JPH09152737A - Substrate for copied image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior weather resistance, fouling resistance and durability at the time of outdoor use by forming a copied image layer consisting of carboxyl modified PVA(polyvinyl alcohol), polyurethane resin and a crosslinking agent. SOLUTION: This substrate has a copied image layer consisting of carboxyl modified PVA, polyurethane resin and a crosslinking agent. The modified PVA is a polymer having structural units derived from a monomer having a carboxyl group such as acrylic acid in the principal chain of PVA. Any polyurethane resin generally used in a urethane resin coating material may be used as the polyurethane resin. The crosslinking agent is a compd. having two or more functional groups capable of reacting with the modified PVA and the polyurethane resin and reacts with them.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a substrate for copied images.

[0002]

2. Description of the Related Art Conventionally, marking films have been used for display, decoration and the like by sticking to the surface of objects such as buildings, vehicles and machinery.

The marking film is usually a polyvinyl chloride film having characters, pictures, etc. printed on one side by screen printing. However,
This method requires labor for color matching when performing multicolor printing, and takes time because printing is performed for each color. Further, when a complicated pattern is to be printed, the screen printing is performed many times, which requires a lot of labor and time.

It is also common practice to apply a transparent coating on the printed surface of a marking film to form a transparent coating film. As the transparent coating, a curable resin is dissolved in an organic solvent. Since things are used, the work environment may deteriorate and there is a risk of fire. Further, there is a drawback that the step of forming the coating film also takes time and the product cost increases.

At present, there is also a method of copying a picture or the like on a film by using a color copying machine. Paper, synthetic paper, polyester, acrylic and the like are used as the material of the film. However, when the film is used outdoors, there are drawbacks in water resistance, durability, moist heat resistance, heat resistance, antifouling property, and the like, and a fluoropolymer has attracted attention as an alternative film material. Fluorine-based polymer has chemical resistance,
It is extremely excellent in stain resistance, weather resistance, etc., has many advantages that it does not react with chemicals, etc., and is insoluble in ordinary solvents. However, a film made of the fluoropolymer has a low surface free energy, and thus it is difficult to draw directly. Therefore, the surface is subjected to an electric discharge treatment to be hydrophilic, and the surface of the film is made hydrophilic by using an adhesive. An overlay method may be considered, but the adhesion to the copy image layer is weak,
It has a drawback that the copied image layer is easily peeled off. In order to solve such a drawback, the present inventor previously proposed a coating composition having excellent adhesiveness with a fluoropolymer and adhesiveness with an image (Japanese Patent Laid-Open No. 7-247463). However, such compositions include inorganic fillers and organic fillers.
It was found that the copied image was blurred by the filler and lacked the sharpness of the image due to the blending of the above. It was also found that the use of the modified polyvinyl alcohol containing a sulfonic acid group has the drawbacks that the adhesiveness with the fluoropolymer film is poor and the water resistance is poor.

[0006]

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluoropolymer film having a low surface free energy and a copy image layer firmly. It is an object of the present invention to provide a copied image substrate which is adhered and has excellent weather resistance, stain resistance and durability for outdoor use.

[0007]

SUMMARY OF THE INVENTION The present invention comprises a hydrophilized fluoropolymer film layer and a copy image layer,
The copy image layer comprises a carboxyl-modified polyvinyl alcohol (A), a polyurethane resin (B) and a crosslinking agent (C).
It is a substrate for copied images, characterized by comprising:

Examples of the "fluorine-based polymer" according to the present invention include tetrafluoroethylene-perfluoroalkylvinylether copolymer, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene-chlorotriene. Fluoroethylene copolymer, trifluoroethylene-tetrafluoroethylene copolymer, trifluoroethylene-tetrafluoroethylene-alkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, fluorine-containing acrylic acid ester Examples thereof include polymers and copolymers of fluorine-containing acrylic acid ester with methacrylic acid and / or methyl methacrylate.

