JPH0872209A - Marking sheet - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a marking sheet which has weather resistance and stain resistance maintained for a long period of time and is excellent in adhesion to and followability to a soft film. [Structure] In a marking sheet 1, a coating layer (A) 3 composed of a solvent-soluble fluororesin, an ultraviolet absorber and a binder resin (a) is laminated on one side of a colored soft vinyl chloride film 2, and the coating layer A coating layer (B) 4 composed of a solvent-soluble fluororesin and a binder resin (b) is laminated on three surfaces of (A), and the binder resin (a) and the binder resin (b) have the same composition. Not used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a marking sheet which is used indoors and outdoors for decoration or display and has excellent weather resistance and stain resistance for a long period of time.

[0002]

2. Description of the Related Art Conventionally, a marking sheet in which a pigment is dispersed in a synthetic resin such as a thermoplastic resin to be colored, and an adhesive layer is provided on one surface thereof has been used for decoration and display.
In particular, those used outdoors are required to have weather resistance against sunlight and pollution resistance against dust, automobile waste gas and the like.

As a conventional weather resistant marking sheet,
For example, a tetrafluoroethylene-ethylene copolymer and a marking sheet obtained by adding an ultraviolet absorber thereto are known as described in JP-A-4-14583. Also, in Japanese Utility Model Laid-Open No. 25547/1990,
A marking sheet is described in which a synthetic resin base sheet is provided with a coating layer containing a hydroxyl group-containing fluororesin and a polyisocyanate compound as main components, and a releasable coating layer is provided thereon.

[0004]

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-14548
The tetrafluoroethylene-ethylene copolymer as described in No. 3 has a high molding temperature, so that the usable pigments are limited, and the molding is an extrusion molding method, and the casting method cannot be applied. Is not suitable for. In addition, when organic UV absorbers are used in various coating agents containing UV absorbers, the duration of UV shielding effect is short, and when inorganic UV absorbers are used, the UV shielding effect lasts for a long time. There is a problem that the binder resin deteriorates due to the photocatalytic reaction by itself and becomes cloudy.

In the marking sheet described in Japanese Utility Model Laid-Open No. 25547/1990, it is described that the coating layer contains a fluororesin, and the weather resistance can be further improved by mixing it with an ultraviolet absorber. The releasable coating layer laminated on this coating layer has the main purpose of water repellency and stain resistance, and cannot be expected to have a particularly long lasting effect of preventing deterioration.

The present invention solves the above-mentioned conventional problems and has a coating layer which maintains weather resistance and stain resistance for a long period of time, and has excellent adhesion and conformability to the soft film. The purpose is to provide a marking sheet.

[0007]

The marking sheet of the present invention has a coating layer (A) comprising a solvent-soluble fluororesin, an ultraviolet absorber and a binder resin (a) laminated on one side of a colored flexible film, A coating layer (B) composed of a solvent-soluble fluororesin and a binder resin (b) is laminated on the surface of the coating layer (A), and the binder resin (a) and the binder resin (b) have the same composition. It is characterized by not being a thing.

Examples of the colored flexible film that can be used in the present invention include cast or calender-molded soft vinyl chloride film, polyolefin resin film, thermoplastic resin film such as polyurethane and polyester. A soft vinyl chloride film formed by casting is preferred in terms of flexibility. The above-mentioned soft film is colored by adding a pigment which has been conventionally used for a coloring film in order to enhance the decorative property and the display effect. Although the thickness of the colored flexible film varies depending on the use, it is generally preferably 50 to 150 μm.

The solvent-soluble fluororesin used for the coating layer (A) is a fluororesin which is soluble in one or more mixed solvents of xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and the like. As such a solvent-soluble fluororesin, for example, a ternary compound of CH ₂ CF ₂ (vinylidene fluoride), C ₂ F ₄ (tetrafluoroethylene) and C ₃ F ₆ (hexafluoropropylene) is used. Typical examples include polymers and the like.

