilament yarn, a multifilament yarn, a short fiber spun (span) yarn, a split yarn, a tape yarn, or the like. Further, as the inorganic fiber for the base sheet, a multifilament yarn such as glass fiber, silica fiber, alumina fiber, carbon fiber or the like can be used. In the present invention, among these fiber yarns, high versatility, polyester fiber, nylon fiber, wholly aromatic polyamide fiber, glass fiber, which has excellent physical property balance such as tensile strength, tear strength, and heat creep property, It is preferable to use a multifilament plain woven fiber woven fabric or a spun plain woven fiber fabric woven from these mixed fibers, mixed fibers, and the like. The weaving of these woven fabrics is performed by shuttle loom, shuttleless loom (rapier method, gripper method,
Weaving can be performed using a conventionally known loom such as a water jet method or an air jet method. Known fiber treatments such as scouring treatment, bleaching treatment, dyeing treatment, softening treatment, water repellent treatment, waterproof treatment,
Antifungal treatment, flameproof treatment, fried treatment, calendar treatment,
Also, it is preferable to use it after treatment such as binder resin treatment.

The fiber cloth used in the present invention is preferably a short fiber spun cloth (span) or a woven fabric composed of multifilament yarns. The number of the short fiber spun yarns is 591 dtex (10th count). (English)) ~ 97dt
Ex (60th) range, especially short fibers such as 591dtex (10th), 422dtex (14th), 370dtex (16th), 295dtex (20th), 246dtex (24th), 197dtex (30th) It is preferable to use spun yarn. Short fiber spun yarn thickness is 370
If it is smaller than dtex (60th), the tear strength of the obtained sheet may be insufficient, and it is 591dt.
When it is larger than ex (10th count), the breaking strength and tear strength of the obtained sheet are improved, but the yarn diameter becomes large and the unevenness of the woven intersection increases, so that the smoothness preferable for printing may be insufficient. . These short fiber spun yarns include single yarns, twin yarns, twisted yarns of three or more single yarns, two-plied yarns thereof, or two-plied yarns as warp yarns and weft yarns. A short fiber spun cloth obtained by driving 30 to 160 strands in 4 mm (1 inch) is preferable, and particularly 591 to
295 dtex (10-20 count) single yarn, or 591-
25.4 with twin yarn of 295 dtex (10-20 count)
50 to 70 warps and 40 to 60 wefts per mm (1 inch)
The short fiber spun cloth obtained by striking the yarn at the woven density of the book can be most suitably used. In addition, the twisting of the yarn includes a single twisted yarn, a single twisted yarn, a single twisted yarn or two or more single twisted yarns which are twisted by S twisting (right) or Z twisting (left) by aligning single yarns or two or more single yarns. Any twisted yarn may be used, such as various twisted yarns in which two or more twisted yarns that are aligned and plied together are aligned and plied, and other strongly twisted yarns. The number of twists of these twisted yarns is 500 to 2000 times for a single twisted yarn and a regular twisted yarn of various twisted yarns /
m, and the number of times of strong twist yarn is preferably 2000 times or more / m. Further, as the range of the twist coefficient of the proportional constant representing the relationship between the yarn count and the twist number, a sweet twist having a twist coefficient of about 1.3 to 3.0, a normal twist having a twist coefficient of about 3.0 to 4.5, Twist factor 4.
Strongly twisted yarns of about 5 to 5.5 are mentioned, and in particular, a twist coefficient of 3.
It is preferable that the normal twisted yarn is in the range of 0 to 4.5.
The porosity (blank ratio) of the short fiber spun cloth is 0 to 8%.
Those of are preferred. If the porosity exceeds 8%, the content of the fiber yarns in the warp and weft direction becomes too small, and the dimensional stability of the obtained sheet may become insufficient.
Further, the tear strength of the sheet and the penetration resistance to the protrusions become insufficient, which may be unsatisfactory in practice. The porosity can be obtained as a value obtained by subtracting 100 from the area of the fiber yarn occupying in the unit area of the fiber cloth as a percentage. For measuring the porosity, it is preferable to use 10 cm in the longitudinal direction × 10 cm in the weft direction as a unit area. The basis weight of the short-fiber spun cloth for a sheet-shaped substrate or base sheet is preferably 100 to 600 g / m ² .

Further, as the fiber cloth used in the present invention, a woven cloth made of multifilament yarn can also be preferably used. For multifilament yarn, 1
Those having a range of 11 to 2222 dtex (100 to 2000 denier), particularly 138 to 1111 dtex (125 to 100)
A 0 denier multifilament yarn is preferred. If the filament yarn is thinner than 111 dtex (100 denier), the tear strength of the resulting sheet may be insufficient, which is 2222 dtex (2000 denier).
If it is thicker than that, the breaking strength and tear strength of the obtained sheet are improved, but the yarn diameter becomes thicker and the unevenness at the woven intersection increases, so that smoothness suitable for printing may not be obtained.
The densities of warp and weft of the woven fabric made of these multifilament yarns are not particularly limited.
A woven fabric obtained by driving 10 to 80 threads of 2 dtex (100 to 2000 denier) as warp and weft for 25.4 mm (1 inch) can be used. For example, 278dtex (2
50 denier) 25.4 mm with multifilament yarn
(1 inch) 18 to 44 lines, 555.6 to 1111.
1-dtex (500-1000 denier) multifilament yarn 25.4 mm (1 inch) 14-38 yarns, 1
A non-blank plain weave fabric or a non-blank plain weave fabric is suitable which is obtained by using a 666.7 dtex (1500 denier) multifilament yarn and a striking design of about 10 to 28 yarns per 25.4 mm (1 inch). These multifilament yarns may be untwisted or twisted. The basis weight of these woven fabrics is 50 to 400 g / m.
² is suitable. Further, it is preferable that the multifilament woven fabric has a porosity (void) of 0 to 30%. If the porosity exceeds 30%, the content of the fiber yarns in the warp and weft direction becomes too small, and the dimensional stability of the obtained sheet may become insufficient. Furthermore, the tear strength of the sheet and the penetration resistance to protrusions In some cases, it becomes unfavorable because it may cause a problem in practical use because the property may become insufficient. The porosity can be obtained as a value obtained by subtracting 100 from the area of the fiber yarn occupying in the unit area of the fiber cloth as a percentage. To measure the porosity, 10 cm in the longitudinal direction and 10 cm in the weft direction
Is preferably used as the unit area.

The short fiber spun yarn or multifilament yarn used in the present invention is preferably polyester fiber in consideration of its versatility. Specific examples of the polyester fiber include polyethylene terephthalate (PET) obtained by polycondensation of terephthalic acid and ethylene glycol, and polybutylene terephthalate (PBT) obtained by polycondensation of terephthalic acid and butylene glycol. Among them, polyester fibers spun from polyethylene terephthalate resin can be preferably used from the viewpoint of fiber strength and melt spinnability. Among the fiber cloths used in the present invention, a short fiber spun cloth having a porosity (blank ratio) of 0 to 8%, particularly a short fiber spun cloth having a porosity of 5% or less, is to be coated with a thermoplastic resin described below. ,
Depping process using a thermoplastic resin solution prepared by dissolving in an organic solvent, a thermoplastic resin emulsion (latex) emulsion-polymerized in water, or a dispersion resin in which the thermoplastic resin is forcibly dispersed in water and stabilized. It is preferable to use (double-sided processing on fiber cloth) or coating processing (single-sided processing or double-sided processing on fiber cloth). In addition, the porosity (blank ratio) 0 to
To apply a thermoplastic resin coating described below to a 30% multifilament woven fabric, particularly a multifilament woven fabric having a porosity of 5% or less, a thermoplastic resin solution prepared by dissolving in an organic solvent or emulsified in water A thermoplastic resin emulsion (latex) prepared by polymerization, or a dispersion resin in which a thermoplastic resin is forcibly dispersed in water and stabilized is used for depping (double-sided processing on fiber cloth) or coating (fiber). One-sided processing on cloth,
Alternatively, it is preferable to perform double-sided processing. Porosity 5-3
The 0% multifilament woven fabric is formed by laminating a film molded product obtained from the below-mentioned thermoplastic resin on one or both sides of the woven fabric with an adhesive or by thermocompression bonding to form a thermoplastic resin coating layer. Suitable for forming.

It is preferable that at least one surface of the above-mentioned fiber cloth is surface-coated with a thermoplastic resin, and particularly in the present invention, that both surfaces of the fiber cloth are surface-coated with a thermoplastic resin, it is waterproof. Is preferable in that the heat fusion bondability is excellent. Specific examples of the coating thermoplastic resin include polyvinyl chloride resin, polyolefin resin, polyurethane resin, acrylic resin, vinyl acetate resin, styrene resin, polyester resin, polyamide resin, and fluorine resin. resin,
And copolymer resins of these resins (thermoplastic elastomers), and the like. These thermoplastic resins may be used alone, or may be used by blending two or more kinds, or may be used by laminating two or more layers. it can. In the present invention, as the thermoplastic resin for covering the fiber cloth, a polyvinyl chloride resin is most preferably used because it is excellent in resin properties, resin durability, moldability and versatility. Further, especially in consideration of environmental problems, when a halogen-free industrial material sheet that does not emit hydrogen halide gas at the time of incineration is desired, a polyolefin resin and a polyurethane resin are most preferably used. It

The above polyvinyl chloride resins include vinyl chloride homopolymers and vinyl chloride copolymer resins, specifically, polyvinyl chloride resins, vinyl chloride-ethylene copolymer resins, vinyl chloride-resin. Vinyl acetate copolymer resin, vinyl chloride-vinyl ether copolymer resin, vinyl chloride-vinylidene chloride copolymer resin, vinyl chloride-maleic acid ester copolymer resin, vinyl chloride- (meth) acrylic acid copolymer resin, Examples thereof include a vinyl chloride- (meth) acrylic acid ester copolymer resin and a vinyl chloride-urethane copolymer resin. These resins may be used alone or in combination of two or more. In the present invention, the thickness of the surface coating layer of the thermoplastic resin is not particularly limited, but the surface coating layer (amount of solid content) is 50 to 50.
0 g / m ^2, it is preferably formed particularly 100~350g / m ^2. If the coating amount of the surface coating layer is less than 50 g / m ² , the abrasion resistance of the coating layer may not be sufficiently obtained, and if it exceeds 500 g / m ² , the mass of the sheet becomes too heavy. Sometimes.

The above polyvinyl chloride resin has a number average molecular weight of P = 700 to 3800, preferably 1000 to 2000, obtained by emulsion polymerization, or a polyvinyl chloride resin obtained by suspension polymerization, and has a number average molecular weight of P.
= 700 to 3800, preferably 1000 to 2000, straight vinyl chloride resin. The copolymer component contained in the vinyl chloride copolymer resin (number average molecular weight, P = 700 to 3800) is preferably 2 to 30% by weight. In the present invention, when a polyvinyl chloride resin is used as the thermoplastic resin that coats the fiber cloth, a known soft blend can be used as the blend, but as a plasticizer used in the soft blend, in particular, In addition to the phthalate ester plasticizer having an average molecular weight of 380 to 560, the average molecular weight is 900 to 6000, particularly 100 from the viewpoint of the plasticizer volatilization prevention effect.
It is preferable to contain a polyester-based plasticizer of 0 to 3200, and from the viewpoint of the plasticizer volatilization prevention effect, ethylene having an average molecular weight of 10,000 or more, particularly 20,000 or more.
Vinyl acetate-carbon monoxide terpolymer resin, ethylene-
It is preferable to use a polymer plasticizer such as a (meth) acrylic acid ester-carbon monoxide terpolymer resin. As the polyester-based plasticizer, those arbitrarily synthesized from dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and phthalic acid and ethylene glycol, 1,2-butanediol, 1,6-hexanediol can be used. . Examples of preferable use of these plasticizers are 1). There is a composition containing 40 to 100 parts by weight as a total amount of the plasticizer with respect to 100 parts by weight of the paste vinyl chloride resin, and 10 to 50% by weight of the plasticizer is preferably a polyester plasticizer. This composition has an organic solvent added to it,
The liquid viscosity can be adjusted to be suitable for coating and depping. 2). The total amount of plasticizer is 5 per 100 parts by weight of straight vinyl chloride resin.
It contains 0 to 100 parts by weight of a plasticizer,
Preferably, 100% by weight is a polyester plasticizer, and the compound composition is calendered
-It is formed into a film by subjecting it to die extrusion molding or the like.
3). For 100 parts by weight of straight vinyl chloride resin,
The total amount of the plasticizer is 60 to 140 parts by weight, and 30 to 100% by weight of the plasticizer is preferably a polymer plasticizer, and the compound composition is calendered or T-die. It is used for extrusion molding to form a film. [Note] In 2) and 3), the paste vinyl chloride resin may be used instead of the straight vinyl chloride resin. In the above vinyl chloride resin composition, the stabilizer may be appropriately selected from known ones and used. , If necessary, lubricant, flame retardant, foaming agent, antistatic agent, surfactant, water repellent, oil repellent, cross-linking agent, curing agent, filler, mildew proofing agent, antibacterial agent, UV absorber, antioxidant Known additives such as agents can be used.

The above-mentioned polyolefin resin includes an olefin-based single resin and an olefin-based copolymer resin, specifically, polyethylene resin, polypropylene resin, ethylene-α-olefin copolymer resin, ethylene-vinyl acetate. Copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin, ethylene-propylene copolymer resin, reactor polymer resin of polypropylene resin and ethylene-propylene copolymer resin, polypropylene resin and ethylene-propylene -Reactor-polymerized resin with a conjugated diene-based copolymer resin and the like can be mentioned, and these resins may be used alone or in combination of two or more kinds. Among these polyolefin-based resins, particularly ethylene-α-olefin copolymer resins include ethylene by a gas phase method, a slurry liquid phase method, or a high pressure method in the presence of a Ziegler-Natta catalyst or a metallocene catalyst. And a C3-C18 α-olefin are preferably copolymerized, and this copolymer has a density of 0.880 to 0.920 g / cm ³ , and a melt index of 0.3 to 10 g / cm ³ . Those of 10 min are preferably used, and examples of the α-olefin monomer include propylene, butene-1,4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-.
1, decene-1, tetradecene-1, hexadecene-
1, heptadecene-1, octadecene-1, etc. are used. These resins are formed into a film by calendering, T-die extrusion or the like.

The ethylene-vinyl acetate copolymer resin is produced by radical copolymerizing ethylene monomer and vinyl acetate monomer, and has a vinyl acetate component content of 6 to 35% by weight, preferably 15 to It is preferably 30% by weight of an ethylene copolymer resin, and
The ethylene- (meth) acrylic acid (ester) copolymer resin is produced by radical copolymerization of an ethylene monomer and a (meth) acrylic acid monomer, and
An ethylene- (meth) acrylic acid copolymer resin having a content of the (meth) acrylic acid component of 6 to 35% by weight, preferably 15 to 30% by weight is preferable, and an ethylene monomer and a (meth) acrylic acid ester monomer are preferable. And a content of the (meth) acrylic acid ester component is 6 to 35% by weight, preferably 15 to
30% by weight of ethylene- (meth) acrylic acid ester copolymer resin and the like are preferable, and these may be used alone or as a mixture of two or more thereof. Specific examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and glycidyl (meth) acrylate. The density of these ethylene-based copolymer resins is preferably 0.925 to 0.960 g / cm ³ , and the melt index thereof is 0.3 to 1
It is preferably 0 g / 10 min. These resins are film-formed by calendering, T-die extrusion or the like.

