JPH11170451A - Flexible sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent durability in antifungal properties and adhesion to a marking film by providing, on one side of a composite sheet, a layer of a specified thickness having a main component of an antifungal polymer of a specified polymerization degree, which is composed of a homopolymer or the like of a phosphonium salt-containing vinyl monomer represented by a specified formula. SOLUTION: An antifungal layer of 1.5-15 μm thickness having a main component of an antifungal polymer, which has a polymerization degree of 50-200, and is a homopolymer or copolymer of a phosphonium salt-containing vinyl monomer represented by formula I or II, is provided on at least one side of a composite sheet. In the formula n represents 9, 13, or 17; R1 , R2 , and R3 are each a 1-18C alkyl group; R1 , R2 , and R3 can be the same or different; m is an integer of 1-4; and X represents a halide ion such as a chloride ion, bromide ion, or the like, or a monovalent anion such as a tetrafluoroborate or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible sheet which does not generate mold on its surface and can be suitably used as a substrate for an electric signboard outdoors.

[0002]

2. Description of the Related Art Illuminated signboards with internal lighting are widely used outdoors to enhance the advertising effect at night, and many of them have a curved shape. For such an illuminated signboard, a translucent acrylic plate formed into a flat or curved shape is often used. However, since the acrylic plate is hard and inflexible, it easily breaks and is dangerous when dropped. Therefore, since the Great Hanshin Earthquake, the use of flexible sheets such as vinyl chloride resin tarpaulin sheets has gradually been replaced.

[0003] There is a problem that the surface of the above-mentioned illuminated signboard develops mold while being exposed to the wind and rain outdoors.
As a countermeasure, in the case of an acrylic plate, a method of containing a fungicide in an acrylic resin has been adopted. However, there is a problem that the fungicide bleeding out on the resin surface runs off due to rain and loses the fungicide property.

The use of a marking film for marking the surface of a flexible sheet used for eaves or tents in stores is disclosed in Japanese Patent Application Laid-Open No. Hei 9-164624.

[0005] A fungicidal sheet having an antibacterial property and a fungicide property by adding an antibacterial agent and a fungicide to the base material of a flexible sheet is also known. However, in addition to the above-mentioned problems, there is also a problem that the adhesiveness to the marking film to be attached to the surface deteriorates with time due to the bleed-out fungicide.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned conventional problems, and provides a flexible sheet which is excellent in mold resistance and adhesion to a marking film, and which can be used for a long time outdoors. The purpose is to do.

[0007]

The flexible sheet of the present invention comprises a homopolymer of a phosphonium salt-containing vinyl monomer represented by the following formula (1) or (2) on at least one surface of a composite sheet made of a synthetic resin. A mildew-proof layer having a thickness of 1.5 to 15 μm, which is mainly composed of a fungicide polymer having a degree of polymerization of 50 to 200, is a copolymer.

[0008]

Embedded image (Where n is 9, 13, 17)

[0009]

Embedded image(However, R₁ , R_Two , R_Three All have 1 to 18 carbon atoms
Consisting of an alkyl group, ₁ , R_Two , R_Three Are the same
Or different ones. m is 1 to 4
Indicates an integer and X^-Are chloride ions, bromide ions, etc.
One of halide ions, tetrafluoroborate, etc.
Shows a valent anion. )

The composite sheet used in the present invention is made of a synthetic resin. Specifically, a flexible synthetic resin sheet is laminated on at least one surface of a molded net made of glass fiber, synthetic resin fiber, or the like. , Glass fiber,
Laminated synthetic resin sheets on a woven or non-woven fabric made of synthetic resin fibers and the like, and those obtained by impregnating the above-mentioned woven or non-woven fabric with a molten synthetic resin, have a certain degree of rigidity and flexibility. As a preferable example, a glass fiber formed net formed by twisting glass fibers and then forming a net shape is heat-laminated with a vinyl chloride resin sheet.

Examples of the synthetic resin include olefin resins such as ethylene resins and propylene resins; vinyl chloride resins; acrylic resins; and ester resins such as ethylene terephthalate resins. A vinyl chloride-based resin is preferred because it can easily impart flexibility and is easy to handle.

The vinyl chloride resin sheet thermally laminated on the above-mentioned base material includes, for example, various modifiers such as a heat stabilizer and an ultraviolet absorber in addition to a vinyl chloride resin, a plasticizer, a pigment and an organic solvent. Can be obtained by applying and drying a vinyl chloride resin organosol containing the compound on a release sheet, followed by heat fusion.

Further, when used for an electric signboard, it is preferable to make the interior lighting equipment in milky white so that the internal lighting equipment cannot be seen in the daytime.

When the thickness of the composite sheet is reduced, sufficient rigidity cannot be obtained, and distortion may occur due to wind and rain. When the thickness is increased, the rigidity increases and a large amount of stress is applied to a fixed portion when the curved surface is applied. Becomes difficult, and the weight per unit area increases, and handling is inconvenient.
2.0 mm is preferred.