The ultraviolet absorber is selected from organic ones such as benzophenone type, benzotriazole type, salicylic acid type and cyanoacrylate type. In the coating layer (A), it is possible to mix and disperse an organic ultraviolet absorber in a larger amount than usual, and to add 0.5 to 50 to 100 parts by weight of the solid content of the solvent-soluble fluororesin.
Weight part is preferable, More preferably, it is the range of 2 to 30 weight part.

The solvent-soluble fluororesin and the ultraviolet absorber are mixed with the binder resin (a) to form a coating layer (A). The binder resin (a) used here has a hardness of 6 in order to improve followability with respect to a soft film.
Those having a low B level are preferable. Further, in order to improve the dispersibility of the solvent-soluble fluororesin and the ultraviolet absorber and to provide the coating layer (A) with flexibility as a whole and to improve the adhesion to the soft film, the acrylic resin is used as the binder resin (a). Resins are preferred.

Examples of the acrylic resin include polyacrylic acid esters such as polymethyl acrylate, polyethyl acrylate, polypropyl acrylate, and 2-ethylhexyl polyacrylate, and 2-ethylhexyl acrylate.
Acrylic acid-copolymers such as vinyl acetate copolymers, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polymethacrylic acid esters such as poly (hexyl methacrylate) and copolymers thereof, Examples include acrylic resins having various functional groups such as acrylic amide, hydroxymethyl methacrylate, glycidyl ether methacrylate, and the like, and a mixture of two or more of these.

Further, fluoroolefin-hydrocarbon-based olefin copolymers such as a copolymer of C ₂ F ₄ and vinyl alcohol may also be mentioned. Examples of the fluoroolefin include tetrafluoroethylene, hexafluoropropylene, chloro-difluoroethylene and the like.

Further, the binder resin contains calcium carbonate, magnesium carbonate, and calcium carbonate within a range not deteriorating the transparency and the physical properties.
Fillers such as silicates and pigments, dyes, etc. may be added for the purpose of coloring.

The amount of the binder resin (a) mixed with the solvent-soluble fluororesin is preferably 10 to 70% by weight of the fluororesin. When the amount of the binder resin is less than 10% by weight, the hardness of the coating layer (A) becomes high, the deformation of the soft film cannot be followed, and cracks and peeling easily occur. On the other hand, if it exceeds 70% by weight, the amount of acrylic resin is large and the weather resistance is lowered. Therefore, the binder resin (a)
The mixing amount of is preferably in the above range.

The coating layer (A) is obtained by dispersing a mixture of a solvent-soluble fluororesin and an ultraviolet absorber in a binder resin (a) and using a soft film as a gravure roll coater, a two roll coater and a reverse roll coater. It may be laminated by applying it with a coating solution and drying it. The thickness of the coating layer (A) is preferably about 5 to 30 μm after drying. If the thickness is less than 5 μm, the ultraviolet absorbing effect is insufficient and sufficient weather resistance cannot be obtained. If it exceeds 30 μm, the physical properties of the fluororesin film will appear strongly on the marking sheet, making it easy to peel off. In particular, when a soft vinyl chloride film is used as the soft film, the flexibility of the soft vinyl chloride film will be lost, or the coating will be lost. The transparency of the layer (A) is deteriorated and the color tone of the soft film is lost.

The coating layer (B) is the same as the solvent-soluble fluororesin dispersed in the binder resin (b), and the binder resin (b) is also the same as the binder resin (a) for the same reason. Acrylic resins are preferred. However, the binder resin (b) is not the same composition as the binder resin (a).

Those not having the same composition are, for example, those having different constitutional components such as the polyacrylic acid ester and polymethacrylic acid ester, and those having different copolymerization components copolymerized with these acrylic resins, When a plurality of these resins are mixed and used, those having different mixing ratios are also included.

Like the coating layer (A), the coating layer (B) preferably has a hardness of about 6B. The coating layer (B) may be applied and dried in the same manner as the coating layer (A) to be laminated on the coating layer (A), and the thickness after drying is 3 to 10 μm.
It is preferably m.