The above-mentioned polyolefin resin is a soft component such as ethylene-propylene rubber or ethylene-propylene-conjugated diene rubber for the purpose of improving its flexibility and processability, and is crosslinked with the above-mentioned polyolefin resin. An olefin-based thermoplastic elastomer (TPO) which is a vulcanized alloy may be contained. In particular, from the purpose of softening and resin modification of the polyolefin resin,
It is preferable to use a styrene copolymer resin blended with the polyolefin resin. The styrene copolymer resin is an ABA type styrene block copolymer resin (A is a styrene polymer block, B is a butadiene polymer block, an isoprene polymer block, or a vinylisoprene polymer block). ), AB
Type styrene block copolymer resin (A and B have the same meaning as above), styrene random copolymer resin, and hydrogenated resin of these styrene copolymer resins (one in which the double bond is replaced by hydrogen). is there. Examples of commercially available products thereof include Shell. Chemical Company's styrene copolymer resin (trademark: Clayton G), Asahi Kasei Corporation's styrene copolymer resin (trademark: Tuftec), Kuraray's styrene copolymer resin (trademark: Hybler, Trademark: Septon), styrene copolymer resin of Japan Synthetic Rubber Co., Ltd. (trademark: Dynaron), and the like. These styrene-based copolymer resins are preferably used by blending 10 to 50 parts by weight with respect to 100 parts by weight of the polyolefin-based resin. In these formulations, if necessary, a stabilizer, a lubricant, a flame retardant, a foaming agent, an antistatic agent,
Known additives such as a surfactant, a cross-linking agent, a curing agent, a filler, a fungicide, an antibacterial agent, an ultraviolet absorber and an antioxidant can be used. These resins are film-formed by calendering, T-die extrusion or the like.

The thermoplastic resin for coating the surface of the fiber cloth includes polyethylene resin, polyvinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl acetate-acrylic acid ester copolymer resin, vinyl acetate-maleic acid. Dibutyl copolymer resin, vinyl acetate-ethylene-vinyl versatate copolymer resin, (meth) acrylic acid (ester) copolymer resin, acrylic ester-styrene copolymer resin, polyester polyurethane resin, polyether polyurethane Resins, polycarbonate-based polyurethane resins, polycaprolactone-based polyurethane resins, acrylic-based polyurethane resins, polyester-based resins, polyamide-based resins, ionomer resins, etc., and mixtures thereof are used, and further, in the polymer molecule of these resins. Hydroxyl group, carbo Acid include emulsion resins such as modified products obtained by introducing and quaternary ammonium base or dispersion resin. Further, as the thermoplastic resin emulsion, a hybrid emulsion having a core-shell type heterophasic structure can also be used. Also, a butadiene polymer,
Of thermoplastic rubbers such as styrene-butadiene copolymer, carboxyl modified styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methylmethacrylate-butadiene copolymer, and 2-vinylpyridine-styrene-butadiene copolymer. Latex can also be used. To form the resin coating layer of the sheet of the present invention, these thermoplastic resins are solubilized in an organic solvent, or by using a resin-containing solution dispersed, or by emulsion polymerization of the thermoplastic resin in water. Using a dispersion-stabilized emulsion resin or a dispersion resin in which the above thermoplastic resin is forcibly dispersed in water, gravure coating method, microgravure coating method, comma coating method, roll coating method, reverse roll coating method, bar coating Method, knife coating method, kiss coating method, flow coating method, or other known coating method, or a dipping method or the like, the resin solution is uniformly applied to the surface of the substrate, and this can be dried to form a resin coating layer. . In the present invention, the thickness of the surface coating layer of the thermoplastic resin is not particularly limited, any of the above coating method, or
Surface coating layer (amount of solids attached) depending on the combination
Is 50 to 500 g / m ² , especially 100 to 350 g / m
It is preferably formed into ² . Surface coating layer is 50g /
If it is less than m ² , the abrasion resistance of the coating layer may not be sufficiently obtained, and if it exceeds 500 g / m ² , not only the number of coating treatments increases, but also the The weight may be too heavy.

The above ethylene-vinyl acetate copolymer resin
For Marujon, the emulsion polymerization of ethylene and vinyl acetate
The resulting product contains 60 to 90% by weight of a vinyl acetate component.
Those that have are included. Vinyl acetate-ethylene-
The vinyl versatate copolymer resin emulsion is
Milk of ethylene with vinyl acetate and vinyl acetate
60-90% by weight vinyl acetate obtained by chemical polymerization
And those containing a vinyl versatate component
To do. In addition, ethylene- (meth) acrylic acid (ester
) As a copolymer resin emulsion, ethylene and
Also obtained by emulsion polymerization with (meth) acrylic acid
Emulsified weight of ethylene and (meth) acrylic acid ester
Obtained by the combination of (meth) acrylic acid
Tellurium) emulsion tree with a content of 60-90% by weight
Fats. What is (meth) acrylic acid ester?
Physically methyl (meth) acrylate, (meth) acrylic acid
Ethyl, butyl (meth) acrylate, (meth) acrylic
Glycidyl acid and the like. In addition, ethylene- (meth) a
As modified resin of acrylic acid (ester) copolymer resin
Is an olefin-α, β-unsaturated carboxylic acid copolymer
As a base resin, 5 to 90% of its carboxyl groups
Ionomer resin dispersions neutralized with metal ions
Can also be used, and the metal ion that neutralizes the ionomer resin can be used.
On, Zn ⁺⁺, Na⁺ Is a metal ion. Well
Dispersion resin contains vinyl acetate component
Ethylene-vinyl acetate copolymer in an amount of 10 to 30% by weight
Resin and (meth) acrylic acid (ester) component content
Of 10 to 30% by weight of ethylene- (meth) acrylic acid
(Ester) Copolymer Forcing a copolymer such as resin into water
A dispersed product can also be used. These emulsions and
And the resin solid content of the dispersion resin is limited
However, the resin solid content is 20 to 70% by weight, especially 30
It is preferably ˜50% by weight.

Ethylene-vinyl acetate copolymer resins, vinyl acetate-ethylene-vinyl versatate copolymer resins, and ethylene- (meth) acrylic acid (ester) copolymer resins which can be used after being dissolved or dispersed in an organic solvent. Is produced by a radical polymerization method of ethylene and a copolymerization component, the content of the copolymer component is 18 to 38% by weight, and the melt index is 1.0 to 10 g / 10 min.
The copolymer resin of is preferably used. The copolymer component content is less than 18, or the melt index is 1.
If it is less than 0, it may be difficult to dissolve in an organic solvent, and the content of the copolymer component exceeds 38,
Alternatively, if the melt index exceeds 10, it may be soluble in an organic solvent, but the resin strength of the resin layer formed by coating may be reduced, and the resin coating layer may become sticky, causing the sheet to wind. Blocking may occur easily during removal. The solid content of these thermoplastic resins with respect to the organic solvent is not particularly limited, but it is preferable to contain 10 to 50% by weight of one or more of the above thermoplastic resins.

Examples of the styrene-acrylic acid copolymer resin include styrene resins obtained by radical polymerization of styrene and (meth) acrylic acid (ester). For example, carbon number of styrene and alkyl group is 2
~ 18 alkyl methacrylate, alkyl groups having 1 to 18 carbon atoms, and α, β-unsaturated acids such as acrylic acid and methacrylic acid, and unsaturated groups such as maleic acid, fumaric acid and itaconic acid The divalent carboxylic acid and the alkyl ester thereof may be used alone or in combination of two or more kinds thereof and copolymerized with styrene. What melt | dissolved this styrene-acrylic acid copolymer resin in the organic solvent at the solid content concentration of 10-40 weight% can be used. A styrene-acrylic acid copolymer resin emulsion or dispersion resin obtained by emulsion polymerization of a styrene monomer and (meth) acrylic acid (ester) can also be used. The solid content of these resins is 20 to 60% by weight, especially 30 to 50%.
It is preferably in the weight%.

As the polyurethane resin, a diisocyanate compound, at least one selected from polyol compounds having two or more hydroxyl groups in the molecular structure, and a compound having a functional group capable of reacting with an isocyanate group are used. Those obtained by the addition polymerization reaction can be used. An aromatic, aliphatic, or alicyclic (including hydrogenated) diisocyanate compound is used as the diisocyanate, and a polyol compound having two or more hydroxyl groups has a molecular weight of 300 to 10,000, preferably 500 to It is 5,000, and one containing an amount that reacts with the diisocyanate compound is used. As the polyurethane-based resin, a polyester-based polyurethane resin, a polyether-based polyurethane resin, a polycarbonate-based polyurethane resin, or a polycaprolactone-based polyurethane resin can be used depending on the type of polyol used. Further, these are preferably dissolved in an organic solvent at a solid content concentration of 10 to 40% by weight. If necessary, a diisocyanate or a polyisocyanate compound containing three or more isocyanate groups in the molecule can be added to improve the film strength and heat resistance. The polyurethane resin used in the present invention is preferably a polyurethane-based resin obtained from an aliphatic, alicyclic (including hydrogenated) diisocyanate and a polyol compound among the above diisocyanate compounds, which are excellent in light resistance. ing. As the polyurethane resin emulsion, a polyurethane resin emulsion obtained by emulsion polymerization of the above diisocyanate and the above polyol compound can be used. The resin solid content in these emulsions is 20 to 60.
It is preferably in the range of 30% by weight, especially 30 to 50% by weight.

In the present invention, it is preferable that the thermoplastic resin coating the fiber cloth is provided with flame resistance by blending a halogen-free flame-retardant compound for use as an industrial material. The antifouling print sheet of the invention preferably complies with the flameproof test stipulated by the Fire Service Law. The halogen-free flame-retardant compound is preferably one or more of phosphorus-containing compounds, nitrogen-containing compounds, and inorganic compounds, and halogen-free flame-retardant with respect to 100 parts by weight of the thermoplastic resin composition. The compound is preferably 10 to 100 parts by weight, more preferably 30 to 8 parts.
Add 0 parts by weight. Specifically, as the phosphorus-containing compound,
Red phosphorus, (metal) phosphate, (metal) organic phosphate, ammonium polyphosphate and the like can be mentioned, and as the nitrogen-containing compound, (iso) cyanurate compound, (iso) cyanuric acid compound, guanidine Inorganic compounds include metal oxides, metal hydroxides, metal composite oxides, metal composite hydroxides, and the like. These halogen-free flame-retardant compounds are preferably blended in combination of two or more. The amount of halogen-free flame-retardant compound is 10
If it is less than 100 parts by weight, flame resistance may be insufficient, and if it exceeds 100 parts by weight, workability and abrasion resistance of the resin coating may be insufficient.

The thermoplastic resin of the antifouling print sheet of the present invention which coats the surface of the fiber cloth may be colorless, but is preferably pigmented, particularly white, pastel or the like. This is preferable because the print can be clearly observed. As the pigment used for pigment coloring, it is particularly preferable that the pigment is colored using only an inorganic pigment, but an organic pigment may be used in combination. When the inorganic pigment and the organic pigment are used in combination, the total content of the inorganic pigments is 70 with respect to the total amount of the pigments used.
It is preferably at least wt%. When the total content of the organic pigments exceeds 30% by weight with respect to the total amount of the pigments used for coloring the thermoplastic resin, the chemical structure of the organic pigment is altered by the redox action of the photocatalyst substance, and the thermoplastic resin The discoloration and fading of the coating layer may be noticeable, which may make it unattractive. Specific examples of preferred inorganic pigments for coloring the thermoplastic resin of the present invention include metal oxides, metal sulfides, metal sulfates, metal carbonates, metal hydroxides, and chromate metal salts,
Carbon black, spinel structure oxide, rutile structure oxide and the like.

As the metal oxide, zinc oxide (zinc
Flower), titanium oxide (rutile type, anatase type), trioxide
Antimony, iron oxide (iron black, red iron oxide), yellow iron oxide,
Ferrocyanide iron (dark blue), a mixture of dark blue and yellow lead
Green), lead oxide (red lead), chromium oxide, dioxide
Ruconium, a composite of cobalt oxide and aluminum oxide
(Cobalt blue), cobalt oxide, tin oxide, and mag oxide
Complex with Nesium (Cerulean Blue), Cobalt Oxide
Complex of lithium oxide and phosphorus pentoxide (cobalt oxide
Olette), cobalt oxide, zinc oxide, and magnesium oxide
Compound with cobalt (cobalt green), cobalt phosphate
(Cobalt violet), manganese phosphate (manganese
Purple) and the like. In addition, as the metal sulfide,
Compound of zinc oxide and barium sulfate (lithopone), calcium sulfide
Cium, strontium sulfide, zinc sulfide, zinc cad
Mium, cadmium sulfide (cadmium yellow), sulfide
Complex of Cadmium and Mercury Sulfide (Cadmium Mercury
Lee red), mercury sulfide (silver vermilion), cadmium sulfide and
Rhenium-cadmium complex (cadmium red, calcium
Domium orange, cadmium yellow), anti-sulfide
Compound of monmon and antimony trioxide (antimon vermilion), etc.
Is mentioned. Examples of metal sulfates include barium sulfate and sulfuric acid.
Calcium acid, lead sulfate, basic lead sulfate, lead molybdate
And a compound of lead sulfate (molybdenum red)
It Further, as the metal carbonate, barium carbonate, carbonate
Lucium, magnesium carbonate, lead carbonate and lead hydroxide composite
The thing (lead white) etc. are mentioned. Also, as a metal hydroxide
For aluminum hydroxide (alumina white), hydroxy
Composite of aluminum chloride and calcium sulfate (satin
White), a composite of aluminum hydroxide and barium sulfate
Ross White), chromic acid hydrate (Viridian), etc.
Can be mentioned. In addition, chromic acid metal salts include chromic acid
Lead (yellow lead), zinc chromate (zinc yellow), chromate barium
, Lead chromate and lead oxide composite (red lead yellow lead), chromium
Compound of lead oxide, lead molybdate, and lead sulfate (chrome bar
Million) and the like. In addition, spinel structure acid
As the compound, "XY ₂ O_Four Oxidation represented by the structural formula
In the product, XY components are Co-Al, Co-Al-C
r, Co-Mg-Sn, Co-Ni-Ti, Co-Zn
-Ni-Ti, Co-Zn-Cr-Ti, Zn-Cr-
Ti, Zn-Cr-Fe, Co-Zn-Cr-Fe, C
o-Ni-Cr-FE-Si, Co-Mn-Cr-F
e, Cu-Mn-Cr, Mn-Fe and other metal composite oxidation
Things can be mentioned. In addition, as the rutile type oxide,
"[Ti (XY) O₂ ]] To the oxide represented by the structural formula
XY components are Pb-Sb, Ni-Sb (titanium
Yellow), Ni-W, Fe-Mo, Cr-Sb, etc.
Examples thereof include metal complex oxides. Other carbon black
Black, titanium black, acetylene black, graphite, siri
Mosquito, white carbon, diatomaceous earth, talc, clay, a
Luminium powder pigment, bronze powder, nickel powder, stainless steel
Depending on the purpose, powders, pearl pigments, etc.
One or a combination of two or more pigments may be used for coloring.
You can

In the present invention, titanium oxide (TiO ₂ ) is used as a part of the inorganic pigment in order to conceal the resin coating layer of the sheet-shaped substrate to be printed. Is preferable from the viewpoint of print clarity. As titanium oxide, rutile type titanium oxide obtained by reacting titanium ore with sulfuric acid to give titanyl sulfate, and calcining hydrous titanium oxide obtained by hydrolyzing this, and anatase type titanium oxide, or reducing titanium ore Examples include rutile titanium oxide obtained by reacting chlorine with the agent and reacting the obtained titanium tetrachloride with oxygen. As the titanium oxide used in the present invention, it is preferable to use rutile type titanium oxide from the viewpoint of weather resistance, and the particle size is 0.05 to 0.5 μm, preferably the average particle size is 0.2 to 0. Titanium oxide having a thickness of 35 μm is suitable because it has excellent concealing properties. Further, in the present invention, these inorganic pigments, using a thermosetting resin coated pigment surface-coated with a thermosetting resin such as melamine resin, benzoguanamine resin, urea resin, phenol resin, epoxy resin. Is also good.

In the sheet-like base material of the present invention, a coloring agent containing an organic pigment may be used in addition to the above-mentioned inorganic pigment for coloring the thermoplastic resin for coating the base sheet made of fiber cloth. It is preferable that the total content of the organic pigments is less than 30% by weight based on the total amount of the pigments. Specifically, organic pigments include azo pigments (insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex salt azo pigments), phthalocyanine pigments (phthalocyanine blue, phthalocyanine green),
Dyeing lake pigment (acid dye lake pigment, basic dye lake pigment), condensed polycyclic pigment (anthraquinone pigment,
Thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments), other nitroso pigments, alizarin lake pigments, metal complex salt azomethine pigments, aniline Examples of such pigments include organic pigments, and one or more of these organic pigments can be used in combination with the above-mentioned inorganic pigment. Further, a thermosetting resin-coated pigment obtained by finely pulverizing and pulverizing a mixture of these organic pigments in a thermosetting resin such as melamine resin, benzoguanamine resin, urea resin, phenol resin, and epoxy resin is used. May be.