It is necessary to use a hydrophilized fluoropolymer film in order to improve the adhesion to the copy image layer. Further, the light transmittance of the fluoropolymer film is preferably 30% or more, particularly preferably 50% or more when an internally-illuminated public notice board is prepared.

When the copy image substrate of the present invention is used outdoors, it is preferable that an ultraviolet absorber layer is laminated on the fluoropolymer film in order to improve durability. Such an ultraviolet absorber layer is a method in which an ultraviolet absorber is added to a fluoropolymer to perform hot melt extrusion molding, a cast film molding method when a solvent-soluble fluoropolymer is used, and the fluoropolymer described below. It is formed by a method of forming an ultraviolet absorber layer by adding an ultraviolet absorber to a hydrophilic resin used for adhering the film layer and the copy image layer. The UV absorber is not limited to any kind as long as it is a normal UV absorber, but it is preferably one which does not deviate the light transmittance of the fluoropolymer film, specifically, 2,4-di-t. -Butylphenyl-
Benzophenone compounds such as 3 ′, 5′-di-t-butyl-4′hydroxybenzoate and 2,4-dihydroxybenzophenone, 2- (2′-hydroxy-5′-t
-Octylphenyl) benzotriazole, 2- (2 '
Examples thereof include benzotriazole compounds such as -hydroxy-5'-methylphenyl) benzotriazole and phenyl salicylate compounds.

The content of the ultraviolet absorber is preferably 0.05 to 5.0% by weight with respect to the fluoropolymer, and 0.1 to 0.5% by weight from the viewpoint of light transmittance and polarization performance. More preferable.

The copy image layer according to the present invention is a layer on which an image can be copied by a copying machine. The copying machine is not particularly limited, and a conventional single-color or multi-color (color) copying machine can be used, but an electrophotographic type in which toner particles are electrostatically fixed is preferable.

Carboxyl-modified polyvinyl alcohol (A) [hereinafter referred to as CA-modified PVA] which forms the copy image layer.
It is referred to as (A). ] Is a polymer having a structural unit derived from a monomer containing a carboxylic acid group in the main chain of polyvinyl alcohol. Examples of the monomer containing a carboxylic acid group include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, and metal salts thereof. In the present invention, CA-modified PVA (A)
As the structural unit derived from the carboxylic acid group-containing monomer is 0. based on all the structural units of the CA-modified PVA (A).
It is preferable to use 1 to 10 mol% from the viewpoint of solubility in a water / organic mixed solvent, and the ratio of the structural units is 2
It is preferable to use the one of about 4 mol%. Also CA
The modified PVA (A) has a number average molecular weight of 200.
It is preferable that the number average molecular weight is 300 to 5,000 and the saponification degree is 80 mol% or more from the viewpoint of water resistance and solubility.
Those having a saponification degree of 2000 and 95 mol% or more are particularly preferable.

This CA-modified PVA (A) is generally obtained by copolymerizing a vinyl alcohol ester such as vinyl acetate and a carboxylic acid group-containing monomer, and then saponifying the ester group in the copolymer to give an alcohol group. It can be manufactured by replacing.

As the polyurethane resin (B), any of the polyurethane resins usually used in polyurethane resin paints can be used, and those which form urethane bonds in the film formation process, urethane bonds in the resin in advance You can use any of those that have. Polyurethane resin for paints is a two-component type composed of a combination of polyol and polyisocyanate, moisture-curable polyurethane resin, block-isocyanate-curable polyurethane resin, oil-modified polyurethane resin, lacquer. There is a one-pack type in which a type polyurethane resin or the like is used as a vehicle, but the present invention is not particularly limited, and any of them can be used.