The fungicidal polymer used in the present invention comprises:
A homopolymer or a copolymer of the above formula (1) or (2), wherein the dimethylalkyl-
The 4-vinylbenzylphosphonium chloride monomer is specifically dimethyldecyl-4-vinylbenzylphosphonium chloride when n = 9, dimethyltetradecyl-4-vinylbenzylphosphonium chloride when n = 13, and dimethyl when n = 17. Octadecyl-4
-Vinylbenzylphosphonium chloride.

In the phosphonium salt-containing vinyl monomer represented by the formula (2), R ₁ , R ₂ and R ₃ each comprise an alkyl group having 1 to 18 carbon atoms, and R ₁ , R ₂ and R ₃ are They may be the same or different.
And X ^- represents chloride, bromide any halide ion, a monovalent anions such as tetrafluoroborate.

That is, specific examples of the compound represented by the formula (2) include the following. 2-methacryloyloxy-ethyltri-n-butylphosphonium chloride, methacryloyloxy-methyltri-n-butylphosphonium chloride, methacryloyloxy-methyltri-n-octylphosphonium chloride, methacryloyloxy-methyldimethyl n-octadecylphosphonium chloride, methacryloyloxy -Methyltri-n-butylphosphonium bromide, methacryloyloxy-methyltri-n-octylphosphonium bromide, 2-methacryloyloxy-ethyltri-n-octylphosphonium chloride, 3-methacryloyloxy-propyltri-n
-Octylphosphonium chloride, 4-methacryloyloxy-butyltri-n-octylphosphonium chloride, 2-methacryloyloxy-ethyltri-n-octylphosphonium bromide, 3-methacryloyloxy-propyltri-n-octylphosphonium bromide, 4-
Methacryloyloxy-butyltri-n-octylphosphonium bromide, methacryloyloxy-methyltri-n-
Butylphosphonium chloride, acryloyloxy-methyltri-n-octylphosphonium chloride, acryloyloxy-methyldimethyl n-octadecylphosphonium chloride, acryloyloxy-methyltri-n-octylphosphonium bromide, acryloyloxy-methyldimethyln-octadecylphosphonium bromide, acryloyloxy-methyltri-n-butylphosphonium tetra Fluoroborate, 2-acryloyloxy-
Ethyltri-n-octylphosphonium bromide, 3-
Acroyloxy-propyltri-n-octylphosphonium bromide.

The phosphonium salt-containing vinyl monomer represented by the formula (1) or (2) may be copolymerized with another vinyl monomer. Examples of such another vinyl monomer include n-butyl acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and the like are included.

If the degree of polymerization of the fungicidal polymer is lower than 50, the polymer bleeds from the fungicidal coating layer, so that not only the fungicide property decreases with time but also the sticking property of the marking film decreases. Will be done. On the other hand, when the polymerization degree exceeds 200, the coating resin has rigidity, and cracks easily occur on the surface of the mildewproof coating layer when the flexible sheet is bent. The method for producing the polymer may be any of conventional polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization and bulk polymerization, but a constant temperature solution polymerization method having a sharp molecular weight distribution and relatively easy control of the degree of polymerization is recommended. .

The thickness of the fungicide applied to the surface of the composite sheet is 1.5 to 15 μm after drying. 1.5μ
When the thickness is smaller than m, the fungicidal function is not exhibited, and when it exceeds 15 μm, it becomes impossible to follow the flexibility of the composite sheet, and cracks are generated on the surface.

The coating method of the fungicide is not particularly limited, and a general-purpose coating device such as a gravure coater can be used.

The flexible sheet of the present invention is suitable for an outdoor signboard having a curved surface, and is usually a decorative chloride such as "Tac Paint" or "Harucolor" (both trade names) manufactured by Sekisui Chemical Co., Ltd. After the vinyl resin pressure-sensitive adhesive sheet is cut into desired characters and shapes, it is transferred to the surface of the flexible sheet and fitted into a frame of a specific shape to be used as a signboard.

(Function) By applying a fungicide polymer having a controlled degree of polymerization, the fungicide does not bleed over the surface of the sheet with the passage of time. It does not cause a decrease in sex.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES (Examples 1 to 5 and Comparative Examples 1 to 6) Preparation of mold-proof polymer Dimethyldecyl-4-vinylbenzylphosphonium chloride was placed in a separable flask capable of constant temperature polymerization equipped with a cooling tube, a thermometer and a stirrer. 20 parts by weight (manufactured by Nippon Chemical Co., Ltd.) and 80 parts by weight of n-dodecanethiol were charged together with 80 parts by weight of ethyl acetate, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, and a suitable amount of a polymerization initiator benzyl peroxide was added dropwise to start the reaction. The liquid temperature during the reaction was controlled at 60 ± 2 ° C., and after 3 hours, the reaction liquid temperature was lowered to stop the reaction, thereby producing five types of fungicidal polymers 1 to 5 having different degrees of polymerization. The degree of polymerization of the obtained fungicidal polymer is as shown in Table 1 in terms of a conversion value based on analysis data by gel permeation chromatography.