There is no limitation on the amount of the colorant based on these inorganic pigments or the colorant used in combination with the inorganic pigment and the organic pigment, which can be appropriately set according to the desired hue. Is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The amount of colorant added is 0.1
If it is less than 50 parts by weight, the coloring effect of the thermoplastic resin coating may be sufficient and the hiding property may be insufficient. If it exceeds 50 parts by weight, the moldability of the thermoplastic resin coating may be deteriorated. In addition, the coating strength and coating abrasion resistance of the thermoplastic resin coating layer may be significantly insufficient. As a product of these colorants, it is preferable to use a processed pigment surface-treated with a dispersant in order to obtain coloration stability during coloring. As the dispersant, sodium lignin sulfonate, sodium alkyl sulfate ester, sodium alkylaryl sulfonate, formalin condensate of sodium naphthalene sulfonate, marcel soap,
Examples thereof include aqueous dispersants such as polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, styrene-maleic acid resins, and polyacrylic acid derivatives, and examples of oil dispersants include lecithin, sorbitan fatty acid esters, and partial fatty acids of polyacrylic acid. Examples thereof include esters, alkylamine fatty acid salts, alkyldiamines, alkyltriamines, and metal naphthenate soaps. These dispersant-treated color pigments are used in addition to vehicles, presscakes, resins, and
Add wax, plasticizer, water, etc. to form flash color, aqueous liquid color, oily liquid color, paste color (vinyl toner color), dry color, moisturizing color, masterbatch, colored pellets, etc. Preference is given to using modified processed pigments. In the present invention, when the thermoplastic resin is a polyvinyl chloride resin as the coloring agent of the thermoplastic resin that covers the base sheet made of the fiber cloth of the sheet-shaped base material, the paste vinyl chloride resin contains a wet color or The form of paste color (vinyl toner color) is preferably used,
For the straight vinyl chloride resin, a dry color or masterbatch form is preferably used. Also,
For melt-kneading processing of thermoplastic resin such as calendar processing, T-die extrusion processing, inflation processing,
The form of dry color, masterbatch, or colored pellet is preferably used. In particular, for molding of polyolefin resin, the form of colored pellets in which a high concentration of an inorganic pigment is filled in a polyolefin resin such as polyethylene or polypropylene together with a dispersant and a wax can be preferably used. Further, when the thermoplastic resin is an aqueous emulsion, the form of an aqueous liquid color can be preferably used, and in the case of a solvent-based paint or printing ink,
Flashed color, paste color, dry color,
A form such as an oily liquid color can be preferably used.

In the antifouling print sheet of the present invention,
The image may be directly printed on the surface of the base material (fiber cloth, film), or the image on the surface of the thermoplastic resin coating layer formed on the surface of the base sheet made of the fiber cloth may be printed. Good. In addition,
A photocatalytic substance-containing outermost surface antifouling layer is formed on the surface of the printed substrate, and a sheet-shaped substrate is provided between the printed substrate surface and the photocatalytic substance-containing outermost surface antifouling layer. An intermediate protective layer for protecting the material and the printed image is preferably formed. In addition, the antifouling print sheet of the present invention may be directly printed on the surface of a substrate (fiber cloth, film), or a heat formed on the surface of the substrate sheet made of the above fiber cloth. A print may be provided on the surface of the plastic resin coating layer.
In addition, a photocatalytic substance-containing outermost surface antifouling layer is formed on the printed substrate surface, and between the printed substrate surface and the photocatalytic substance-containing outermost surface antifouling layer. It is preferable that the intermediate protective layer and the transparent thermoplastic resin layer are formed. Further, the antifouling print sheet of the present invention has an intermediate protective layer between the substrate (fiber cloth, thermoplastic resin-coated fiber cloth substrate, film) and the photocatalytic substance-containing outermost surface antifouling layer. In a configuration including a transparent resin layer, it is preferable that an image is printed on the transparent resin layer surface and the image printed surface is bonded to face the sheet-shaped substrate.

Printing on the surface of the substrate (fiber cloth, thermoplastic resin-coated fiber cloth substrate, film or synthetic paper),
Alternatively, the printing on the transparent resin layer surface can be performed by any known method such as gravure (engraving intaglio) printing, screen (screen stencil) printing, offset printing, and transfer printing, and the image to be printed is a pattern or a pattern. ,
It may be a photograph, a design, characters, etc. and is not particularly limited. The ink composition for printing these images includes a colorant component of an organic pigment or an inorganic pigment,
Binder components, film softeners such as plasticizers and softeners, abrasion resistance improvers, pigment dispersants, color separation inhibitors, defoamers, thickeners, anti-settling agents, leveling agents, and gloss. Those composed of components such as eraser and diluent can be used. Among these, as organic pigments, conventionally known pigments, for example, insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, indigo pigments, benzidine pigments, thioindigo pigments, perinone pigments, perylene pigments, Examples of inorganic pigments such as isoindolinone-based and polyazo-based include titanium oxide, calcium carbonate, barium sulfate, cadmium yellow, cadmium red, chrome yellow, chrome vermillion, navy blue, ultramarine, yellow iron oxide, red iron oxide, iron black, Examples include carbon black. In the present invention, the surface of the base material (fiber cloth, film) is directly printed, or the surface of the thermoplastic resin coating layer formed on the surface of the base sheet of the fiber cloth or the like is printed and printed. Between the substrate surface and the outermost antifouling layer containing the photocatalytic substance,
In the structure including the intermediate protective layer, 20% by weight of the inorganic pigment component is contained in the coloring pigment contained in the print layer.
From the viewpoint of weather resistance, the above content is preferable. In other cases, in a structure including an intermediate protective layer / transparent resin layer between the printed substrate surface and the photocatalytic substance-containing outermost surface antifouling layer, the inorganic pigment contained in the printed layer There is no limit to the content rate of the components. Also, as the binder component of the ink, depending on the type of ink,
Polyurethane resin, polyester resin, polyamide resin (condensate of dimer acid and diamine), acrylic resin, vinyl acetate resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, Chlorinated polypropylene resin (chlorination degree 2
5 to 65% by weight), nitrocellulose, cellulose esters, cellulose ethers, cured rosin (metal salt with abithienic acid), dimerized rosin, rosin ester, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, rosin-modified Phenol resin, ketone resin, terpene resin,
It is appropriately selected and prepared from cyclized rubber, chlorinated rubber and the like, and can be used as a gravure printing ink, a screen printing ink, an offset printing ink and a transfer printing ink, respectively.

In the antifouling print sheet of the present invention, it is preferable that the image is printed by ink jet printing. In inkjet printing, digital images captured by a digital camera or computer are printed in color directly on an output medium, so there is no need to make gravure engraving rolls, screen printing, etc., which were essential in conventional printing methods. Highly accurate photographic image prints can be easily obtained. Inkjet printing includes a method of printing with a solvent ink and an oil-based ink, and a method of printing with a water-based ink. In the sheet of the present invention, it is possible to print by any method, but especially printing with an oil-based ink is required. Are preferable from the viewpoint of weather resistance. The water-based ink is mainly composed of water and a water-soluble organic solvent as a dispersion solvent for pigments and dyes.
Among water-soluble organic solvents, polyhydric alcohols and pyrrolidones are used as wetting agents, and glycol ethers are used as penetrants. As the content of the pigment,
It is in the range of 50 to 90% by weight with respect to the total weight of the water-based ink.
Additives such as an aqueous polymer dispersant, a chelating agent, an antifoaming agent and an antiseptic / antifungal agent are used. The oil-based ink is an ink mainly composed of gas oil, naphtha, or an organic solvent having a boiling point of 150 ° C. or higher as a pigment dispersion solvent. The solvent-based ink is an ink mainly composed of an organic solvent having a boiling point of 150 ° C. or lower, such as cyclohexane, acetone, or methyl ethyl ketone, as a pigment dispersion solvent. In the composition of solvent-based inks and oil-based inks, in addition to organic pigments, coloring agents such as dyes and organic solvents, binder resins such as phenol resins, acrylic resins, maleic acid resins, rosin resins, epoxy resins, butyral resins, etc. Thermoplastic resins are included, and as additives, additives such as surfactants, chelating agents, antiseptic and antifungal agents are included. Dyes that can be used in water-based inks include natural dyes,
Known dyes such as synthetic dyes, for example, nitroso type, nitro type, azo type, stilbene type, diphenylmethane type, triarylmethane type, quinoline type, methine type, polymethine type, thiazole type, indamine type, indophenol type, azine type Oxazine-based, thiazine-based, aminoketone-based, oxyketone-based, anthraquinone-based, indigoid-based, and phthalocyanine-based dyes can be used. Further, as the pigment that can be used for the water-based ink, the solvent-based ink, and the oil-based ink, conventionally known pigments such as organic pigments and inorganic pigments, for example, azo-based, phthalocyanine-based, quinacridone-based, anthraquinone-based, dioxazine-based, indico-based ,
Benzidine, thioindico, perinone, perylene, isoindolinone, titanium oxide, cadmium,
Examples include iron oxide-based pigments and carbon black-based pigments.

The antifouling print sheet of the present invention is
In order to improve printability by inkjet printing, it is preferable to form a thermoplastic resin coating layer on the surface of a base sheet such as a fiber cloth or a film, and this thermoplastic resin coating layer has ink fixability and color developability. It is preferable to contain a fixing agent and / or white fine particles for the purpose of improving the above. Particularly when printing with an aqueous ink, in these thermoplastic resins, a cellulose derivative such as carboxymethyl cellulose, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polyvinyl pyrrolidone resin, polyamine resin, polyamine resin, Acrylamide resin, polyethyleneimine resin, polyethylene polyamide resin, polyamide epichlorohydrin resin, polyamine epichlorohydrin resin, polyamide polyamine resin, polyamide polyamine epichlorohydrin resin, dicyandiamide resin, polyethylene oxide resin, polyethylene oxide-polypropylene oxide co A hydrophilic resin such as a polymer resin is contained in an amount of 5 to 30% by weight based on 100 parts by weight of the thermoplastic resin. By use, printed images is improved wettability of the aqueous ink becomes clear. Further, for the purpose of improving the wear resistance of the resin coating layer and improving the water resistance, a curing agent or a cross-linking agent may be contained, and for example, an epoxy-based curing agent, a melamine-based curing agent, an isocyanate-based cross-linking agent, a carbodiimide. A system crosslinking agent, an oxazoline system crosslinking agent, etc. can be used in an appropriate amount depending on the type and amount of the functional group of the resin compounding system used.

Further, it is preferable that the thermoplastic resin coating layer or the transparent resin layer, which is subjected to ink jet printing, contains a fixing agent (waterproofing agent) for the purpose of improving fixing of the water-based ink. As the fixing agent, it is preferable to use a cationic compound capable of forming a complex insoluble in water by ionic bonding with a sulfonic acid group or a carboxylic acid group contained in the molecular structure of the ink. It can be selected from cationic resins in consideration of color developability and elution properties. Examples of the cationic resin include polyethyleneimine salt, dimethylamine epihalohydrin condensate, polyalkylene polyamine dicyandiamide ammonium condensate, polyvinylamine salt, polyallylamine salt, alkyl (meth) acrylate quaternary ammonium salt,
(Meth) acrylamidoalkyl quaternary ammonium salt,
Polydimethyldiallylammonium salt, polystyrene 4
Grade ammonium salt, polyvinyl pyridinium halide,
Polyvinylbenzyltrimethylammonium salt or the like is preferably used in combination with 5 to 30% by weight based on 100 parts by weight of the thermoplastic resin.

In addition, a thermoplastic resin coating layer for inkjet printing, and gravure printing, screen printing,
The thermoplastic resin coating layer for offset printing or the like preferably contains white fine particles for the purpose of improving fixing of the printing ink. As white fine particles,
Silica, zeolite, sepiolite, hydrotalcite, hydrated alumina, calcium carbonate, magnesium carbonate, aluminum hydroxide, aluminum oxide, talc,
Barium sulfate, aluminum silicate, magnesium silicate,
Calcium silicate, diatomaceous earth, inorganic compound fine particles such as titanium oxide, and nylon-based resin fine particles, urea-based resin fine particles, organic compound fine particles such as benzoguanamine-based resin fine particles, and other fine particles, cellulose fine particles,
Examples include organic compound fine particles derived from natural products such as keratin fine particles, chitosan fine particles, alginic acid polymer fine particles, amino acid polymer fine particles (protein), and collagen-modified compound fine particles. Among them, silica is particularly preferably used. As the silica (silicon dioxide), it is preferable to use synthetic amorphous silica obtained by a wet method in which sodium silicate, mineral acid (sulfuric acid) and salts are reacted in an aqueous solution. Amorphous silica synthesized by this wet method is a water-containing material that has, as bound water, water bound to silanol groups (Si-OH groups) on the surface of silica by hydrogen bonds and water present as hydroxyl groups contained in the silanol groups themselves. It is silica. As the average agglomerated particle size of the silica, it is preferable to use amorphous hydrous silica having an average agglomerated particle size (Coul-counter method) of 1 to 20 μm, particularly 2 to 10 μm. As the water content of the amorphous hydrated silica, 3 to 15% by weight, particularly 5 to 10% by weight of the amorphous hydrated silica is used in an amount of 10 to 80% by weight based on 100 parts by weight of the thermoplastic resin. Is preferred. If the content of silica is less than 10% by weight, the ink absorption and color development of the resulting sheet may be insufficient, and if the content of silica exceeds 80% by weight, the thermoplastic resin coating may be used. The abrasion resistance of the layer may be inadequate.

The thickness of the thermoplastic resin coating layer is preferably such that the weight of the coating layer (amount of solid content) is 50 to 500 g.
/ M ² , more preferably 100 to 350 g / m ² . When the weight of the coating layer is less than 50 g / m ^2, the abrasion resistance of the obtained coating layer may not be sufficiently obtained, and when it exceeds 500 g / m ² , the mass of the sheet becomes too heavy. Sometimes. Further, among these, particularly the formation of the thermoplastic resin coating layer to be subjected to inkjet printing, only the outermost layer may be a configuration adapted to the inkjet printing, on the thermoplastic resin coating layer, the fixing agent, And / or the thermoplastic resin print-compatible layer containing white fine particles is preferably 5 to 60 g / m ² , more preferably 10 to 35 in terms of solid content.
It can be formed at g / m ² . If the solid content adhesion amount of the thermoplastic resin print compatible layer is less than 5 g / m ² , the printability and color developability of the sheet of the present invention may not be sufficiently obtained. As the inkjet printing method for the sheet of the present invention, known printing methods and commercially available inkjet printers can be used.

In the antifouling print sheet of the present invention,
Resins that can be used for the intermediate protective layer include silicone resins, fluorine resins, melamine resins, epoxy resins,
Examples include phosphazene resins. These resins are coating agents having a viscosity, and those having a film forming property by heat or light are preferable. Among them, the silicone-based resin is a linear silicone obtained by hydrolyzing chlorosilane or an alkoxysilane having an alkyl group, an alkenyl group, or an allyl group, or a plurality of kinds of them are hydrolyzed in a solvent-free or organic solvent. Resins, copolymerized silicone resins, silicone rubbers, etc. are used. Particularly, as the copolymerized silicone resin, Si-OH group and / or Si-OMe is used.
A modified silicone having two or more functional groups (for example, a methylphenyl silicone resin having a silanol group or an alkoxy group) and an alcoholic hydroxyl group-containing resin,
Silicone modified products obtained by reacting in the presence of an alkyl titanate catalyst, for example, acrylic modified silicone resin, acrylic-urethane modified silicone resin, urethane modified silicone resin, urethane modified silicone-fluorine copolymer resin, epoxy modified silicone resin, Polyester-modified silicone resin, alkyd-modified silicone resin, phenol-modified silicone resin and the like can be used. Further, a siloxane-crosslinkable silicone-modified copolymer, a siloxane-crosslinkable silicone-modified oligomer, an isocyanate-crosslinkable silicone-modified copolymer, an isocyanate-crosslinkable silicone-modified oligomer and the like can also be used. The content of the silicone-modifying component in these silicone resins is preferably 20 to 75% by weight in terms of solid content in the intermediate protective layer.