The isocyanate compound for the polyurethane resin is tolylene diisocyanate, 4,4-
Diphenylmethane diisocyanate, Polymeric-
4,4-Diphenylmethane diisocyanate, xylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tolidine diisocyanate
Tetramethylyl xylylene diisocyanate, 3,
Aromatic diisocyanates such as 3'-dichloro-4,4'-diphenylmethane diisocyanate; hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenation Alicyclic rings such as xylylene diisocyanate, isopropylidene bis (4-cyclohexyl diisocyanate), cyclohexyl diisocyanate, 2,2,4-trimethyl-1,6-hexane diisocyanate Formula or aliphatic diisocyanate; lysine diisocyanate; dimer of these
Examples thereof include compounds, trimer compounds, and carbodiimidated compounds. These isocyanate compounds may be used alone or in combination of two or more kinds.

When the two-component type polyurethane resin (B) is used, the above isocyanate compound or an isocyanate resin previously prepared by using the isocyanate compound together with polyol is used. And are used to obtain these polyol and isocyanate resins,
Immediately before forming a copy image layer on one side of the above-mentioned fluoropolymer film, it is mixed with CA-modified PVA (A) in a specific ratio, and the layer is formed by polymerizing by urethane bond formation.

Examples of the polyol include low molecular weight polyols such as ethylene glycol, diethylene glycol, 1,4-butanediol and hexamethylene glycol.
Polyethylene glycol, polyoxypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene ether glycol and other polyether polyols; poly-β-methyl-δ-valerolactone, Polyester-polyols such as polyesters consisting of polycaprolactone, diole and dibasic acids such as adipic acid, azelaic acid, sebacic acid, isophteric acid and terephthalic acid; polycarbonate-polyols;
Examples include polyester polyol; acrylic polyol; epoxy polyol; liquid butadiene having a hydroxyl group; neoprene having a hydroxyl group. Of these, polyester polyols are particularly preferred because yellowing hardly occurs.

When an isocyanate resin is used as the isocyanate component, the above-mentioned isocyanate is used.
Compound to ethylene glycol, propylene glycol
, Butanediol or other diol, glycerin, pentaerythritol, polyisocyanate prepolymer obtained by reacting with one or more kinds of other trifunctional or higher functional polyols, Isocine such as burette or isocyanurate type polyfunctional trimer
Resin can be used.

When a one-component moisture-curable polyurethane resin is used as the polyurethane resin (B),
A conventionally known moisture-curable polyurethane resin used as a paint can be used.

As the polyurethane resin (B), 1
When a liquid block isocyanate-cure polyurethane resin is used, the above-mentioned isocyanate compound or isocyanate resin may be added to alcohol, phenol or active methylene (for example, acetoacetic acid, lactam or oxime). It is possible to use a mixture of the above low molecular weight polyol or high molecular weight polyol by reacting with a blocking agent such as (1) to block the isocyanate group for stabilization.

Further, when a one-pack type oil-modified polyurethane resin is used as the polyurethane resin (B), the drying oil is transesterified with a polyhydric alcohol, and then the polyisocyanate compound as described above is reacted. The urethanized oil, the drying oil fatty acid-modified alkyd resin and the like obtained in this way can be used. When a one-pack type lacquer type polyurethane resin is used as the polyurethane resin (B), a high molecular weight diisocyanate-terminated prepolymer obtained by reacting a difunctional polyester polyol with a diisocyanate compound is used. It is possible to use those to which a chain extender composed of glycol or amine having a molecular weight is added.

In the present invention, from the viewpoint of workability, it is preferable to use, as the polyurethane-based resin (B), Mercury polyurethane-based resins among the various polyurethane resins described above. In particular, it is preferable to use the self-emulsifying type. In adjusting the copy image layer of the present invention, the polyurethane resin (B) can be used in any form such as liquid, solution, dispersion liquid, and solid form.

In the copy image layer of the present invention, the CA-modified PVA is used.
(A) and polyurethane resin (B) (A): (B)
= 99.9: 0.1-0.1-99.9, especially 5: 9
It is preferably used in a ratio of 5 to 30:70 (weight ratio). Although CA-modified PVA (A) is heat-meltable, it dissolves in water, and therefore CA-modified PVA (A) is CA-modified PVA from the viewpoint of water resistance of the layer.
It is preferable to increase the amount of the polyurethane resin (B) than that of (A).