When the same binder resin composition is used for the coating layer (A) and the coating layer (B), the interface between the two layers is formed of the same continuous material with respect to the binder resin. The ultraviolet absorber contained in (3) easily migrates to the coating layer (B), and its volatilization from the surface and dissipation due to runoff are not prevented. However, when binder resins having different compositions are used as the two layers as in the present invention, the interface itself between the two layers having different compositions serves as a blocking layer that blocks migration of the ultraviolet absorber, and the effect of the ultraviolet absorber does not dissipate. Can be maintained for a long time.

[0021]

[Function] Coating layer (A) and coating layer (B)
Since the binder resin with different composition is used, the interface itself between both layers with different composition acts as a blocking layer that blocks migration of the UV absorber, and the effect of the UV absorber does not dissipate and lasts for a long time. be able to. or,
Since the coating layer (B) as the surface layer contains the fluororesin, dirt is unlikely to adhere. Furthermore, when an acrylic resin is used as the binder resin for both layers, the coating layers (A) and (B) have appropriate flexibility, and have excellent adhesion and followability to a soft film,
Even when the soft film is stretched or bent along the bent portion of the adherend during the construction, cracks and peeling do not occur.

[0022]

EXAMPLES Next, examples of the marking sheet of the present invention will be described. Example 1 An acrylic resin (2-ethylhexyl acrylate-acrylic acid-vinyl acetate-hydroxyethyl methacrylate copolymer) was added to a terpolymer of CH ₂ CF ₂ , C ₂ F ₄ and C ₃ F _6. Of 50% by weight and dissolved in a mixed solvent of methyl ethyl ketone, xylene, and methyl isobutyl ketone (solvent-soluble fluororesin paint (Asahi Glass Co., Ltd., trade name: Fluorotop), and a benzophenone-based ultraviolet absorber ( Asahi Denka, product name: MAR
10 parts by weight of K1413) was added to 100 parts by weight of the solid content of the above solution.

The solvent-soluble fluororesin coating material containing the ultraviolet absorber is applied and dried on one surface of a cast soft blue vinyl chloride film using a gravure coater so that the thickness after drying becomes 10 μm. To form a coating layer (A).

A solvent-soluble fluororesin comprising a terpolymer of CH ₂ CF ₂ , C ₂ F ₄ and C ₃ F ₆ and an acrylic resin (ethyl acrylate-acrylic acid-methyl methacrylate-hydroxyethyl) Acrylate copolymer) 4
Solvent-soluble fluororesin paint blended with 0% by weight and dissolved in the same mixed solvent as above (Sumitomo Cement, trade name: ZR
The coating) was applied to the surface of the coating layer (A) using a gravure coater so that the thickness after drying was 5 μm and dried to form a coating layer (B) to obtain the marking sheet of the present invention. Further, an adhesive layer and a release paper were laminated on the other surface of the soft vinyl chloride film.

FIG. 1 is a sectional view of the marking sheet 1 obtained in Example 1, in which one surface of the soft vinyl chloride film 2 is coated with a solvent-soluble fluororesin, an ultraviolet absorber and a binder resin (a). A layer (A) 3 is formed, and a coating layer (B) 4 comprising a solvent-soluble fluororesin and a binder resin (b) is laminated on the coating layer (A), and the soft vinyl chloride film 2
The pressure-sensitive adhesive layer 5 and the release paper 6 are laminated on the other surface.

(Example 2) A terpolymer of CH ₂ CF ₂ , C ₂ F ₄ and C ₃ F ₆ was added to an acrylic resin (2-ethylhexyl acrylate-acrylic acid-vinyl acetate-ethyl methacrylate copolymer). 40% by weight, and a solvent-soluble fluororesin paint (manufactured by Central Glass Co., Ltd., trade name: Cefural Coat) dissolved in a mixed solvent of methyl ethyl ketone, xylene and methyl isobutyl ketone,
A benzotriazole type ultraviolet absorber (trade name: LA32, manufactured by Asahi Denka Co., Ltd.) was added in an amount of 10 parts by weight based on 100 parts by weight of the solid content of the above solution.