Further, as the fluororesin for the intermediate protective layer,
Vinyl ether-fluoro olefin copolymer resin, vinyl ester-fluoro olefin copolymer resin, and
Examples thereof include a combination composition of these fluorine-based resins and an isocyanate compound. Further, as the melamine-based resin for the intermediate protective layer, cyanuramide, cyanuric acid triamide, cyanuric acid amide, 2,4,6-triamino-1,
1 selected from 3,5-triazine and derivatives thereof
One or more melamine compounds and formalin were reacted, the initial condensation product of methylolated melamine was modified with butanol and solubilized in an organic solvent as butylated methylolmelamine, and further butylated methylolmelamine with an alkyd resin in an organic solvent. And the like solubilized in.

The epoxy resin for the intermediate protective layer is obtained by a ring-opening addition reaction of epichlorohydrin with a polyhydric phenol, and is generally a polycondensate obtained by a reaction of epichlorohydrin with bisphenol A or a resole. Can be used, can be used with amines, organic acids, curing agents such as acid anhydrides and polyisocyanate compounds in organic solvents, and those used in combination with alkyd resins, melamine resins, butylated melamine resins, etc. To be As the phosphazene-based resin for the intermediate protective layer, (PNCl ₂ ) _n (n = 1, 2,
3, 4) and other linear phosphazene chloride oligomers, or (PNCl ₂ ) _n (n
= 2, 3, 4), a 4-membered, 6-membered, or 8-membered cyclic chlorophosphazene chloride is used as a raw material, and an ultraviolet-cured product of a reactive phosphazene compound in which chlorine is substituted with an acrylic acid compound. Examples of the acrylate compound added to and substituted with the phosphazene compound include (meth) acrylic acid,
Examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.

The concentration can be adjusted by adding an organic solvent to the coating liquid used for forming the intermediate protective layer.
Thereby, the coating thickness of the intermediate protective layer can be appropriately set. As such an organic solvent, for example,
Alcohol solvents such as isopropanol and n-butanol, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane and heptane,
Alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, ketone solvents such as methyl ethyl ketone and cyclohexanone, N, N-dimethylacetamide,
One or more selected from amide solvents such as N-methyl-2-pyrrolidone, ester solvents such as ethyl acetate and butyl acetate, and tetrahydrofuran can be appropriately used.

In the present invention, the intermediate protective layer preferably contains a silicon compound, and examples of the silicon compound include polysiloxane, colloidal silica and silica. The polysiloxane is preferably one obtained by hydrolyzing and polycondensing an alkoxysilane compound by a sol-gel method. For example, the alkoxysilane is represented by the general formula: Y _n SiX _4-n (n = 1 to 3). One or more hydrolytic condensates of silicon compounds,
Co-hydrolyzed compounds are suitable. In the above general formula, Y
Can be, for example, an alkyl group, a fluoroalkyl group, a vinyl group, a mercapto group, an amino group or an epoxy group, and X can be, for example, a halogen, a methoxyl group, an ethoxyl group, or an acetyl group. Specifically, alkyl group-substituted trichlorosilane, alkyl group-substituted tribromosilane, alkyl group-substituted trimethoxysilane, alkyl group-substituted triethoxysilane, alkyl group-substituted triisopropoxysilane, alkyl group-substituted tri-methoxysilane.
Examples of the alkyl group include t-butoxysilane and the like. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an n-group.
A hexyl group, an n-decyl group, an n-octadecyl group and a phenyl group. Further, specifically, the alkyl group of the alkyl-substituted silane compound is changed to a trifluoropropyl group, the alkyl group of the alkyl-substituted silane compound is changed to a vinyl group, the alkyl group of the alkyl-substituted silane compound is Those in which the γ-methacryloxypropyl group is changed, those in which the alkyl group of the alkyl-substituted silane compound is changed to γ-aminopropyl group, those in which the alkyl group of the alkyl-substituted silane compound is changed to γ-mercaptopropyl group, etc. Is mentioned.

As the colloidal silica for the intermediate protective layer,
Examples thereof include silica sol (SiO ₂ ) as an aqueous dispersion medium obtained by cation exchange of a sodium silicate solution. The colloidal silica used for the intermediate protective layer is an organic solvent such as an alcohol solvent such as methanol, isopropanol and n-butanol, an aromatic hydrocarbon solvent such as toluene and xylene, and an aliphatic hydrocarbon solvent such as hexane and heptane. Solvents, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, ketone solvents such as methyl ethyl ketone and cyclohexanone, N, N
-Amide-based solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, ester-based solvents such as ethyl acetate and butyl acetate, and others such as tetrahydrofuran
It is preferable that the dispersion medium contains any one or more kinds of organic solvents selected from the above, and the BET average particle diameter of the colloidal silica is 10 to 20 nm. In addition, silica (S
Examples of iO ₂ ) include synthetic amorphous silica obtained by a wet method in which sodium silicate is reacted with mineral acid (sulfuric acid) and salts in an aqueous solution. Synthetic amorphous silica is
It is a hydrated silica having water bound to a silanol group (Si-OH group) on the surface by a hydrogen bond and water present as a hydroxyl group contained in the silanol group itself as bound water. The average agglomerated particle size of the amorphous hydrous silica is 1 to 20 μm, especially 2
It is preferable to use amorphous hydrous silica of 10 μm, and it is preferable to use hydrous silica having a water content of 3 to 15% by weight, particularly 5 to 10% by weight. These silicas can be used after being surface-treated with a silane coupling agent.

As the content of the silicon compound contained in the intermediate protective layer, one or more kinds of weight selected from the above polysiloxane, the above colloidal silica, and the above silica can be used.
It is preferably 5 to 35% by weight based on the total weight of the intermediate protective layer. Silicon compound content of the intermediate protective layer is 5
If it is less than 35% by weight, the adhesion between the intermediate protective layer and the photocatalytic substance-containing outermost surface antifouling layer may be insufficient, and if it exceeds 35% by weight, the intermediate protective layer and the photocatalytic substance are contained. The adhesion to the outermost surface antifouling layer is improved, but this time the adhesion between the silicon compound-containing resin layer and the print forming surface may be insufficient, and the abrasion strength of the intermediate protective layer may be insufficient. There is.

Method of applying coating agent for forming intermediate protective layer
There is no particular limitation to these coating agents.
Printed image formation surface of the sheet-shaped substrate, on the printed image formation surface
On the transparent resin layer further formed on or in the transparent resin layer
The transparent resin film that forms the
Opposite side of transparent resin film with print image formed on
Coating method that can be applied uniformly and evenly to the surface
Is desirable, for example, gravure coating method, microgravure method
Via coat method, comma coat method, roll coat method, riba
Roll coating, bar coating, kiss coating, fur coating
A low coat method or the like is suitable. Intermediate with the above coating agents
The thickness of the protective layer is not particularly limited, but the above coating method
Solids content by any of the methods or combinations
2 to 20 g / m in adhesion amount² , Especially 3 to 10 g / m² In shape
To achieve. 2 g / m solids deposit ² Less than a book
The antifouling print sheet of the invention has sufficient antifouling property and durability.
It may not be obtained in minutes, and it is 20g / m² 
If it exceeds the limit, the bending strength of the intermediate protective layer deteriorates and the printed picture
It may obscure patterns and colors and blur the printed image.
is there. 2-5g / m² To set the coating weight to
Set a large amount of organic solvent contained in the coating agent
Can be controlled by. The intermediate protective layer is
With a thickness of 0.5 μm or more.
Formed and haze value (ASTM D1003) of 10 or more
Underneath, or have a light transmittance of 80% or more.
And are preferred.

In the antifouling print sheet of the present invention,
An intermediate protective layer and a thermoplastic transparent resin layer may be included between the photocatalytic substance-containing outermost surface antifouling layer and the sheet-shaped substrate. That is, the intermediate protective layer can be provided on the thermoplastic transparent resin layer provided on the surface of the sheet-shaped substrate. Further, in the present invention, an intermediate protective layer and a thermoplastic transparent resin layer are arranged between the photocatalytic substance-containing outermost surface antifouling layer and the sheet-shaped substrate, and an image is printed on the thermoplastic transparent resin layer. May be provided so that the print forming surface is in contact with the substrate surface side. This thermoplastic transparent resin is
Polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene resin, polypropylene resin, polymethylpentene resin, ionomer resin, polyvinyl alcohol resin,
Ethylene-vinyl alcohol copolymer resin, polystyrene resin, polymethylmethacrylate resin, nylon resin, polyester resin, polyethylene terephthalate resin, amorphous polyethylene terephthalate resin, polycarbonate resin, polyurethane resin, silicone resin, fluorine-based copolymer resin, etc. A transparent film molded from the thermoplastic resin can be used, and the transparent film may be a film having a multilayer structure composed of two or more kinds of the thermoplastic resin layers. The thermoplastic resin used for these transparent films is preferably the same as the thermoplastic resin used for coating the surface of the fiber cloth from the viewpoint of adhesion to the substrate, and further, the haze value (ASTM
D1003) It is preferable that the transparency is 10 or less, or the light transmittance is 80% or more. For example, a fiber cloth is surface-coated with a colored soft polyvinyl chloride resin, a transparent soft polyvinyl chloride resin layer is formed on a sheet-shaped substrate having a surface of the resin coating layer printed thereon, and an intermediate protective layer is formed thereon. To form a photocatalytic substance-containing outermost surface antifouling layer,
To form a transparent ethylene-vinyl acetate copolymer layer on the surface of the resin coating layer on which the surface of the fiber cloth is coated and the surface of the resin coating layer is printed. A combination of an intermediate protective layer and a photocatalytic substance-containing outermost surface antifouling layer formed thereon, or a fiber cloth whose surface is coated with a colored polyurethane resin, and the surface of the resin coating layer is printed on a substrate. A transparent polyurethane resin layer is formed on the material, and an intermediate protective layer and a photocatalytic substance-containing outermost surface antifouling layer are formed on the transparent polyurethane resin layer. In these, the print may be applied to the transparent soft polyvinyl chloride resin layer, the transparent ethylene-vinyl acetate copolymer resin layer, and the transparent polyurethane resin layer side instead of the substrate side. These films are
Known film manufacturing methods such as T-die extrusion method, T-die
Molded by die co-extrusion method, calender method, inflation method, can be laminated on the printed surface of the substrate by thermal lamination or by applying an adhesive. It is also possible to form a plastic resin layer.
Further, the transparent thermoplastic resin layer may be an uncolored one having transparency, or one obtained by being slightly colored with a small amount of an organic pigment. Haze value (ASTM D of the transparent thermoplastic resin layer provided with the intermediate protective layer)
1003) is 10 or less, or the light transmittance is 80.
It is preferable to have a transparency of at least%. The thickness of these transparent resin layer films is preferably 20 to 300 μm.
And more preferably 50 to 200 μm.
When the thickness of the film exceeds 300 μm, the thickness of the obtained sheet may be excessively large, resulting in poor handleability.

The outermost surface antifouling layer containing the photocatalytic substance preferably contains 10 to 70% by weight of the photocatalytic substance, and further the metal oxide gel and / or the metal hydroxide gel 25 to 90.
It is preferable to contain 1% to 20% by weight and a silicon compound. The outermost antifouling layer containing a photocatalytic substance is applied to the surface of the above-mentioned silicon compound-containing resin layer with a coating agent containing these photocatalytic substance, metal oxide gel and / or metal hydroxide gel, and a silicon compound, and dried. Formed. The metal oxide gel and / or metal hydroxide gel contained in the photocatalytic substance-containing outermost antifouling layer fixes the photocatalytic substance, and also firmly adheres the outermost antifouling layer to the intermediate protective layer surface, Furthermore, since these metal oxide gel and / or metal hydroxide gel are porous, they have a large surface area,
Therefore, the photocatalytic activity can be effectively exhibited.
The content of the metal oxide gel and / or the metal hydroxide gel contained in the outermost surface antifouling layer containing the photocatalytic substance is 25 to 90.
It is preferably in the weight%. This content is 25% by weight
If it is less than 90% by weight, the adhesion to the intermediate protective layer may be insufficient, and if it exceeds 90% by weight, the content of the photocatalytic substance may be so small that the photocatalytic activity may not be sufficiently exhibited. Further, the specific surface area of the dried product of the metal oxide gel and / or the metal hydroxide gel is 100 m ² / g or more, so that the adhesion of the outermost surface antifouling layer to the intermediate protective layer and the photocatalytic activity exhibiting efficiency can be improved. It is preferable from the viewpoint.

Examples of the metal oxide gel and / or metal hydroxide gel include silicon, aluminum, titanium,
One or two selected from metals such as zirconium, magnesium, niobium, tantalum, tungsten and tin.
It is preferably an oxide gel or hydroxide gel of one or more kinds of metals, and specific examples thereof include silica sol, alumina sol, zirconia sol, niobium oxide sol and the like. Further, as a mixed gel of these, it can be used as a complex oxide gel obtained by a coprecipitation method. These metal oxide gels and / or metal hydroxide gels and photocatalytic substances can be mixed by mixing them in a sol state before forming these gels, or at a stage of a raw material before adjusting the sol. Mixing is preferred. Methods for preparing a metal oxide gel and / or a metal hydroxide gel include a method of hydrolyzing a metal salt, a method of neutralizing decomposition, a method of ion exchange, and the like. Any method can be used as long as it can be uniformly dispersed. As the oxide sol used in the photocatalytic substance-containing outermost surface antifouling layer of the antifouling print sheet of the present invention, zirconium and aluminum oxide sols are preferably used in terms of durability.