Further, the cross-linking agent (C) forming the copy image layer according to the present invention comprises CA-modified PVA (A) and a compound having two or more functional groups capable of reacting with the polyurethane resin (B). By reacting with the modified PVA (A) and the polyurethane resin (B), a water-insoluble coating layer is formed on the fluoropolymer film. Examples of the cross-linking agent (C) include epoxy compounds, aldehyde compounds, aziridine compounds, aminoplast compounds and polyvalent metal compounds. In some cases, the blocked polyisocyanate compound can be used as the crosslinking agent (C) separately from the polyurethane resin (B).

As the epoxy compound, any of compounds having two or more epoxy groups represented by glycidyl groups in the molecule can be used. Specifically, sorbitol polyglycidyl ether and glycero can be used. -Diglycidyl ether, glycerol triglycidyl ether, polyethylene glycol diglycidyl ether, polyamide epichlorohydrin resin and the like can be mentioned, of which glyceryl diglycidyl ether is preferred.

As the aldehyde compound, any compound can be used as long as it generates an aldehyde during the formation of a copy image layer. Specifically, formalin, acetaldehyde, propionaldehyde, butyraldehyde and other monoaldehydes, Polyhydric aldehydes such as glyoxal, glutaraldehyde and dialdehyde starch, polyaldehydes, condensates of formalin and ammonia such as hexamethylenetetramine, and acrylamide glyoxer
And a reaction copolymer. Of these, glyoxal is preferred.

As the aziridine-based compound, those having two or more ethyleneimine derivative groups in the molecule can be used.

As the aminoplast compound, a condensate of a compound having an amino group such as melamine, a urea-aldehyde condensate or an aniline-aldehyde condensate with an aldehyde, or a methylated product or an alkoxylated product thereof.
Alkoxymethylated products, amidated products and the like can be used.

The amount of the crosslinking agent (C) added is CA-modified PV.
Generally, CA-modified PV, though it depends on the types of A (A), polyurethane resin (B) and crosslinking agent (C).
0.05 to 30 parts by weight, particularly 0.3 to 2 per 100 parts by weight of the total amount of A (A) and polyurethane resin (B)
It is preferably 0 parts by weight.

In the present invention, the above-mentioned CA-modified PVA is used.
(A), polyurethane resin (B) and crosslinking agent (C)
The image is electrostatically copied on the copy image layer consisting of, but the dye, pigment, colorant, etc. are mixed in the copy image to form a colored layer directly on the layer, or characters and patterns are directly formed. You can also draw.

The above-mentioned mixture of CA-modified PVA (A), polyurethane resin (B) and crosslinking agent (C) is
It is preferably dispersed or dissolved in a liquid solvent such as water, a mixed solvent of water and alcohol, an alcohol, or a mixed solvent of a polar solvent other than alcohol, to adjust. In particular,
It is preferable to use water or alcohol as a medium from the viewpoint of solubility, work safety, prevention of air pollution and the like.

The viscosity of the preparation liquid of the mixture is CA-modified PV.
Although it may vary depending on the mixing ratio of A (A), polyurethane resin (B) and cross-linking agent (C), the degree of polymerization, etc., it is generally about 10-900 cps, 30-90 cps when measured by the Bruckner method at a temperature of 25 ° C. About 200 cps is preferable. The total solid content concentration in the adjustment liquid varies depending on the type of each component, the mixing ratio, the type of liquid medium, etc., but is generally about 3 to 40% by weight, preferably about 5 to 20% by weight. .

In the present invention, the copy image layer is generally well-known coating methods such as brush coating, roller coating, spray coating, cast coating and coating, screen coating,
Any method such as a calendar coat or a dip coat can be adopted, and the thickness of the layer can be appropriately adjusted according to the application, but generally, the thickness of the copy image layer after drying is 2
The range of -100 μm, especially 5-40 μm is preferable.