The solvent-soluble fluororesin coating material containing the above ultraviolet absorber was applied to one surface of the same soft vinyl chloride film as used in Example 1 and dried in the same manner as in Example 1 to obtain a thickness after drying. A 15 μm coating layer (A) was formed.

After that, CH ₂ CF ₂ , C ₂ F ₄ and C ₃
30% by weight of acrylic resin (ethyl methacrylate-hydroxymethyl methacrylate-acrylic acid-butyl acrylate copolymer) was mixed with the terpolymer of F ₆ and dissolved in the same mixed solvent as above -Type fluororesin coating (Asahi Glass Co., Ltd., trade name: Fluoro Top) is applied to the surface of the coating layer (A) using a gravure coater so that the thickness after drying is 5 μm and dried to form the coating layer (B) Then, the marking sheet of the present invention was obtained. Further, an adhesive layer and a release paper were laminated on the other surface of the soft vinyl chloride film.

Example 3 A fluoroethylene-hydrocarbon-based olefin copolymer (copolymer of C ₂ F ₄ and vinyl alcohol) was used as the binder resin for the coating layer (A) of Example 2. A marking sheet similar to that of Example 2 was obtained.

Comparative Example 1 A marking sheet similar to that of Example 1 was obtained except that the coating layer (B) was not laminated.

Comparative Example 2 A marking sheet was obtained in the same manner as in Example 1 except that the same coating layer (A) as in Example 1 was formed as the coating layer (B).

The weather resistance and stain resistance of the above Example 1 and Comparative Examples 1 and 2 were evaluated by the following methods. or,
In addition to those of Examples 2 and 3, the adhesion to the adherend was evaluated. The results are shown in Table 1. (1) Evaluation of weather resistance The color difference between those subjected to the accelerated exposure test and those not subjected to the accelerated exposure test was measured. (Exposure tester; manufactured by Dainippon Plastics Co., Ltd., product name: Super UV Tester: UV irradiation conditions 64 ° C, 6
(4% RH, 90 mW / cm ² ) (2) Evaluation of pollution resistance Visual evaluation of dirt adhesion state after 6 months and 1 year after outdoor construction (outdoor construction site: Shioe, Amagasaki City, construction: 45 ° southward elevation angle) went). 5 Almost no dirt adhered 4 Slightly adhered dirt 3 Partially thin dirt adhered 2 Thinly adhered dirt all over the surface and partially remarkable dirt adhered 1 Overall marked dirt adhered 1

[0033]

[Table 1]

As is clear from Table 1, there is no difference in stain resistance between Examples 1 to 3 and Comparative Example 1, but the weather resistance of Examples 1 to 3 is marked for a long period of time. The color of the sheet does not change much and it has excellent weather resistance. However, it can be seen that the thing of Comparative Example 1 has a large change in color with time and is inferior in weather resistance.

[0035]

EFFECTS OF THE INVENTION The marking sheet of the present invention has the above constitution, and since the coating layers (A) and (B) are different in binder resin composition,
The ultraviolet absorber contained in the coating layer (A) does not dissipate and its effect can be maintained for a long time, and weather resistance and stain resistance are maintained for a long time. Furthermore,
The coating layers (A) and (B) have excellent adhesion to and followability to the soft film, and are free from cracks and peeling.

[0036]

[Brief description of drawings]

FIG. 1 is a sectional view showing an embodiment of a marking sheet of the present invention.

[Explanation of symbols]

 1: Marking sheet 2: Soft vinyl chloride film 3: Coating layer (A) 4: Coating layer (B) 5: Adhesive layer 6: Release paper

Claims (1)

[Claims] 1. A coating layer (A) comprising a solvent-soluble fluororesin, an ultraviolet absorber and a binder resin (a) is laminated on one side of a colored flexible film, and the solvent is applied on the coating layer (A) side. A coating layer (B) composed of a soluble fluororesin and a binder resin (b) is laminated to form a binder resin (a) and a binder resin (b).
Is a marking sheet characterized by not being the same composition.