As the photocatalytic substance, TiO₂ , Zn
O, SrTiO₃ , CdS, GaP, InP, GaA
s, BaTiO₃ , K₂ NbO₃ , Fe₂ O₃ , Ta₂ 
O_Five , WO₃ , SnO₂ , Bi₂ O₃ , NiO, Cu₂ 
O, SiC, SiO₂ , MoS₂, InPb, RuO
₂ , CeO₂ And so on, and these
Pt, Rh, RuO as photocatalytic substance₂ , Nb, Cu, S
Known metal and metal oxides such as n and NiO added
All things can be used. Of these photocatalytic substances,
Titanium oxide (TiO₂ ), Titanium peroxide (peroxothiophene)
Tannic acid), (zinc oxide (ZnO), tin oxide (SnO)
₂ ), Strontium titanate (SrTiO 3₃ ), Oxidation
Tungsten (WO₃ ), Bismuth oxide (Bi₂ O
₃ ), Iron oxide (Fe₂ O ₃ ) And these photocatalytic substances
Uses a metal oxide selected from porous fine particles supporting
Preferably. Especially titanium oxide has a band gap
High energy, chemically stable, versatile metal oxide
It is preferable to use titanium oxide because it is
Yes. In titanium oxide as a photocatalytic substance, sulfuric acid is used.
Titan such as titanyl, titanium chloride, titanium alkoxide
Titanium oxide sol obtained by thermal hydrolysis of
Oxidation obtained as an alkali neutralized product of titanium oxide sol
Titanium, etc., and titanium hydroxide and titanium oxide
Peroxonize the fine particles with peroxide such as hydrogen peroxide
Anatase-type peroxotitanic acid dispersion dispersed in water
Is preferred. Titanium oxide is anatase type
Either chill type can be used, but anatase type oxidized titanium
Is preferable from the viewpoint of the degree of photocatalytic activity. Specifically
Is a peptized anatase of hydrochloric acid with an average crystallite size of 5 to 20 nm
Type titania sol, nitric acid deflocculating type anatase type titaniazo
Can be preferably used. Small particle size of photocatalytic substance
Since the better is the photocatalytic activity, the average particle size is 50 nm or less.
Below, more preferably a photocatalytic substance of 20 nm or less is suitable
There is. Also, as titanium oxide, hydrous titanium oxide, hydrated
Titanium oxide, metatitanic acid, orthotitanic acid, hydroxide
Also includes tongue. Outermost antifouling layer containing photocatalytic substance
The higher the photocatalyst content, the higher the photocatalytic activity.
70% by weight or less from the viewpoint of adhesiveness with the intermediate protective layer
And preferably 10 to 70% by weight.
More preferable. 10% by weight of photocatalytic substance
If it is full, the photocatalytic activity may be insufficient, and
If the content of photocatalytic substance exceeds 70% by weight, the photocatalytic activity becomes
But the adhesion with the intermediate protective layer becomes insufficient,
Furthermore, the surface wear strength of the outermost antifouling layer containing the photocatalytic substance is
It may not be sufficient, so it may not be possible to obtain sufficient outdoor durability.
Not always. Used for the outermost antifouling layer containing photocatalytic substances
Polysiloxane can be used as the silicon compound
And hydrolyze the alkoxysilane compound by the sol-gel method.
Those obtained by decondensing and polycondensing can be preferably used. This
These alkoxysilane compounds have the antifouling property of the present invention.
Which can be used for the intermediate protective layer of the heat-resistant print sheet
What was illustrated as a silane compound can be used. these
Of the silicon compound on the outermost antifouling layer containing the photocatalytic substance
It is preferable to use 1 to 20% by weight. Photocatalytic substance
There is no special limitation on the method of applying the coating material containing quality.
However, an intermediate coating agent containing these photocatalytic substances is used.
A coater that can be applied uniformly and uniformly on the surface of the protective layer.
A coating method is preferable, for example, a gravure coating method or a mask method.
Microgravure coating method, comma coating method, roll coating
Method, reverse roll coating method, bar coating method, KISCO
A coating method and a flow coating method are suitable. Above coat
The thickness of the outermost antifouling layer containing a photocatalytic substance with a coating agent is
Any or combination of the above coating methods
It is desired to form a film with a thickness of 0.1-10 μm
Good The outermost antifouling layer containing a photocatalytic substance has a thickness of 0.1.
When it is less than μm, the antifouling print sheet of the present invention has
The antifouling property and durability may not be sufficiently obtained.
Also, if it exceeds 10 μm, the print pattern and color will be hidden.
It may be masked and make it look unattractive. Antifouling property of the present invention
To produce the print sheet (1), for example, in sheet form
Image on at least the surface of both the front and back of the substrate
Printed, on the printed side of the sheet substrate
The sheet-shaped substrate and the printed image on the photocatalyst
Form an intermediate protective layer to protect from the action of volatile substances,
The outermost antifouling layer containing a photocatalytic substance on the intermediate protective layer
To form. Manufacture the antifouling print sheet (2) of the present invention
To make it, for example,
Print an image on the surface of at least the sheet-shaped substrate.
A thermoplastic resin on the printed side of the material, and
Form a transparent transparent resin layer, on the transparent resin layer,
Inside to protect the transparent resin layer from the action of photocatalytic substances
A protective layer is formed on the intermediate protective layer, and a photocatalytic substance is formed on the intermediate protective layer.
The outermost surface antifouling layer containing is formed. In this case,
A laminated film composed of a clear resin layer and an intermediate protective layer was prepared.
You may keep it. Antifouling print sheet of the present invention (3)
In one method of making a
Print an image on one side of a transparent film and create a sheet
Of the front and back surfaces of the base material, at least on the surface thereof,
Laminate the printed side of the transparent film, and
On the unprinted side of the transparent film
For protecting the transparent resin layer from the action of the photocatalytic substance
An intermediate protective layer is formed, and a photocatalytic substance is formed on the intermediate protective layer.
The outermost surface antifouling layer including the quality is formed. Antifouling pretreatment of the present invention
In another method for producing a printed sheet (3)
Is a transparent film containing thermoplastic resin on one side.
Print an image and place it on the other side of the transparent film.
Intermediate protective layer for protecting it from the action of photocatalytic substances
To form at least one of the front and back surfaces of the sheet-shaped base material.
On top of that, put the printed side of the transparent film
The outermost layer including a photocatalytic substance, which is laminated on the intermediate protective layer.
Form a surface antifouling layer.

The antifouling print sheet of the present invention is joined (overlapped and adhered) by high frequency welding using a high frequency welder in a portion where the photocatalytic substance-containing outermost antifouling layer and the intermediate protective layer are not formed. It can be easily performed by fusing. As a high frequency fusion method, a sheet is placed between two electrodes (one electrode is a weld bar), and high pressure (1 to 200 MH is applied while pressure is applied by the weld bar.
By applying a potential difference that oscillates in z), the resin layer of the sheet is melted by molecular friction heat and bonded. Also,
As another joining method, the amplitude of ultrasonic energy (16 to 30 KHz) generated from the ultrasonic vibrator is amplified in the portion of the sheet where the photocatalytic substance-containing layer is not formed, and is generated at the boundary surface of the film material. An ultrasonic welder fusion method that uses frictional heat to perform fusion, or hot air that is steplessly set to 20 to 700 ° C. by electric control of a heater,
A hot air fusion method that blows between film materials through a nozzle to instantly melt the surface of the film material, and immediately after that, the film material is pressure-bonded and bonded
Alternatively, the joining can be performed by a hot plate fusion method in which an adherend is pressure-bonded and adhered using a mold (trowel) having a built-in heater and heated to a temperature higher than the melting temperature of the thermoplastic resin.

[0059]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples. In the following Examples and Comparative Examples, the test evaluation of the performance such as discoloration / fading prevention and stain resistance of the print sheet is based on the following methods.

(I) Evaluation of Antifouling Property by Outdoor Exposure Test A print sheet having a width of 20 cm and a length of 2 m was placed on the exposure table facing south, with the surface of the outermost antifouling layer containing the photocatalytic substance being the front side. Was continuously stretched by 1 m in the direction of 30 ° of inclination and in the vertical direction, and an outdoor exposure test was conducted for 18 months. Samples were taken after 6 months, 12 months, and 18 months of outdoor exposure, and the surface of the sample was wiped with absorbent cotton to remove the color difference ΔE (JIS-Z-8729).
Then, the stain resistance was evaluated according to the following criteria. * Outdoor exposure started in April in Soka City, Saitama Prefecture. ΔE = 0 to 2.9: ⊚ = Good with no stain. The initial state is maintained. ΔE = 3 to 4.9: ◯ = Somewhat dirty, but no problem. ΔE = 5 to 9.9: Δ = dirt and rain lines are noticeable. ΔE = 10 to: × = Stain and dirt are severe, and there is a practical problem.

(II) Change of printed part due to outdoor exposure test
The surface of the sample after 6 months, 12 months, and 18 months of outdoor exposure collected from the same exposure test as the evaluation (I) of the fading prevention property was wiped with absorbent cotton to remove the color difference ΔE based on the initial value. (JIS-Z-8729), and the degree of discoloration and fading was evaluated according to the following criteria. ΔE = 0 to 2.9: A = No discoloration and good. The initial state is maintained. ΔE = 3 to 4.9: ◯ = Slightly discolored, but no problem. ΔE = 5 to 9.9: Δ = Discoloration is noticeable. ΔE = 10 to: × = Discoloration is severe and there is a practical problem.

(III) Light fastness test A light fastness test (JIS-L-0842) with a sunshine carbon weather meter was used for 240 hours for 6 hours with the photocatalytic substance-containing layer forming surface of the print sheet as the irradiation surface.
Performed for 00 hours and 1000 hours, and based on the sample before the acceleration, the degree of discoloration / fading of the printed portion was determined by the color difference ΔE (JIS
-Z-8729) and digitized, and evaluated according to the following criteria. ΔE = 0 to 2.9: A = No discoloration and good. The initial state is maintained. ΔE = 3 to 4.9: ◯ = Slightly discolored, but no problem. ΔE = 5 to 9.9: Δ = Discoloration is noticeable. ΔE = 10 to: × = Discoloration is severe and there is a practical problem.

[Example 1]-(i) Coating treatment of fiber cloth (A) with a thermoplastic resin-Fiber cloth (A): No. 5 polyester fiber plain weave spun base cloth (polyester short fiber spun yarn: yarn density warp 295 dtex
(20th count) · 51 twin yarns / 2.54 cm × weft 295 dt
ex (20th count), 48 yarns / 2.54cm: Mass 250
g / m ² ) is used as a base sheet for a base material, and this is used as a paste vinyl chloride resin compounding composition of the following composition: PV
After dipping (immersing) C (1) in an organosol bath diluted with a solvent and impregnating the fiber cloth (A) with PVC (1), the fiber cloth (A) impregnated with the resin is pulled up by a mangle roller. Nip (press), fiber cloth (A)
On the other hand, 145 g / m ² of PVC (1) was uniformly impregnated and adhered on both surfaces of the fiber cloth (A), and then 140 ° C.
Immediately after 1 minute of drying in a hot air drying oven of No. 1 and heat treatment in a hot air drying oven of 175 ° C. for 1 minute to gelate the resin.
This was hot-pressed by passing it through a hot roll (pressing 0.2 Mpa) at 80 ° C. Next, the resin-coated cloth is again PV
After dipping in the C (1) bath and further adhering the resin, this time, resin coating was performed with a doctor knife. This base material was dried in a hot air drying oven at 140 ° C. for 1 minute, and then heat-treated in a hot air drying oven at 175 ° C. for 1 minute to gelate the resin, and immediately after that, a hot roll at 180 ° C. (press 0.2
Mpa), heat-press the resin-coated substrate, and
A sheet-like base material having a thickness of 0.46 mm and a mass of 490 g / m ² which was surface-coated with C (1) was obtained. <Vinyl chloride resin composition: PVC (1)> Paste Vinyl chloride resin (P = 1600) 100 parts by weight DOP (plasticizer) 40 parts by weight Adipic acid polyester 30 parts by weight Epoxidized soybean oil (ESBO) 4 parts by weight Calcium carbonate 10 parts by weight Ba-Zn stabilizer 2 parts by weight Rutile titanium oxide 5 parts by weight UV absorber 0.3 parts by weight Antioxidant 0.2 parts by weight Solvent (toluene) 20 parts by weight [Note] Vinyl chloride resin: Trademark : ZEST-P21 (Shin Daiichi Vinyl Co., Ltd.) DOP: Trademark: Sanso Sizer DOP (Shin Nippon Rika Co., Ltd.) Adipic polyester: Trademark: Adeka Sizer PN-446 (Asahi Denka Kogyo Co., Ltd.) Soybean oil: Trademark: ADEKA CIZER O-130P (Asahi Denka Kogyo Co., Ltd.) Calcium carbonate: Trademark: Ryton BS (Bihoku Powder Industry Co., Ltd. ) Ba-Zn stabilizer: Trademark: KV-400B (Kyodo Pharmaceutical Co., Ltd.) Rutile titanium oxide: Trademark: Titanium oxide CR: (Ishihara Sangyo Co., Ltd.) UV absorber: Trademark: Biosorb 510 (benzotriazole-based) : Kyodo Pharmaceutical Co., Ltd. Antioxidant: Trademark: Irganox E201 (Vitamin E: Ciba Specialty Chemicals Co., Ltd.)

-(Ii) Printing on Resin-Coated Substrate (Gravure Printing) -Next, on one surface of the resin-coated sheet-shaped substrate obtained in (i), 1
Using a printing machine having a gravure roll engraved with a 00 mesh stripe pattern, a 10 cm wide emerald green color stripe was printed and dried at 80 ° C. <Gravure Ink> Stripe (Emerald green color: Inorganic pigment content 71% by weight) Trademark: VCFL79 (grass): Toyo Ink Mfg. Co., Ltd .: Solid content 37% by weight I. Pigment: Green-36 content 8% by weight 38 parts by weight Trademark: VCFL61 (white): Toyo Ink Mfg. Co., Ltd .: Solid content 44% by weight C.I. I. Pigment: White-4 content 12% by weight 62 parts by weight Trademark: Matte medium (silica 15% by weight content clear): Toyo Ink Mfg. Co., Ltd. 10 parts by weight Trademark: ULS-933LP: Benzotriazole-based polymer UV absorber : On the other hand, Yushisha Oil & Fat Co., Ltd. 3 parts by weight Trademark: Irganox E201 (Vitamin E: Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight Diluent: Toluene / methyl ethyl ketone (50/50 weight ratio) 30 parts by weight Part [Note] Inorganic pigment: organic pigment blending weight ratio = 93: 38

-(Iii) Formation of Intermediate Protective Layer-Next, the following treatment liquid for forming the intermediate protective layer was applied to the entire surface of the resin-coated substrate on which the print was to be formed, using a 80 mesh gravure roll coater at 15 g / m ^2. Wet 1
It was dried for 1 minute in a hot air drying oven at 00 ° C. (Amount of deposited solid matter: 3 g / m ² ) <Treatment liquid for forming intermediate protective layer> 1). Ethanol-ethyl acetate (50/50 weight ratio) solution containing 8 weight% (solid content) of acrylic-silicone resin having a silicone content of 3 mol% 100 weight parts 2). Methyl silicate MS51 (Colcoat Co., Ltd.) 20 wt% ethanol solution 8 parts by weight as a polysiloxane 3). γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by weight

-(Iv) Formation of Outermost Surface Antifouling Layer Containing Photocatalytic Substance-Next, the following treatment liquid for forming the outermost surface antifouling layer containing a photocatalytic substance was applied to a 100 mesh gravure on the entire surface of the intermediate protective layer. Apply 12g / m ^{2 with} roll coater (wet)
Then, it was dried in a hot air drying oven at 100 ° C. for 1 minute to prepare a vinyl chloride resin-coated print sheet having a stripe pattern and having a mass of 493 g / m ² . <Treatment liquid for forming outermost antifouling layer containing photocatalytic substance> 1). 100 parts by weight of a water-ethanol (50/50 weight ratio) solution in which a nitric acid-acidified titanium oxide sol corresponding to a titanium oxide content of 10 weight% is dispersed 2). 100 parts by weight of a water-ethanol (50/50 weight ratio) solution in which a nitric acid acidic silica sol having a silicon oxide content of 10% by weight is dispersed.

Example 2 — (i) Formation of Inkjet Printed Layer— The same textile fabric (A) substrate sheet as in Example 1 was coated on one side,
A resin-coated cloth obtained by surface-coating with the same PVC (1) as in Example 1 was coated with a surface-treating agent composed of an acrylic resin having the following composition in an amount of 4 g / m ² using an 80-mesh gravure coater. The amount of solids applied is applied, and the solvent is dried by passing through a hot air drying oven at 80 ° C for 2 minutes to form an inkjet printing layer, thickness 0.46 mm, mass 494.
A sheet-like base material having a g / m ² was obtained. <Acrylic surface treatment agent> Trademark: Sony Bond SC-474: Sony Chemical Co., Ltd. acrylic copolymer resin (solid content 30 wt%: solvent xylene, methyl cellosolve, MEK) 100 parts by weight Trademark: E-170: Nippon Silica Industrial Co., Ltd .: Hydrous silica (water content 6 wt%) 15 parts by weight Trademark: ULS-933LP: Benzotriazole-based polymer UV absorber: Meitesha Oil & Fat Co., Ltd. 2 parts by weight Diluent: MEK (methyl ethyl ketone) 50 parts by weight Parts [Note] The content of silica contained in this surface-treated layer was 50% by weight.

-(Ii) Printing on a resin-coated sheet-shaped substrate (inkjet printing) -On the inkjet-printed layer surface of the PVC (1) -coated sheet-shaped substrate obtained in (i), a product manufactured by Muto Kogyo Co., Ltd. Solvent ink drawing type inkjet printer (Ramiless PJ-1
Using the 304NX (on-demand system), a music CD jacket design (artist name: YNGWIE JO
HANN MALMSTEEN / Title: Concert Suite
In E flat minor "New Century" / Standard number: PCCY-01211
/ (Pony Canyon Co., Ltd.), 1200 mm x 1200
Full-color enlarged output (inkjet printing) to mm size. Printing was performed at an output of 384 dpi using four color inks of cyan, magenta, yellow and black.