The copy image layer can be directly coated on the surface of the fluoropolymer film that has been subjected to the hydrophilic treatment, but a hydrophilic resin can be used as an adhesive in order to further enhance the adhesiveness of both layers. . As such a hydrophilic resin, those conventionally used as an adhesive such as a marking film can be used, and a polyester resin, a polymethacrylate ester resin, a polyacrylic acid resin, a vinyl chloride resin, Vinylidene chloride resin, isobutylene resin, polyurethane resin, solvent-soluble fluoropolymer resin, cellulose resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyacrylonitrile resin, ethylene-vinyl acetate resin Resin etc. can be mentioned. Of these, polyester resins, polyurethane resins, and polymethacrylic acid ester resins are preferable from the viewpoint of adhesiveness with the fluoropolymer film. The film thickness of the hydrophilic resin is preferably 2 to 150 μm, particularly preferably 3 to 60 μm.

Further, in order to raise the image by changing the color behind the image or blur the image to form a different image, a metal vapor deposition layer, a primer layer, an intermediate coating layer together with the above hydrophilic resin are formed. Can be provided.

The copy image substrate of the present invention uses the surface of the fluorine-based film as a surface. Therefore, it is necessary to invert and copy the image on the copy image layer. Therefore, caution is required when copying characters and the like.

The copy image substrate of the present invention has a thickness of 1
If it is less than 50 μm, the process passability in electrostatic copying may become a problem, and since the toner transfer requires a temperature of 70 ° C. or more, a protective sheet (film) is attached to the surface of the fluororesin film. Preferably. As the sheet, polyester resin, polyolefin resin, polymethacrylic acid ester resin, paper or the like can be used, and it is preferable to stick with an acrylic adhesive.
The acrylic pressure-sensitive adhesive is preferable because it does not remain on the fluoropolymer film when the sheet is peeled from the fluoropolymer film.

The base substrate for a copied image of the present invention forms an image on the copied image layer by copying, etc., and an adhesive such as an acrylic adhesive is applied to the copied image layer, and the coated surface is an acrylic plate or the like. It can be attached to and used as a signboard announcement. Since the outermost surface of the notice of the signboard is a fluoropolymer film, conventional problems such as ultraviolet rays, moisture, temperature, chemicals, stains, etc. can be solved, and further, since a specific mixture is used as the copy image surface, Images such as copied images are clear, and the adhesion of the coloring agent is excellent, and a highly durable signboard advertisement can be obtained.

[0040]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
In the following examples, parts and% are unless otherwise specified.
They mean parts by weight and% by weight, respectively. The measurement in each example was performed by the following method. (1) Adhesion test with image A fluoropolymer film was coated with a copy image layer and then dried, and an image was formed on the copy image by electrostatic copying.
Then, after sticking a cellotepe on the image layer, it was peeled off momentarily by holding the end of the cellotepe, and the presence or absence of the image toner adhering to the adhesive surface of the cellotepe was examined, and the following evaluations were made. I went. ◯: No image toner was attached to the adhesive surface of the tape. (Triangle | delta): 10-50% of the image toner adhered to the adhesive surface of the tape. X: 50% or more of the image toner adhered to the adhesive surface of the cellotepe. (2) Adhesion test between fluoropolymer film and copy image layer A copy image layer was applied to the fluoropolymer film and then dried, and a serote was formed on the copy image layer formed as a result.
After sticking the tape, the film and the end portions of the cellotepe are held at an angle of 180 degrees to be peeled off instantaneously, and the presence or absence of a copy image layer attached to the adhesive side of the cellotepe is examined. When the peeled portion is 0 to 5%, it is Class A, and when it is 5 to 30%, it is B
Grade, and the case of 30 to 100% was designated as C grade.