[0025]

[Table 1]

Preparation of vinyl chloride resin composite sheet Vinyl chloride resin (Sumitomo Chemical Co., Ltd., trade name "Smirit PX-N (4)", polymerization degree 1300): 100 parts by weight Plasticizer (Asahi Denka Co., Ltd., product number "PN250") )) 30 parts by weight Benzotriazole-based ultraviolet absorber (Asahi Denka Co., Ltd., trade name "ADK STAB LA-32") 1 part by weight Heat stabilizer (Asahi Denka Co., Ltd., trade name "MARK AC-167") 1 part by weight Titanium oxide 20 parts by weight Xylene 100 parts by weight The above composition was stirred with a dissolver at 23 ° C for 40 minutes to obtain an organosol. A sheet was formed by covering a formed net formed by bundling glass fibers into a mesh with the above-mentioned organosol to obtain a vinyl chloride resin composite sheet having a thickness of 1.5 mm.

Adjustment primer for fungicide (Nippon Shokubai Co., Ltd., trade name "Polyment NK-35")
0 ") 100 parts by weight, a benzotriazole-based ultraviolet absorber (trade name" ADK STAB LA-32 "manufactured by Asahi Denka Co., Ltd.)
5 parts by weight and 10 parts by weight of the fungicidal polymer shown in Table 1 were blended to prepare a fungicide.

Preparation of a Flexible Sheet A fungicide was applied to each of the vinyl chloride resin composite sheets obtained by the above method using a Meyer bar, and dried at 100 ° C. for 2 minutes to form a flexible sheet having the composition shown in Table 2. A flexible sheet provided with a mold layer was obtained.

(Examples 6 to 10, Comparative Examples 7 to 12) Instead of dimethyldecyl-4-vinylbenzylphosphonium chloride, 2-methacryloyloxy-ethyltri-n-butylphosphonium chloride was used as a fungicide-resistant monomer. Except for this, five kinds of fungicidal polymers 6 to 10 having different polymerization degrees were produced in the same manner as in Examples 1 to 5, and using these, fungicides were obtained in the same manner as in Examples 1 to 5.

The above fungicide was applied to the vinyl chloride resin composite sheet in the same manner as in Examples 1 to 5, and the fungicide shown in Table 1 was applied and dried to form a fungicide layer having the structure shown in Table 3. The provided flexible sheet was obtained.

Evaluation of physical properties The fungicidal flexible sheets obtained in Examples 1 to 10 and Comparative Examples 1 to 12 were evaluated for physical properties by the following methods.
The results are shown in Tables 2 and 3. (1) Fungicidal PDA medium: potato dextrose (Nippon Pharmaceutical Co., Ltd.)
39 g was dissolved in 1 liter of water, sterilized at 121 ° C. for 20 minutes, placed in a sterile petri dish, and allowed to cool. Bacterial dispersion water: 20 g of dioctyl sulfone succinic acid is added to water 40
Mold spores were dispersed in the solution dissolved in 0 cc. Mold culture: A piece of a vinyl chloride resin flexible sheet (2 cm × 2 cm) was placed on the PDA medium adjusted in the above, and 1 cc of the bacterial dispersion water adjusted in the above was poured, and cultured at 28 ° C. for 10 days. The state of occurrence was observed and evaluated on a 5-point scale based on the following criteria. 5: No mold generation 4: Slight mold formation 3: 50% of the sheet piece area is covered with mold 2: 80% of the sheet piece area is covered with mold 1: Mold is covered on the entire sheet piece Outbreak

(2) Adhesiveness of Marking Film A marking film (trade name “Tac Paint # TP03”, 25 mm width, manufactured by Sekisui Chemical Co., Ltd.) was applied to a flexible sheet fixed to a metal plate with a double-sided adhesive tape at 23 ° C. , And after 24 hours at 23 ° C., the peeling force was measured. (Peeling speed 300mm
/ Min)

(3) Flexibility of the mold-proof layer The sample sheet (50 mm × 80 mm) of the flexible sheet coated with the mold-proof layer is held in both hands in the longitudinal direction, and the sample is bent 200 times so that the sample is bent back and forth. The state of cracks on the surface of the mold preventive layer was evaluated on the following two levels. ：: No cracks on the surface ×: Cracks occurred on the surface

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

As described above, the flexible sheet of the present invention has the above-mentioned structure. By coating a composite sheet with a fungicide polymer having a controlled degree of polymerization and providing a fungicide layer,
It has excellent durability in terms of mold resistance and adhesion to the marking film, and can be used for a long time on outdoor illuminated signs and the like.

Claims (1)

[Claims] 1. At least a composite sheet made of synthetic resin
Is also represented by the following formula (1) or (2)
Homopolymer or co-polymer of a vinyl salt-containing vinyl monomer
Mold-resistant poly which is united and has a polymerization degree of 50 to 200
Fungicide layer with a thickness of 1.5 to 15 μm, mainly composed of
Flexible Seat characterized by being provided with
G. [0001](Where n is 9, 13, 17)(However, R₁ , R_Two , R_Three All have 1 to 18 carbon atoms
Consisting of an alkyl group, ₁ , R_Two , R_Three Are the same
Or different ones. m is 1 to 4
Indicates an integer and X^-Are chloride ions, bromide ions, etc.
One of halide ions, tetrafluoroborate, etc.
Shows a valent anion. )