-(Iii) Formation of Thermoplastic Transparent Resin Layer-Next, the following PVC (2) composition is added to the printed surface having the printed pattern of the PVC (1) -coated substrate obtained in (ii), in the amount of 165.
A thermoplastic resin transparent film having a thickness of 0.1 mm and a haze value of 0.6 obtained by kneading under a heat condition of ℃ and calender rolling, and using a laminator equipped with a heat roll set at 160 ℃ And laminated by thermocompression bonding to a thickness of 0.55
A layered product having a size of mm and a mass of 612 g / m ² was obtained. <Vinyl chloride resin composition: PVC (2)> Straight vinyl chloride resin (P = 1050) 100 parts by weight DOP (plasticizer) 40 parts by weight Adipic acid polyester 30 parts by weight Epoxidized soybean oil (ESBO) 4 parts by weight Ba- Zn stabilizer 2 parts by weight Ultraviolet absorber 0.3 parts by weight Antioxidant 0.2 parts by weight [Note] Vinyl chloride resin: Trademark: ZEST1000S (Shin-Daiichi PVC Co., Ltd.) DOP: Trademark: Sanso Sizer DOP ( Shin Nippon Rika Co., Ltd. Adipic polyester: Trademark: ADEKA CIZER PN-446 (Asahi Denka Kogyo Co., Ltd.) Epoxidized soybean oil: Trademark: Adeka Sizer O-130P (Asahi Denka Co., Ltd.) Ba-Zn system Stabilizer: Trademark: KV-400B (Kyodo Chemical Co., Ltd.) UV absorber: Trademark: Biosorb 510 (Kyodo Chemical Co., Ltd.) Antioxidant: quotient Mark: Irganox E201 (Vitamin E type: Ciba Specialty Chemicals Co., Ltd.)

-(Iv) Formation of Intermediate Protective Layer-In the same manner as in Example 1, an intermediate protective layer was formed on the entire surface of the thermoplastic transparent resin layer. (Amount of solid matter attached: 3 g / m ² )-
(V) Formation of photocatalytic substance-containing outermost antifouling layer-A photocatalytic substance-containing layer was formed on the entire surface of the intermediate protective layer in the same manner as in Example 1 to have a thickness of 0.56 mm and a mass of 615.
A vinyl chloride resin-coated antifouling print sheet of g / m ² was prepared.

[Example 3]-(i) Coating treatment of the fiber cloth (A) with a thermoplastic resin-The same fiber cloth (A) as in Example 1: No. 5 polyester fiber spun plain woven cloth was used as a base sheet, A polyurethane resin emulsion composition having the following composition:
Dip (immerse) in the PU (1) bath and apply P to the fabric (A)
Fiber cloth (A) impregnated with U (1) and then impregnated with resin
Nip (compress) with mangle roller at the same time
And PU of 78 g / m ^{2 with} respect to the fiber cloth (A)
(1) is uniformly impregnated and adhered to both surfaces of the fiber cloth (A), then dried in a hot air drying oven at 100 ° C. for 2 minutes, and immediately after that, passed through a hot roll (press 0.2 Mpa) at 180 ° C. to obtain a resin-coated cloth. Was heat pressed. Next, this resin-coated cloth was again dipped in the PU (1) bath to further attach the resin, and this time, resin coating was performed with a doctor knife. This resin-coated cloth was dried in a hot air drying oven at 100 ° C. for 2 minutes, and immediately after that, heated on a 180 ° C. hot roll (press 0.2
It was passed through Mpa) and hot-pressed to obtain a resin-coated cloth having a thickness of 0.40 mm and a mass of 394 g / m ² which was surface-coated with PU (1). <Polyurethane resin composition: PU (1)> Trademark: Permusen RU-40-350: Avicia Co., Ltd. Polycarbonate urethane resin emulsion: (solid content 40% by weight) 100 parts by weight Trademark: MC-640: Melamine cyanurate: Nissan Chemical Co., Ltd. 25 parts by weight Trademark: Carbodilite V-02: Nisshinbo Co., Ltd .: Carbodiimide compound (solid content 40% by weight) 3 parts by weight Trademark: Ryudai-W69 White: Dainippon Ink and Chemicals, Inc .: Water-based pigment (White: Titanium oxide: Solid content 50% by weight) 6 parts by weight Trademark: ULS-383MG: Heiwasha Oil & Fat Co., Ltd .: Benzophenone-based polymer emulsion (solids content 30% by weight) 4 parts by weight Trademark: Irganox E201: Vitamin E type: 0.2 parts by weight of Ciba Specialty Chemicals Co., Ltd.

-(Ii) Formation of inkjet printing layer- On one side of the fiber cloth (A) surface-coated with PU (1),
A surface treatment agent consisting of a polyurethane resin having the above composition was added to 80
4g / m using a mesh gravure coater ² Solid of
The coating amount is applied and the mixture is passed through a hot air drying oven at 80 ° C for 2 minutes.
Inkjet print layer is formed by drying the solvent.
Thickness 0.40 mm, mass 398 g / m²Sheet-shaped substrate
I got the material. <Polyurethane surface treatment agent> Trademark: Takelac E-350: Takeda Pharmaceutical Company Limited:     Polyester polyurethane (solid content 26 wt%: solvent IPA, toluene)                                                             100 parts by weight Trademark: E-170: Nippon Silica Industry Co., Ltd .: Hydrous silica (water content 6 wt%)                                                               15 parts by weight Trademark: ULS-933LP: Benzotriazole polymer UV absorber     : 2 parts by weight of one-sided company Yushi Kogyo Co., Ltd. Diluent: MEK (methyl ethyl ketone) 50 parts by weight (The content of silica contained in this surface-treated layer was 50% by weight.)

-(Iii) Printing on Resin Coated Substrate (Inkjet Printing)-On the inkjet printing layer surface of the PU (1) coated substrate obtained in (ii), a solvent ink drawing type inkjet printer manufactured by Muto Kogyo Co., Ltd. (Using Ramirez PJ-1304NX (on-demand method), a jacket design of a music CD (artist name: BLACKMORE'S NIGH
T / Title: SHADOW OF THE MOON
/ Standard number: PVCP-6022 / BMG Japan Co., Ltd.) was subjected to full color enlarged output (inkjet printing) to a size of 1200 mm × 1200 mm. Printing is performed using four color inks of cyan, magenta, yellow and black.
It was performed at 84 dpi.

-(Iv) Formation of Thermoplastic Transparent Resin Layer-Next, 165 of the following PU (2) composition was applied to the printed surface of the PU (1) -coated substrate having the print pattern obtained in (iii). A thermoplastic transparent resin film having a thickness of 0.1 mm and a haze value of 0.6 obtained by kneading under a heat condition of ℃ and calender rolling was used with a laminator equipped with a heat roll set at 160 ℃. Layered by thermocompression bonding to a thickness of 0.56 mm,
A transparent resin layer coated sheet having a mass of 594 g / m ² was obtained. <Polyurethane resin compounding composition: PU (2)> Trademark: Molsen PE192-100: Ether-type non-yellowing polyurethane: Hardness 75A: Asahi Glass Co., Ltd. 100 parts by weight Trademark: Irganox E201: Vitamin E: Ciba Specialty Chemicals Co., Ltd. 0.2 part by weight Trademark: Licowax E: Montanate ester wax: Clariant Japan 0.2 part by weight

-(V) Formation of Intermediate Protective Layer-In the same manner as in Example 1, an intermediate protective layer was formed on the entire surface of the thermoplastic transparent resin layer of (iv). (Amount of solid content 3 g /
m ² )-(vi) Formation of photocatalytic substance-containing outermost surface antifouling layer-In the same manner as in Example 1, a photocatalytic substance-containing outermost surface antifouling layer was formed on the entire surface of the intermediate protective layer of (v). , Thickness 0.50
A polyurethane resin-coated antifouling print sheet having a mass of 524 g / m ² was prepared.

[Example 4]-(i) Coating treatment of the fiber cloth (A) with a thermoplastic resin-The same fiber cloth (A) as in Example 1: No. 5 polyester fiber plain weave spun cloth was used as a base sheet, An ethylene-vinyl acetate copolymer resin emulsion composition having the following composition: dip (immersion) in EVA (1) bath
Then, the fiber cloth (A) is impregnated with EVA (1), and then the resin-impregnated fiber cloth (A) is pulled up and simultaneously nipped (compressed) with a mangle roller to obtain 72 g / of the fiber cloth (A). m ² of EVA (1) was uniformly impregnated and adhered on both surfaces of the fiber cloth (A), then dried in a hot air drying oven at 100 ° C. for 2 minutes, and immediately thereafter, passed through a hot roll at 180 ° C. (press 0.2 Mpa). And heat-pressed. Next, the resin-coated cloth was again dipped in the EVA (1) bath to further deposit the resin, and then the resin coating was applied with a doctor knife. This resin-coated cloth was dried in a hot air drying oven at 100 ° C for 2 minutes, and immediately after that, it was passed through a hot roll (press 0.2 Mpa) at 180 ° C to be hot-pressed, EVA
Surface coated by (1), thickness 0.40mm, mass 3
A 80 g / m ² sheet-shaped substrate was obtained. <Ethylene-vinyl acetate copolymer resin compounding composition: EVA (1)> Trademark: Sumikaflex S-951: Sumitomo Chemical Co., Ltd .: Ethylene-vinyl acetate copolymer emulsion (solid content 55% by weight) 70 parts by weight Trademark: Ricabond BE-1502: Chuo Rika Kogyo Co., Ltd .: Ethylene-vinyl acetate copolymer emulsion (solid content 50% by weight) 30 parts by weight Trademark: MC-640: Melamine cyanurate: Nissan Chemical Co., Ltd. 25 parts by weight Trademark: Carbodilite V-02: Nisshinbo Co., Ltd .: Carbodiimide compound (solid content 40% by weight) 3 parts by weight Trademark: Ryudai-W69 White: Dainippon Ink and Chemicals, Inc .: Water-based pigment (white: titanium oxide: solid content) 50% by weight) 6 parts by weight Trademark: ULS-383MG: Onsensha Yushi Kogyo Co., Ltd .: Benzophenone-based polymer emulsion (Solid content 30 wt%) 4 parts by weight trademark: Irganox E201: Vitamin E systems: Ciba Specialty Chemicals Corp., 0.2 part by weight

-(Ii) Printing on resin-coated sheet-like substrate (screen printing)-(1) On one side of the EVA (1) -coated sheet-like substrate obtained in (i),
An image was printed using a screen stencil in which "HIRAOKA" alphabet / Gothic characters were made with a 225 mesh line and the following screen ink. <Screen ink composition> 70B-red: solid content 56% by weight: polyazo red (CI Pigment: Red 144) content 12% by weight: inorganic extender pigment 14% by weight: Seiko Advance Co., Ltd. 40 parts by weight 70B-white : Solid content 64% by weight: Rutile type titanium oxide (CI Pigment: White-4) Content 26% by weight: Inorganic extender pigment 10% by weight: Seiko Advance Co., Ltd. 60 parts by weight Trademark: Irganox E201: Vitamin E type: Ciba Specialty Chemicals Co., Ltd. 0.2 parts by weight Diluent: Cyclohexanone / xylene (30/70) 10 parts by weight * Inorganic pigment: Organic pigment = 12:39 (inorganic pigment content 76 weight%)

-(Iii) Formation of thermoplastic resin transparent layer-Next, EVA (1) having the character print obtained in (ii)
On the printed surface of the coated substrate, the following EVA (2) composition 136
A thermoplastic resin transparent film having a thickness of 0.1 mm and a haze value of 1.1 obtained by kneading under a heat condition of ℃ and calender rolling, and using a laminator equipped with a heat roll set to 130 ℃ And laminated by thermocompression bonding to a thickness of 0.50
A base material having a mass of 486 g / m ² was obtained. <Ethylene-vinyl acetate copolymer resin composition: EVA (2)> Trademark: Evaflex EV2805: Vinyl acetate component content 28% by weight: MFR 6 g / 10 min: Mitsui DuPont Polychemical Co., Ltd. 100 parts by weight Trademark: IRGA Knox E201: Vitamin E system: Ciba Specialty Chemicals Co., Ltd. 0.2 part by weight Trademark: LTP-2: Phosphate ester lubricant: Kawaken Fine Chemical Co., Ltd. 0.5 part by weight

-(Iv) Formation of Intermediate Protective Layer-In the same manner as in Example 1, an intermediate protective layer was formed on the entire surface of the thermoplastic transparent resin layer (iii). (Solid content 3
g / m ² )-(v) Formation of outermost surface antifouling layer containing photocatalytic substance-The same as in Example 1, except that the outermost surface antifouling layer containing a photocatalytic substance is formed on the entire surface of the intermediate protective layer of (iv) above. Formed, thickness 0.5
An ethylene-vinyl acetate copolymer resin-coated antifouling print sheet having a weight of 0 mm and a mass of 490 g / m ² was prepared.

[Example 5]-(i) Coating treatment of fiber cloth (B) with thermoplastic resin-Fiber cloth (B): polyester fiber plain woven base cloth (555dt)
ex polyester multifilament yarn: yarn density warp 2
3 threads / 2.54 cm x weft 23 threads / 2.54 cm: mass 10
0 g / m ² ) was used as the base sheet. Separately, a vinyl chloride resin compound composition having the following composition: PVC (3) 1
By kneading under heat conditions of 65 ° C and calender rolling,
A film having a thickness of 0.18 mm was obtained. Next, using a laminator equipped with a heat roll set to 160 ° C., a PVC (3) film was laminated on both sides of the fiber fabric (B) by a thermocompression bonding method to give a thickness of 0.44 mm and a mass of 528 g / m. A sheet-shaped base material ² was obtained. <Vinyl chloride resin composition: PVC (3)> Straight vinyl chloride resin (P = 1050) 100 parts by weight DOP (plasticizer) 40 parts by weight Adipic acid polyester 30 parts by weight Epoxidized soybean oil (ESBO) 4 parts by weight Calcium carbonate 10 parts by weight Ba-Zn-based stabilizer 2 parts by weight Rutile titanium oxide 5 parts by weight UV absorber 0.3 parts by weight Antioxidant 0.2 parts by weight [Note] Vinyl chloride resin: Trademark: ZEST1000S DOP: Trademark: Sanso Sizer DOP (New Japan Rika Co., Ltd.) Adipic polyester: Trademark: ADEKA SAIZER PN-446 (Asahi Denka Kogyo Co., Ltd.) Epoxidized soybean oil: Trademark: ADEKA SIZER O-130P (Asahi Denka Co., Ltd.) Calcium carbonate: Trademark: Ryton BS (Bihoku Powder Industry Co., Ltd.) Ba-Zn stabilizer: Trademark: KV-400B (Kyodo Pharmaceutical Co., Ltd.) Rutile type titanium oxide: Trademark: Titanium oxide CR: (Ishihara Sangyo Co., Ltd.) UV absorber: Trademark: Biosorb 510 (benzotriazole type: Kyodo Yakuhin Co., Ltd.) Oxidation Inhibitor: Trademark: Irganox E201 (Vitamin E: Ciba Specialty Chemicals Co., Ltd.)

-(Ii) Printing on Resin-Coated Substrate (Gravure Printing) -Next, on one surface of the resin-coated sheet-shaped substrate obtained in (i), 1
Using a printer having a gravure roll engraved with a 00 mesh stripe pattern, a 10 cm wide orange stripe image was printed and dried at 80 ° C. <Gravure Ink> Stripe (orange: inorganic pigment content 70% by weight) Trademark: VCFL182 (red): Toyo Ink Mfg. Co., Ltd .: Solid content 36% by weight I. Pigment: Red-57 content 7% by weight 20 parts by weight Trademark: VCFL262 (yellow): Toyo Ink Mfg. Co., Ltd .: Solid content 38% by weight C.I. I. Pigment: Yellow-12 content 8% by weight 20 parts by weight Trademark: VCFL61 (white): Toyo Ink Mfg. Co., Ltd .: Solid content 44% by weight C.I. I. Pigment: White-4 content 12% by weight 60 parts by weight Trademark: Matte medium (silica 15% by weight content clear): Toyo Ink Mfg. Co., Ltd. 10 parts by weight Trademark: ULS-933LP: Benzotriazole-based polymer UV absorber : On the other hand 3 parts by weight of Yushisha Kogyo Co., Ltd. Trademark: Irganox E201: Vitamin E type: Ciba Specialty Chemicals Co., Ltd. 0.1 part by weight Diluent: Toluene / methyl ethyl ketone (50/50 weight ratio) 30 parts by weight Inorganic pigment: organic pigment blending weight ratio = 12: 5

-(Iii) Formation of Intermediate Protective Layer-The same intermediate protective layer as in Example 1 was formed on the entire printed surface of (ii) above. (Amount of deposited solid matter: 3 g / m ² )-(iv) Formation of outermost surface antifouling layer containing photocatalytic substance- Forming an outer surface protective layer, thickness 0.44
A polyvinyl chloride resin-coated antifouling print sheet having a mass of 529 g / m ² was prepared.

Example 6- (i) Formation of Inkjet Printing Layer-The same fiber cloth (B) as in Example 5 was used for the same P as in Example 5.
The surface was coated with VC (3), and a surface treatment agent made of an acrylic resin having the same composition as in Example 2 was applied to one surface of the surface by using an 80 mesh gravure coater in the same manner as in Example 2.
An ink jet printing layer was formed by coating with a solid content deposition amount of g / m ² to obtain a sheet-shaped substrate having a thickness of 0.44 mm and a mass of 494 g / m ² . -(Ii) Printing on a resin-coated sheet-like substrate (inkjet printing) -On the inkjet printing layer surface of the PVC (3) -coated substrate obtained in (i), a solvent ink drawing type inkjet printer (manufactured by Muto Kogyo Co., Ltd.) Using a Ramirez PJ-1304NX (on-demand system), a music CD jacket design (artist name: CRADEL OF FILTH /
Title: Cruelty And The Beats
t / standard number: PCCY-01244 / Pony Canyon Co., Ltd.) was subjected to full color enlarged output (inkjet printing) to a size of 1200 mm × 1200 mm. Printing is cyan,
The output was 384 dpi using four color inks of magenta, yellow and black.

-(Iii) Formation of Transparent Layer of Thermoplastic Resin-Next, the PVC (3) having the printed pattern obtained in (ii)
On the printed surface of the coated substrate, the same thickness as in Example 2, 0.1 mm,
A PVC (2) thermoplastic transparent resin film having a haze value of 0.6 is laminated by a thermocompression bonding method to give a thickness of 0.54 mm and a mass of 6
A transparent resin layer coating body of 29 g / m ² was obtained. -(Iv) Formation of Intermediate Protective Layer-The same intermediate protective layer as in Example 1 was formed on the entire surface of the PVC (2) thermoplastic transparent resin layer. (Solid content 3
^{g / m 2) - (v} ) formation of the photocatalytic material-containing outermost stain resistant coating - on the entire surface of the intermediate protective layer, and form the same photocatalytic material-containing outermost stain resistant coating as in Example 1, the thickness 0.54 mm, mass 63
A vinyl chloride resin-coated antifouling print sheet of 3 g / m ² was prepared.

[Example 7]-(i) Coating treatment of fiber cloth (B) with a thermoplastic resin-The same fiber cloth (B) as in Example 5: polyester fiber plain weave base cloth was used as a base sheet. Separately, a polyurethane resin compound composition comprising the following composition: PU (3) at 165 ° C.
The mixture was kneaded under the above heat conditions and was subjected to calender rolling to obtain a film having a thickness of 0.18 mm. Next, using a laminator equipped with a heat roll set at 160 ° C., the PU (3) film was laminated on both sides of the fiber fabric (B) by thermocompression bonding, and the thickness was 0.44 mm and the mass was 506 g / m. A sheet-shaped base material ² was obtained. <Polyurethane resin composition: PU (3)> Trademark: Estane 54640: Ether polyurethane: Hardness 85A: Kyowa Hakko Kogyo Co., Ltd. 100 parts by weight Trademark: MC-640: Melamine cyanurate: Nissan Kagaku Co., Ltd. 25 parts by weight trademark : Irganox E201: Vitamin E type: Ciba Specialty Chemicals Co., Ltd. 0.2 parts by weight Trademark: Licowax E: Montanate wax: Clariant Japan 0.2 parts by weight Trademark: Titanium oxide CR: Rutile type: (Ishihara Sangyo Co., Ltd. 5 parts by weight

-(Ii) Printing on the thermoplastic transparent resin layer (back side) (gravure printing) -0.1 mm in thickness and 0.6 in haze value obtained from the same PU (2) composition as in Example 3 Of 5 colors (blue, red, yellow, green, black) using a 5-color printing machine having a gravure roll engraved with a 100 mesh stained glass pattern on the back surface of the PU (2) thermoplastic transparent resin film A glass pattern was printed and dried at 80 ° C. The stained glass design has a blue, red, yellow, and green solid print area of 18% each.
The solid black print area of the color border line was set to 28%. <Gravure ink: blue> * Inorganic pigment: organic pigment ratio = 8: 0 Trademark: VCFL39 (Ai): Toyo Ink Mfg. Co., Ltd .: Solid content 36% by weight C.I. I. Pigment: Blue-27 content 7% by weight 80 parts by weight Trademark: VCFL61 (white): Toyo Ink Mfg. Co., Ltd .: Solid content 44% by weight C.I. I. Pigment: White-4 content 12% by weight 20 parts by weight Trademark: Matt medium (silica 15% by weight content clear): Toyo Ink Mfg. Co., Ltd. 10 parts by weight Trademark: ULS-933LP: Benzotriazole-based polymer UV absorber On the other hand, 3 parts by weight of Yushisha Kogyo Co., Ltd. Trademark: Irganox E201 (Vitamin E type: Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight Diluent: Toluene / methyl ethyl ketone (50/50 weight ratio) 30 parts by weight Part <Gravure Ink: Red> * Inorganic pigment: Organic pigment ratio = 3: 7 Trademark: VCFL182 (red): Toyo Ink Mfg. Co., Ltd .: Solid content 36% by weight C.I. I. Pigment: Red-57 content 7% by weight 80 parts by weight Trademark: VCFL61 (white): Toyo Ink Mfg. Co., Ltd .: Solid content 44% by weight C.I. I. Pigment: White-4 content 12% by weight 20 parts by weight Trademark: Matt medium (silica 15% by weight content clear): Toyo Ink Mfg. Co., Ltd. 10 parts by weight Trademark: ULS-933LP: Benzotriazole-based polymer UV absorber On the other hand, 3 parts by weight of Yushisha Kogyo Co., Ltd. Trademark: Irganox E201 (Vitamin E type: Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight Diluent: Toluene / methyl ethyl ketone (50/50 weight ratio) 30 parts by weight Part <gravure ink: yellow> * Inorganic pigment: organic pigment ratio = 3: 8 Trademark: VCFL262 (yellow): Toyo Ink Mfg. Co., Ltd .: Solid content 38% by weight C.I. I. Pigment: Yellow-12 content 8% by weight 80 parts by weight Trademark: VCFL61 (white): Toyo Ink Mfg. Co., Ltd .: Solid content 44% by weight C.I. I. Pigment: White-4 content 12% by weight 20 parts by weight Trademark: Matt medium (silica 15% by weight content clear): Toyo Ink Mfg. Co., Ltd. 10 parts by weight Trademark: ULS-933LP: Benzotriazole-based polymer UV absorber On the other hand, 3 parts by weight of Yushisha Kogyo Co., Ltd. Trademark: Irganox E201 (Vitamin E type: Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight Diluent: Toluene / methyl ethyl ketone (50/50 weight ratio) 30 parts by weight Part <Gravure Ink: Green> * Inorganic pigment: Organic pigment ratio = 3: 8 Trademark: VCFL79 (grass): Toyo Ink Mfg. Co., Ltd .: Solid content 37% by weight C.I. I. Pigment: Green-36 content 8% by weight 80 parts by weight Trademark: VCFL61 (white): Toyo Ink Mfg. Co., Ltd .: Solid content 44% by weight C.I. I. Pigment: White-4 content 12% by weight 20 parts by weight Trademark: Matt medium (silica 15% by weight content clear): Toyo Ink Mfg. Co., Ltd. 10 parts by weight Trademark: ULS-933LP: Benzotriazole-based polymer UV absorber : On the other hand 3 parts by weight of Yushisha Kogyo Co., Ltd. Trademark: Irganox E201 (Vitamin E: Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight Diluent: Toluene / methyl ethyl ketone (50/50 weight ratio) 30 parts by weight Part <Gravure Ink: Black> * Inorganic pigment: Organic pigment ratio = 6: 0 Trademark: VCFL94 (Black): Toyo Ink Mfg. Co., Ltd .: Solid content 32% by weight C.I. I. Pigment: Black-7 content 6% by weight 100 parts by weight Trademark: Matte medium (silica 15% by weight content clear): Toyo Ink Mfg. Co., Ltd. 10 parts by weight Trademark: ULS-933LP: Benzotriazole polymer UV absorber On the other hand, 3 parts by weight of Yushisha Kogyo Co., Ltd. Trademark: Irganox E201 (Vitamin E: Ciba Specialty Chemicals Co., Ltd.) 0.1 parts by weight Diluent: Toluene / methyl ethyl ketone (50/50 weight ratio) 30 parts by weight The obtained printed thermoplastic transparent resin film was
Using a laminator with a thermo roll set to ℃,
The printed surface was laminated with PU (3) so as to be in contact with one surface of the laminated fiber cloth (B) to obtain a transparent resin layer-coated body having a thickness of 0.54 mm and a mass of 621 g / m ² .

-(Iii) Formation of Intermediate Protective Layer-The same intermediate protective layer as in Example 1 was formed on the entire surface of the thermoplastic transparent resin layer (non-printed surface) of (ii) above. (Solid content deposition amount 3 g / m ² ) — (iv) Formation of photocatalytic substance-containing outermost surface antifouling layer— Forming an outermost antifouling layer containing
A polyurethane resin-coated antifouling print sheet having a thickness of 0.54 mm and a mass of 625 g / m ² was prepared.

[Example 8]-(i) Coating treatment of fiber cloth (B) with thermoplastic resin-The same fiber cloth (B) as in Example 5: polyester fiber plain weave base cloth was used as a base sheet. Separately, an ethylene-vinyl acetate copolymer resin compound composition having the following composition: E
VA (3) was kneaded under a heat condition of 136 ° C., and calender-rolled to form a film having a thickness of 0.18 mm.
Then, using a laminator equipped with a heat roll set to 130 ° C., the EVA was applied to both sides of the fiber fabric (B).
(3) Films are laminated by thermocompression bonding to a thickness of 0.44 mm,
A sheet-shaped substrate having a mass of 378 g / m ² was prepared.

-(Ii) Printing on the thermoplastic resin transparent layer (back surface) (screen printing)-Obtained from the same EVA (2) composition as in Example 4, having a thickness of 0.1 mm and a haze value of 1.1. EVA (2) Stained glass pattern of 5 colors (blue, red, yellow, green, black) was printed on the back side of the thermoplastic transparent resin film using 5 screen stencil plates with a 225 mesh stained glass pattern. And dried at 80 ° C. Stained glass picture is one for each color
Using screen stencil sheets, the solid print areas of blue, red, yellow, and green were set to 18%, and the black solid print area of the four-color border lines was set to 28%. <Screen ink: Blue> 70B-Blue: Solid content 56% by weight: Cyanine blue (CI Pigment: Blue-15) Content 12% by weight: Inorganic extender pigment 14% by weight: Seiko Advance Co., Ltd. 80% by weight Part 70B-White: Solid content 64% by weight: Rutile type titanium oxide (CI Pigment: White-4) Content 26% by weight: Inorganic extender pigment 10% by weight: Seiko Advance Co., Ltd. 20 parts by weight : Irganox E201: Vitamin E: Ciba Specialty Chemicals Co., Ltd. 0.2 part by weight Diluent: Cyclohexanone / Xylene (30/70) 10 parts by weight <Screen ink: Red> 70B-Red: Solid content 56 parts by weight %: Polyazo red (CI Pigment: Red-144) Content 12% by weight: Inorganic material Quality pigment 14% by weight: Seiko Advance Co., Ltd. 80 parts by weight 70B-White: solid content 64% by weight: rutile type titanium oxide (CI Pigment: White-4) content 26% by weight: inorganic extender pigment 10% by weight: Seiko Advance Co., Ltd. 20 parts by weight Trademark: Irganox E201: Vitamin E: Ciba Specialty Chemicals Co., Ltd. 0.2 parts by weight Diluent: Cyclohexanone / Xylene (30/70) 10 parts by weight < Screen ink: Yellow> 70B-Yellow: Solid content 56% by weight: Disazo yellow (CI Pigment: Yellow-12) Content 12% by weight: Inorganic extender pigment 14% by weight: Seiko Advance Co., Ltd. 80% by weight Part 70B-White: Solid content 64% by weight: Rutile type titanium oxide (CI Pigment: content-4) Content 26% by weight: Inorganic extender pigment 10% by weight: Seiko Advance Co., Ltd. 20 parts by weight Trademark: Irganox E201: Vitamin E: Ciba Specialty Chemicals Co., Ltd. 0.2 parts by weight Agent: cyclohexanone / xylene (30/70) 10 parts by weight <screen ink: green> 70B-green: solid content 56% by weight: phthalocyanine green (CI Pigment: Green-7) content 12% by weight: inorganic System extender pigment 14% by weight: Seiko Advance Co., Ltd. 80 parts by weight 70B-White: Solid content 64% by weight: Rutile titanium oxide (CI Pigment: White-4) Content 26% by weight: Inorganic system body Pigment 10% by weight: Seiko Advance Co., Ltd. 20 parts by weight Trademark: Irganox E201: Vitami E system: Ciba Specialty Chemicals Corp., 0.2 parts by weight of diluent: cyclohexanone / xylene (30/70) 10 parts by weight <Screen Ink: Black> 70B- Black: solids 56% by weight: carbon black (C ． I. Pigment: Black-7) Content 10% by weight: Inorganic extender pigment 14% by weight: Seiko Advance Ltd. 95 parts by weight 70B-White: Solid content 64% by weight: Rutile titanium oxide (CI Pigment) : White-4) Content 26% by weight: Inorganic extender pigment 10% by weight: Seiko Advance Co., Ltd. 5 parts by weight Trademark: Irganox E201: Vitamin E: Ciba Specialty Chemicals Co., Ltd. 0.2 parts by weight Diluent: cyclohexanone / xylene (30/70) 10 parts by weight

-(Iii) Formation of Intermediate Protective Layer-The same intermediate protective layer as in Example 1 was formed on the entire surface of the thermoplastic resin transparent film (non-printed surface) of (ii) above. (Solid content deposition amount: 3 g / m ² ) A thermoplastic resin transparent film having an intermediate protective layer on the front surface and a print pattern on the back surface was prepared using a laminator equipped with a heat roll set at 130 ° C. The printed surface is laminated in a direction in which it contacts one surface of the fiber cloth (B) laminated with EVA (3), and the thickness is 0.54 mm and the mass is 485 g /
A base material of m ² was obtained.

-(Iv) Formation of outermost surface antifouling layer containing photocatalytic substance- The same outermost surface antifouling layer containing a photocatalytic substance as in Example 1 was formed on the entire surface of the intermediate protective layer of (iii) above. , Thickness 0.54
An ethylene-vinyl acetate copolymer resin-coated print sheet having a mass of 486 g / m ² was prepared.

Table 1 shows the constitution and performance test evaluation results of the antifouling print sheets of Examples 11 to 8.

[Table 1]

[Performance of Antifouling Print Sheets of Examples 1 to 8] The antifouling print sheets obtained in Examples 1 to 8 were spread outdoors (Test I), and the degree of contamination was measured every 6 months. As a result of observing for one and a half years, the dust and dirt (environmental stain) on the surface of the print sheet was extremely small, and therefore, the print pattern was clear and the aesthetics of the sheet could be maintained. Further, according to the detailed observation every month, the dust dust adhering to the surface of the print sheet is
It was confirmed that accumulated dust on these sheets, such as most of the adhered stains being washed away, was successively decomposed by the photocatalytic substance and was always placed in a state where it was easily detached from the surface of the sheet. This self-cleaning function
The small sample collected from the outdoor spreading sheet can be easily removed by soaking it in tap water for 10 minutes, exposing it to running tap water and rubbing the surface lightly with the pad of your finger. It was clear. Further, the results of the light-proofing accelerated test of the printed pattern (Test III) for 240 to 1000 hours are particularly shown in the sheets printed with the gravure ink (Examples 1, 5 and 7) and the sheet printed with the screen ink ( In Examples 4 and 8), cracks, fading, and extreme discoloration of the sheet surface were not observed at all,
It had good color retention. 10 of these sheets
The color difference ΔE values after irradiation for 00 hours were all within 3.0, and the color difference ΔE values were all within 5.0 even in the sheet printed by the inkjet method. Also,
The sheets of Examples 1 to 8 had a aesthetically-maintaining property of printed images in actual outdoor use (Test II). As a result of simultaneous observation of stains in an outdoor spreading test, cracks on the sheet surface of any of the sheets, No fading or extreme discoloration was observed, and all color difference ΔE values were 5.0 even after one and a half years.
It was within the range, and the result (good color retention) with the same tendency as the acceleration test (III) was obtained. Further, in the print sheet of Example 3, 4, 7, 8 containing the resin coating layer for the sheet-shaped base material containing the polyurethane resin or the ethylene-vinyl acetate copolymer resin, nitrogen content is particularly contained in the resin coating layer. By blending a compound (melamine cyanurate compound) as a halogen-free flame retardant, flame resistance required for tent film materials (JIS L-1091: A-2 method category 3)
Was able to be given. Further, as a color pigment of the resin coating layer of the sheet-shaped substrate obtained in Examples 1 to 8 and a color pigment component for a printing ink composition, particularly by using an inorganic pigment in combination in a specific amount or more, In the resin coating layer, the thermoplastic transparent resin layer, and the printing ink composition,
By adding antioxidants, especially by selecting and adding vitamin E compounds as antioxidants,
It has become possible to improve the durability of the resin coating layer and the thermoplastic transparent resin layer and to keep the color quality of printing beautiful. Therefore, the antifouling print sheet of the present invention has the above (I).
From the test results of ~ (III), it is possible to maintain the colorfulness of the colorful print pattern for a long time, and also to have the self-cleaning function by the photocatalytic substance without damaging the print pattern and the sheet film material itself. Therefore, it is suitable as a sheet for outdoor decoration, particularly as a tent film material.

[Comparative Example 1] A thermoplastic resin for which the intermediate protective layer was omitted from the sheet of Example 1 and the substrate was coated:
From the composition of PVC (1), 0.2 parts by weight of an antioxidant (trademark: Irganox E201: Vitamin E: Ciba Specialty Chemicals Co., Ltd.) is omitted, and the composition of the gravure ink used for printing is omitted. Antioxidant (trademark: Irganox E201: Vitamin E type:
A print sheet was prepared in the same manner as in Example 1 except that 0.1 part by weight of Ciba Specialty Chemicals Co., Ltd. was removed.

Comparative Example 2 The intermediate protective layer and the thermoplastic transparent resin layer: PVC (2) were omitted from the sheet of Example 2, and the thermoplastic resin for coating the base material: PVC (1).
Antioxidant (trademark: Irganox E
201: Vitamin E type: Ciba Specialty Chemicals Co., Ltd. A print sheet was prepared in the same manner as in Example 2 except that 0.2 part by weight was omitted.

[Comparative Example 3] The intermediate protective layer and the thermoplastic transparent resin layer: PU (2) were omitted from the sheet of Example 3,
Further, from the compounding composition of the thermoplastic resin: PU (1) coating the base material, the antioxidant (trademark: Irganox E20)
1: Vitamin E type: Ciba Specialty Chemicals Co., Ltd. A print sheet was prepared in the same manner as in Example 3 except that 0.2 part by weight was omitted.

[Comparative Example 4] The intermediate protective layer and the thermoplastic transparent resin layer: EVA (2) were omitted from the sheet of Example 4, and the thermoplastic resin: EVA (1) covering the base material was omitted.
Antioxidant (trademark: Irganox E
201: Vitamin E type: Ciba Specialty Chemicals Co., Ltd. A print sheet was prepared in the same manner as in Example 4 except that 0.2 part by weight was omitted.

Table 2 shows the constitution and performance of each print sheet of Comparative Examples 1 to 4.

[0099]

[Table 2]

[Performance of Print Sheets of Comparative Examples 1 to 4]
The print sheets obtained in Comparative Examples 1 to 4 were spread outdoors (Test I), and the stain degree was observed every 6 months for one and a half years. As a result, the sheets of Comparative Examples 1 to 4 had an intermediate protective layer. By omitting, the photocatalytic substance-containing outermost surface layer fell off from the sheet by 80% or more 6 months after the spreading, and the stain resistance was insufficient due to this influence. The sheets obtained from the polyurethane resin of Comparative Examples 3 and 4 (PU (1)) and the ethylene-vinyl acetate copolymer resin (EVA (1)) have a resin composition containing no plasticizer, and therefore, after one and a half years In the state of No. 1, no extreme dust pollution was reached, but especially Comparative Example 1
Polyvinyl chloride resin containing plasticizers Nos. 2 and 3: PVC
In (1), the plasticizer exudes on the surface of the sheet,
A large amount of soot dust adhered to this, and after a year and a half, the soot dust became conspicuous, and the image-printed pattern was dirty. In addition, at the same time, the aesthetic appearance retention (test II) of the printed images of the sheets of Comparative Examples 1 to 4 was noticeably discolored and discolored in any of the sheets. The pigment component of the ink used for printing was decomposed and deteriorated by the oxidative action of the photocatalytic substance during the initial period of about 6 months, which was fixed to No. 1, and this was the cause of fading and discoloration. Degradation and deterioration of the pigment component by the photocatalytic substance was extremely fading for about the first 6 months after the lapse of 6 months when 80% or more of the outermost layer containing the photocatalytic substance had fallen off, and the discoloration did not proceed. Further, the results of 240 to 1000 hours of the light fastness test (test III) of the printed pattern showed that the sheet printed by the inkjet method was discolored and the discoloration was remarkable. In particular, in the case of the inkjet-printed sheet of Comparative Example 2, the sheet was soiled during outdoor spreading, and the color of the print pattern was fading and discoloration was not so noticeable, but the color difference ΔE value was 17.4 after 1000 hours of the light fastness test. became. Particularly, polyvinyl chloride resin of Comparative Examples 1 and 2: PVC
(1) Outdoor stretching test (II) and accelerated light resistance test (I)
In the sheets of Comparative Examples 3 and 4, the same tendency was observed in the fading and discoloring behaviors, except that the correlation with II) was not obtained due to the influence of dust contamination due to the seepage of the plasticizer. Further, as a comparison other than Comparative Examples 1 to 4, when a sheet using a coloring pigment of a resin coating layer of a sheet and a coloring pigment component of a printing ink composition, in particular, a specific amount of an organic pigment or more was spread outdoors, intermediate protection was performed. It was found that the absence of layers was a major factor, and these organic pigments were quickly decomposed by the oxidizing action of the photocatalytic substance, resulting in extreme fading and discoloration. Furthermore, since no antioxidant (particularly vitamin E compound) was added to the resin coating layer, the thermoplastic transparent resin layer, and the printing ink composition, the surface of the resin coating layer and the thermoplastic transparent resin layer was In some cases, fine cracks were generated, or it was impossible to keep the color of the print beautiful. Therefore, it was revealed that the sheet of Comparative Example is not suitable for practical use because it has insufficient antifouling property, and the photocatalytic effect damages the aesthetic appearance of the print pattern and the sheet film material itself.

[0101]

As is clear from the above Examples and Comparative Examples, the antifouling print sheet of the present invention utilizes the oxidizing action of the photocatalytic substance to prevent dust and dirt (environmental stains) from adhering to it for a long period of time. It has a self-cleaning effect to prevent, and at the same time, it is possible to maintain the vivid colors and aesthetics of the printed pattern for a long time. In addition, the base material to which the technique of the present invention can be applied has a wide range of applications such as a film, a fiber cloth, and a fiber cloth coated with a thermoplastic resin. Further, as a thermoplastic resin for covering the fiber cloth, soft polyvinyl chloride is used. Since thermoplastic resins other than resins can also be applied,
It has a wide range of applications and is highly useful. Therefore, the antifouling print sheet of the present invention can be suitably used as a sheet for industrial materials, especially for applications such as shade tents, medium and large-sized tents, which are required to have colorful hues and print patterns.

[Brief description of drawings]

FIG. 1 is a cross-sectional explanatory view showing an example of a laminated structure of an antifouling print sheet of the present invention.

FIG. 2 is a sectional explanatory view showing another example of the laminated structure of the antifouling print sheet of the present invention.

FIG. 3 is a sectional explanatory view showing still another example of the laminated structure of the antifouling print sheet of the present invention.

FIG. 4 is a sectional explanatory view showing still another example of the laminated structure of the antifouling print sheet of the present invention.

[Explanation of symbols]

1 ... Sheet-shaped substrate 1a ... Base sheet (fiber cloth, film, etc.) 1b, 1c ... Resin coating layer 2 ... Printed image 3 ... Intermediate protective layer 4 ... Outermost surface antifouling layer 5 ... Transparent resin layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B41M 1/30 B41M 1/30 Z 3/06 3/06 J 7/02 7/02 F term (reference) 2H113 AA01 AA03 AA04 AA06 BA03 BA05 BA09 BB02 BB06 BB07 BB32 DA07 DA08 DA09 DA10 DA12 DA15 DA41 DA47 DA48 DA49 DA52 DA55 DA56 DA57 DA60 DA62 DA64. AK41 AK52C AK52D AK53C AK53D AK80C AK80D AR00B AR00D AS00C AT00A BA03 BA04 BA05 BA07 BA10A BA10B CA13A CA13C CA30B DE01A DG10A DG11A DG12 DJ10A EA061 EG002 EH462 EJ862 EJ91C EJ91D GB07 GB90 HB00A HB00D HB31A HB31D JB16C JL00 JL06B JL08B JL10A JM10A JN01A JN01C JN01E JN02A JN30C JN30D JN30E

Claims (24)

[Claims] 1. A sheet-like base material, and an outermost antifouling layer formed on at least the surface of the front and back surfaces of the sheet-like base material and containing a photocatalytic substance. An image is printed on the surface of a material, and between the printed surface of the sheet-shaped substrate and the outermost surface antifouling layer, the sheet-shaped substrate and the printed image, the photocatalytic property An antifouling print sheet, characterized in that an intermediate protective layer is formed for protection from the action of substances. 2. A sheet-shaped substrate, and an outermost surface antifouling layer formed on at least the surface of both front and back surfaces of the sheet-shaped substrate and containing a photocatalytic substance. An image is printed on the surface of the material, in the middle of the printed surface of the sheet-shaped substrate, and the outermost surface antifouling layer, containing a thermoplastic resin, and a transparent transparent resin layer, An intermediate protective layer formed on the printed surface of the sheet-shaped substrate, and between this transparent resin layer and the outermost surface antifouling layer, protects the transparent resin layer from the action of the photocatalytic substance. An antifouling print sheet, which is formed. 3. A sheet-shaped substrate, and an outermost antifouling layer formed on at least the surface of both front and back surfaces of the sheet-shaped substrate and containing a photocatalytic substance. In the middle of the material and the outermost surface antifouling layer, on the surface of the sheet-shaped substrate, containing a thermoplastic resin,
And a transparent transparent resin layer is formed, and between the transparent resin layer and the outermost surface antifouling layer, an intermediate protective layer for protecting the transparent resin layer from the action of the photocatalytic substance is formed, An antifouling print sheet, wherein an image is printed on the surface of the transparent resin layer that is bonded to the sheet-shaped substrate. 4. The sheet-shaped substrate is selected from fiber cloth, plastic film and synthetic paper.
The antifouling print sheet according to any one of 1. 5. The sheet-shaped substrate comprises a base sheet and at least one resin coating layer which is formed on at least one surface of the substrate sheet and contains a thermoplastic resin. At least one of the resin coating layers is provided. The antifouling print sheet according to claim 1 or 2, wherein an image is printed on the surface of one layer. 6. The substrate according to claim 3, wherein the sheet-shaped substrate is composed of a base sheet and at least one resin coating layer formed on at least one surface of the base sheet and containing a thermoplastic resin. Antifouling print sheet described. 7. The antifouling print sheet according to claim 5, wherein the base sheet of the sheet-shaped substrate is selected from fiber cloth, plastic film and synthetic paper. 8. The antifouling print sheet according to claim 1, wherein the sheet-shaped substrate is colorless or colored. 9. The antifouling print sheet according to claim 8, wherein the colorless or colored sheet-shaped substrate is transparent or opaque. 10. The antifouling print sheet according to any one of claims 1 to 9, wherein the image is printed by an inkjet printing method. 11. The image according to claim 1, which is printed by at least one printing method selected from gravure printing, screen printing, offset printing, and transfer printing. Antifouling print sheet. 12. The antifouling print sheet according to claim 1, wherein the printed image is formed with an ink containing 20% by weight or more of an inorganic pigment. 13. The intermediate protective layer comprises a silicone resin, a fluorine resin, a melamine resin, an epoxy resin,
The antifouling print sheet according to any one of claims 1 to 12, containing at least one selected from phosphazene resins. 14. The antifouling print sheet according to claim 1, wherein the intermediate protective layer further contains a silicon compound. 15. The antifouling print sheet according to any one of claims 1 to 14, wherein the silicon compound for the intermediate protective layer is selected from polysiloxane, colloidal silica, and silica. 16. The antifouling print according to claim 1, wherein the intermediate protective layer has a haze value of 10 or less (ASTM D1003) and / or a light transmittance of 80% or more. Sheet. 17. The antifouling print sheet according to claim 2, wherein the transparent resin layer has a haze value of 10 or less (ASTM D1003) and / or a light transmittance of 80% or more. 18. A composite layer comprising the transparent resin layer and the intermediate protective layer formed thereon, as a whole,
The antifouling print sheet according to claims 2 to 12, which has a haze value of 10 or less (ASTM D1003) and / or a light transmittance of 80% or more. 19. The outermost surface antifouling layer is 9 to 70% by weight.
25 to 90% by weight of at least one selected from a metal oxide gel and a metal hydroxide gel.
The antifouling print sheet according to any one of claims 1 to 18, which contains a seed and 1 to 20% by weight of a silicon compound. 20. The photocatalytic substance of the outermost surface antifouling layer,
Titanium oxide (TiO ₂ ), Titanium peroxide (peroxothiophene)
Tannic acid), zinc oxide (ZnO), tin oxide (SnO)₂ ),
Strontium titanate (SrTiO₃ ), Oxide tongue
Stainless (WO ₃ ), Bismuth oxide (Bi₂ O₃ ),as well as
Iron oxide (Fe₂ O₃ ), And the above compounds
From porous fine particles carrying one or more of
20. The method according to claim 1, which comprises at least one selected from
The antifouling print sheet according to the item 1. 21. An image is printed on at least the surface of the front and back surfaces of the sheet-shaped substrate, and the sheet-shaped substrate and the printed image are photocatalysted on the printed surface of the sheet-shaped substrate. Forming an intermediate protective layer for protecting from the action of a functional substance, and forming an outermost antifouling layer containing a photocatalytic substance on the intermediate protective layer, a method for producing an antifouling print sheet, . 22. An image is printed on at least the front surface and the back surface of the sheet-shaped substrate, and a transparent transparent resin layer containing a thermoplastic resin is provided on the printed surface of the sheet-shaped substrate. Formed, on the transparent resin layer, to form an intermediate protective layer for protecting this transparent resin layer from the action of the photocatalytic substance, on the intermediate protective layer, the outermost surface antifouling layer containing a photocatalytic substance. A method for producing an antifouling print sheet, which comprises: forming. 23. An image is printed on one surface of a transparent film containing a thermoplastic resin, and the printed surface of the transparent film is laminated on at least the surface of both sides of the sheet-like substrate. The laminated transparent film, on the surface not printed, to form an intermediate protective layer for protecting the transparent resin layer from the action of the photocatalytic substance, on the intermediate protective layer, photocatalytic A method for producing an antifouling print sheet, comprising forming an outermost antifouling layer containing a substance. 24. An intermediate protective layer for printing an image on one side of a transparent film containing a thermoplastic resin and protecting the other side of the transparent film from the action of a photocatalytic substance. Of the front and back surfaces of the sheet-shaped substrate, at least on the surface thereof, the printed surface of the transparent film is laminated, and the outermost antifouling layer containing a photocatalytic substance on the intermediate protective layer. A method for producing an antifouling print sheet, which comprises: forming.