(3) Evaluation Criteria for Coloring and Sharpness of Image (Evaluation with the naked eye) The copied image was evaluated by 10 panelists. ◯: 8 or more out of 10 were judged to be good. Δ: 5 to 7 out of 10 were judged to be good. X: Less than 54 out of 10 were judged to be good. (4) Water resistance After immersing the substrate in water at room temperature for 30 minutes and then drying, and then sticking a serothepe on the copy image layer, hold the film and the end of the serothepe respectively. It is peeled off instantaneously at an angle of 180 degrees, and the presence or absence of the copy image layer attached to the adhesive surface of the cellotepe is checked. When the peeled portion is 0 to 5%, it is A grade, and when it is 5 to 30%, it is B grade. Grade, and the case of 30 to 100% was designated as C grade. (5) Moisture and heat resistance test Acrylic adhesive (EXCELAR2000
A, made by BRADY) and attached to an aluminum plate, 60
The sample was allowed to stand for 1 week at 90 ° C. and 90% RH, and the color change of the image was visually observed. ◯: No change Δ: Slight change is observed ×: Fading is remarkable

(6) Fading test A fluoropolymer film surface of an electrostatically copied substrate was irradiated with ultraviolet rays under the following equipment and conditions to carry a portable spectral colorimeter (NF).
-90 type, manufactured by Nippon Denshoku Industries Co., Ltd.) was used to evaluate the fading property. The control tables of the degree of color fading (ΔE) and ΔE and sensory evaluation are shown below, and the ultraviolet irradiation time until ΔE = 5 was shown. Ultraviolet irradiation device: EYE Super UV Tester (suv-w type, manufactured by Dainippon Plastic Industries Co., Ltd.) Ultraviolet irradiation conditions: Wavelength region 295 to 450 nm, 50 mW / cm ² Black panel temperature 45 ° C Humidity 70% RH ΔE = [(L ^{_{1 -L 0) 2 + (a}} 1 ~a 0) 2 + (b 1
-B ₀ ) ² ] ^1/2 L ₁ , a ₁ , b ₁ : Measured value after UV irradiation L ₀ , a ₀ , b ₀ : Measured value before UV irradiation (Note that the larger the L value, the higher the brightness. , The larger the a (+) value, the larger the red degree, the larger the a (-) value, the larger the green degree, the larger the b (+) value, the larger the yellow degree, and the larger b (-) value. The higher the degree of blue, the greater the degree of blueness.) △ E Content of sensory evaluation of fading property 0 to 0.5 fading 0.5 to 1.5 slightly fading 1.5 to 3.0 fading faintly 3.0 to 6.0 Fading to a noticeable level 6.0 to 12.0 Greatly fading 12.0 or more Greatly fading

Example 1 EXCELAR # 20 was used as a fluoropolymer film.
00 (manufactured by BRADY Co., containing an ultraviolet absorber, light transmittance of 76%, treated on one side to be hydrophilic), and using a polymethylmethacrylate / acetone solution on the hydrophilic surface, the thickness after drying is 7 μm A resin layer was formed. Then CA
40% of modified PVA (A) (Kuraray, KL-118)
Dissolved methanol solution and water-soluble polyurethane (B) (Izelux S-7100NC, solid content concentration 40%, Hodogaya Chemical Co., Ltd.) were used at (A) :( B) = 10: 90 (weight ratio). After mixing, 1.8 parts of trimethylolpropane-tri-β-aziridinylpropionate as a crosslinking agent (C) was added to 100 parts by weight of the total amount of (A) and (B) to prepare a mixed solution. Create and use the app bar to
The hydrophilic resin layer surface was coated so that the thickness after drying was 15 μm, and heat treatment was performed at 100 ° C. for 30 minutes to accelerate the crosslinking reaction. A 200 μm-thick blank paper was attached to the fluorine-based film surface opposite to the formed copy image layer surface using an acrylic adhesive having an adhesive force of 500 g / 25 mm to prepare a substrate. Fuji XEROX, A color
Electrostatic copying was performed at 635 to form an image. Adhesiveness and color development of the toner were good, and clear images were obtained. Then, the acrylic adhesive (EXCELAR200
OA, manufactured by Brady) was applied and attached to an acrylic plate to produce a billboard advertisement. Each evaluation was carried out for this signboard announcement, and the results are shown in Table 1.

Example 2 In Example 1, A color-63 manufactured by Fuji XEROX Co., Ltd.
Instead of 5, RICHO, manufactured by RECHO, 71
A black and white image was copied using the 60. The adhesion of the toner was good and a clear image was obtained. Also, a signboard advertisement was prepared and evaluated in the same manner as in Example 1. Table 1 shows the results.

Example 3 In Example 1, the following was used as the copy image layer. (A) CA-modified PVA (B) Polyoxane solution of polyurethane resin in dioxane (solid content concentration 10%) (C) Water-based blocked isocyanate (Elastron B)
N-08, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (A) :( B) = 25: 75 10 parts of (C) to 90 parts of the total amount of (A) and (B) were carried out using the mixture. A hydrophilic resin image was applied in the same manner as in Example 1, dried, and then subjected to a crosslinking reaction under heating conditions at 130 ° C. for 5 minutes to obtain a substrate. The thickness of the copied image layer is 10 μm
Met. An image was formed in the same manner as in Example 1 to obtain a billboard advertisement. Table 1 shows the evaluation results.

Example 4 A substrate was prepared and an image was formed in the same manner as in Example 1 except that a KFC film (manufactured by Kureha Chemical Co., Ltd.) containing an ultraviolet absorber and having a thickness of 50 μm was used instead of EXCELAR # 2000. , Made a billboard advertisement. The toner adhesion, color development and color vividness of the image were all good. Table 1 shows the evaluation results.

Example 5 In place of polymethylmethacrylate, which is a hydrophilic resin in Example 1, a polyurethane resin made from a polyol was used as a raw material, and a dioxane solution of the resin was applied to form a polyurethane resin having a thickness of 1
A substrate was prepared, an image was formed, and a signboard advertisement was prepared in the same manner except that a 5 μm layer was used. The toner adhesion, color development and color vividness of the image were all good. Table 1 shows the evaluation results.

Example 6 Instead of EXCELAR # 2000 in Example 1,
Using a 50 μm-thick NEOFLON ETFE film (manufactured by Daikin Chemical Co., Ltd.) that has been subjected to oxygen plasma treatment on both sides,
A substrate was prepared, an image was formed, and a signboard advertisement was prepared in the same manner except that an ultraviolet absorber was added to a polymethylmethacrylate solution which is a hydrophilic resin. The toner adhesion, color development and color vividness of the image were all good. Table 1 shows the evaluation results.

COMPARATIVE EXAMPLE 1 In Example 1, the CA-modified PV constituting the copy image layer was used.
A substrate was prepared in the same manner except that sulfonic acid-modified polyvinyl alcohol (HM-NO4 manufactured by Kuraray) was used in place of A, and a signboard advertisement was prepared using the substrate. The substrate and the billboard advertisement were evaluated, and the results are shown in Table 1.

COMPARATIVE EXAMPLE 2 In Example 1, the CA-modified PV forming the copy image layer was used.
Instead of the 40% methanol solution of A, sulfonic acid-modified polyvinyl alcohol (Kuraray, HM-NO4) 4
A substrate was prepared in the same manner except that 0 / 60-methanol / aqueous solution was used, and a signboard advertisement was prepared using the substrate.
The substrate and the billboard advertisement were evaluated, and the results are shown in Table 1.

[0051]

[Table 1]

[0052]

The substrate for copied images of the present invention can form images excellent in color developability and color sharpness, and by using the substrate, fading, water resistance, heat and humidity resistance, and anti-proof property. It is possible to obtain signboard announcements that are extremely rich in stain resistance and chemical resistance.

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Claims (1)

[Claims] 1. A hydrofluoric-treated fluoropolymer film layer and a copy image layer, the copy image layer comprising a carboxyl-modified polyvinyl alcohol (A), a polyurethane resin (B) and a crosslinking agent (C). A substrate for copied images, characterized by comprising: