JPH0428750Y2 - - Google Patents

Description

[Detailed description of the invention] [Technical field] The present invention relates to an antifouling sheet.More specifically, the present invention relates to an antifouling sheet that does not cause a difference in gloss due to wrinkles formed during use. It concerns the seat.

[Conventional technology]

Conventionally, antifouling sheets are known in which a soft synthetic resin layer is formed on at least one side of a base fabric made of fiber fabric, and an antifouling synthetic resin layer is formed thereon.

For example, JP-A-56-60247 and JP-A-59-150743
No. 1, No. 2003-11-103 discloses an antifouling sheet obtained by forming an intermediate layer made of a polyvinyl chloride resin on a base fabric, and forming a surface layer made of a fluorine-containing polymer resin on this intermediate layer.

In addition, in JP-A-59-165653 and JP-A-58-147355, a polyurethane resin intermediate layer is formed on the base fabric,
An antifouling sheet having a fluorine-containing polymer surface layer formed thereon is disclosed.

Further, JP-A-59-146847 and JP-A-59-129146 disclose antifouling sheets in which a polyvinyl chloride resin intermediate layer is formed on a base fabric, and an acrylic polymer resin surface layer is formed thereon. There is.

Furthermore, JP-A-58-147356 and 59-156744
No. 1, No. 2003-11-112 discloses an antifouling sheet in which a polyurethane resin intermediate layer is formed on a base fabric, and an acrylic polymer resin surface layer is formed thereon.

These antifouling sheets have high antifouling properties and are widely used. However, wrinkles that occur when these conventional antifouling sheets are bent or folded during use are difficult to recover, and when light hits these wrinkled areas, the gloss becomes uneven and the wrinkles disappear. It has been recognized that there is a noticeable defect in appearance.

The above drawbacks can be overcome by forming fine irregularities on the surface of the surface layer made of antifouling synthetic resin by embossing, etc.
Dirt easily settles in these recesses, impairing the original function of the antifouling sheet, making it impossible to put it to practical use.

[The problem that the idea aims to solve]

The present invention aims to provide an antifouling sheet in which wrinkles formed during use are not noticeable.

[Means and effects for solving the problem]

The antifouling sheet of the present invention comprises a base fabric made of a fiber fabric, an intermediate layer made of a soft synthetic resin formed on at least one surface of the base fabric, and a fluorine-containing polymer formed on the surface of the intermediate layer. It has a surface layer made of an antifouling synthetic resin containing at least one selected from resin and acrylic polymer resin, and has fine particles on at least one bonding surface of the intermediate layer and the surface layer that are bonded to each other. It is characterized by the formation of unevenness.

In the antifouling sheet 1 of the present invention shown in FIG. 1, a soft synthetic resin intermediate layer 3 is formed on the surface of a base fabric 2 made of fiber cloth, and an antifouling synthetic resin surface layer 4 is laminated thereon. It is tied together. In FIG. 1, fine irregularities 5 are formed on the surface of the intermediate layer 3. The unevenness 5 may be formed on the back surface of the surface layer 4 as shown in FIG.

In the antifouling sheet of the present invention, at least one of the intermediate layer and the surface layer has a bonding surface having fine irregularities that has a refractive index lower than that of the soft synthetic resin of the intermediate layer, as shown in FIG. It may be coated with a synthetic resin layer 6 having a certain ratio.

The base fabric used in the antifouling sheet of the present invention is made of fiber fabric. The fibers constituting this fabric include natural fibers such as cotton and linen, inorganic fibers such as glass fiber, recycled fibers such as viscose rayon and Kyupra, and semi-synthetic fibers such as G and triacetate fibers. , and synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, and polyolefin fibers. . The fibers in the fabric are short fiber spun yarn,
It may be in any form such as long fiber yarn, split yarn, or tape yarn, and the fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite fabric thereof. Generally, the fibers used in the antifouling sheet of the present invention are preferably polyester fibers, preferably in the form of long fibers (filaments), and preferably in the form of a plain woven fabric. The base fabric made of fiber fabric is useful for maintaining the mechanical strength of the resulting laminate at a high level.

An intermediate layer made of a soft synthetic resin is formed on at least one surface of the base fabric.

The soft synthetic resins used in this invention include polyvinyl chloride resin, ethylene-vinyl acetate-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, polyvinylidene chloride resin, other vinyl-based synthetic resins, and polyurethane resin. Or it contains a mixture of two or more of these resins.

The soft synthetic resin may contain plasticizers, stabilizers, colorants, ultraviolet absorbers, and other functional agents.

The intermediate layer can be formed on the base fabric using a soft synthetic resin film, paste, straight, or the like, by a conventionally known method such as topping, calendering, coating, taping, or the like.

This intermediate layer has a sufficient weight, e.g. 30 to 1000 g/ ^m2 , and a sufficient thickness, e.g. 0.05mm or more, preferably 0.05-1.0mm
It has a thickness of .

an intermediate layer formed on the base fabric as described above;
And/or fine irregularities are formed on the bonding surface of the surface layer formed thereon.The method for forming fine irregularities is not particularly limited, and conventionally known surface roughening methods, such as Embossing method (especially satin embossing method), low temperature plasma treatment method, etching method,
A sputtering method, a granular material embedding method, etc. can be used. There are no particular limitations on the shape or size of the unevenness formed on the bonding surface of at least one of the intermediate layer and the surface layer, as long as the object of the present invention is achieved, but for example, the unevenness may have a diameter of 5 to 200 microns,
Preferably 10-100 microns, depth 0.01-5
It is preferred to form a finely textured surface in which a large number of depressions of microns, preferably 0.05 to 2 microns, are formed at intervals of 5 to 100 microns, preferably 10 to 50 microns.

A surface layer made of antifouling synthetic resin may be formed directly on the finely uneven surface. Further, this finely uneven surface is covered with a synthetic resin layer having a refractive index lower than that of the intermediate layer soft synthetic resin, and an antifouling synthetic resin surface layer is formed on this low refractive index synthetic resin layer. Good too.

When the surface layer is formed directly on the intermediate layer as described above, the adhesion between the intermediate layer and the surface layer will occur at many points (convex parts) on the finely uneven surface, and the adhesive strength between the two will be reduced. You may be dissatisfied. Such problems can be solved by providing a low refractive index synthetic resin layer between the two to cover the finely uneven surface.

Generally, the soft synthetic resin used for the intermediate layer is
Since it has a refractive index of 1.3 or more, the low refractive index synthetic resin may have a refractive index lower than that of the intermediate layer synthetic resin used, and is generally 1.30 to 1.55, preferably 1.35 to 1.53. selected from those having a refractive index of

Such low refractive index synthetic resins include polytrifluoroethyl methacrylate, polytrifluorochloroethylene, polytrifluoroethyl acrylate, polytetrafluoroethylene, polypentadecafluorooctyl acrylate, and tetrafluoroethylene-hexafluoropropylene copolymer. fluorine-containing compounds such as polydimethylsiloxane, silicon compounds such as polydimethylsilane, vinyl polymers such as polyvinyl acetate, polyvinyl formate, polyvinyl acetal, polyvinyl alcohol, polytertiary butyl methacrylate, polyisobutyl methacrylate, poly n-propyl methacrylate,
Methacrylic acid ester polymers such as polyethyl methacrylate and polymethyl methacrylate, polybutyl acrylate, polyethyl acrylate,
Examples include acrylic acid ester polymers such as polymethyl acrylate, vinyl ether polymers such as polyvinyl isobutyl ether, and polyvinyl ethyl ether. Of course, the low refractive index synthetic resin used in the present invention is not limited to these, and may also be a combination of two or more types.

It is sufficient that the low refractive index coating layer is used in an amount that fills the dents in the finely uneven surface, and generally
Formed with a weight of 0.01-10g/ ^m2 .

The finely textured surface of the intermediate layer and/or surface layer is
It is effective in reducing uneven gloss due to wrinkles formed on the sheet and improving the appearance of the antifouling sheet.

Furthermore, the low refractive index synthetic resin coating layer covering the finely uneven surface can improve the adhesive strength between the intermediate layer and the surface layer without impairing the effect of the finely uneven surface.

The surface layer of the antifouling sheet of the present invention is formed from an antifouling synthetic resin. Examples of such antifouling synthetic resins include fluorine-containing polymer resins and acrylic polymer resins.

Examples of the fluorine-containing polymer resin used in the present invention include tetrafluoroethylene-hexafluoropropylene copolymer resin (FFP), tetrafluoroethylene-perfluoroalkyl copolymer resin (PFA), and polychlorotrifluoroethylene resin. (PCTFE), polyvinylidene fluoride resin (PVDF), polyvinyl fluoride resin (PVF), polydichlorodifluoroethylene resin,
and chlorotrifluoroethylene-ethylene copolymer resin (ECTFE).

The acrylic polymer resin used in the present invention is preferably one mainly composed of polyalkyl methacrylate. The polyalkyl methacrylate resin is preferably a single polymer of methyl methacrylate, ethyl methacrylate, propyl methacrylate, or butyl methacrylate, or a copolymer of two or more of these. Acrylic resin contains alkyl acrylate, vinyl acetate,
Single polymers such as vinyl chloride, styrene, acrylonitrile, methacrylonitrile, or two of these
A small amount of copolymers of more than one species may be mixed,
Further, the above monomer may be copolymerized with the above alkyl methacrylate.

The above fluorine-containing polymer resin and acrylic polymer resin have extremely good weather resistance, but
For the purpose of protecting the intermediate layer, ultraviolet absorbers and other functional agents such as colorants may be added to these resins.

The surface layer is generally manufactured by attaching a film of antifouling synthetic resin to the surface of the intermediate layer, but it is also possible to apply a paste or straight antifouling synthetic resin using a conventionally known coating method. It can also be formed by

The surface layer generally preferably has a weight of 1 to 100 g/m ² , more preferably 3 to 50 g/m ² . The thickness of the surface layer is preferably in the range of 1 to 50 microns, more preferably in the range of 2 to 40 microns.

The antifouling synthetic resin that forms the surface layer of the antifouling sheet of the present invention forms a relatively hard film, and therefore, when fine irregularities are formed on the surface of the surface layer that joins the intermediate layer, the antifouling synthetic resin forms a relatively hard film. It has the advantage of being easy to store and maintaining its effects.

〔Example〕

The present invention will be explained below using examples.

Example 1 The following textile structure: Polyester spun yarn 20 ^S / 1 × 20 ^S / 1 / 92 pieces / 25.4 mm × 55 pieces / 25.4 mm Weight: 195 g / m ² Structure: Plain weave polyester spun yarn fabric smelted by conventional method This was dried and used as a base fabric.

Separately, a composition having the following composition: 100 parts by weight of polyvinyl chloride (PCV), 75 parts by weight of DOP (plasticizer), 3 parts of zinc stearate, and 2 parts of color pigment was kneaded in a calendar to produce a sheet with a thickness of 0.1 mm.

The PCV sheet was heated and adhered to the surface of the base fabric at 180°C to produce an intermediate laminate sheet with a thickness of 0.58 mm. Both sides of this intermediate laminate sheet are preheated to a temperature of 100°C, and then pressed using a water-cooled embossing roll.
A satin finish embossing process was performed at 3.5 kg/cm to form a finely uneven surface in which many depressions with a diameter of 50 microns and a depth of 2 microns were formed at intervals of 10 to 50 microns.

The KFC sheet (polyvinylidene fluoride resin layer (2 to 3 microns thick)/acrylic polymer resin layer (2 to 4 microns thick)/polyvinylidene fluoride resin layer (2 to 4 microns thick)/polyvinylidene fluoride resin layer (2 to 4 microns thick)/polymer The polyvinyl chloride resin layer side of a polyvinyl chloride resin (45 micron thick) laminated sheet (manufactured by Kureha Chemical Industry Co., Ltd.) was heated and extrusion bonded to such an extent that it did not fill the dents in the finely uneven surface.

A test piece with dimensions of 10 cm x 10 cm was taken from the obtained antifouling sheet and subjected to a hand-rubbing process to form wrinkles in the sheet. When this wrinkled antifouling sheet was observed with the naked eye under light, it was found that the nonuniformity of the gloss due to the wrinkles was not clear and it had a good appearance.

For comparison, the steps of the above example were repeated. However, the surface layer was formed without embossing the intermediate laminate sheet. This comparative sheet had extremely uneven gloss due to the wrinkles and had a poor appearance.

Example 2 Vinylon spinning canvas (plain weave) with the following structure: Structure: 20 ^S / 3 x 20 ^S / 4 / 45 pieces / 25.4 mm x 38 pieces / 25.4 mm Fabric weight: 360 g / m ² was boiled, dried and made into a base. Made of cloth.

This base fabric was treated with a processing liquid having the following composition: Polyvinyl chloride resin 80 parts by weight Butylbenzine phthalate 68 Epoxidized soybean oil 7 Calcium carbonate 20 Cadmium-barium stabilizer 3 Pigment 8 Toluene (solvent) 130 The amount of adhered liquid was adjusted to 100% of the weight of the base fabric by immersing it in PVC and squeezing it with a roller, drying it at 90℃ for 1 minute, and then heat-treating it at 180℃ for 1 minute to make PVC. was gelled and fixed, and this was pressed using a roll with a smooth surface. The refractive index of the formed intermediate layer was 1.62. Moreover, both surfaces of the obtained intermediate layer were smooth. A matte embossing process was applied to one side of this smooth surface at a temperature of 100°C to form a large number of depressions similar to those in Example 1.

A 10% aqueous dispersion of polybutyl acrylate (refractive index = 1.35) was applied to the resulting finely uneven surface to a thickness of 3 to 5 microns to fill the dents in the surface of the intermediate layer, and dried.

Then apply a layer of polybutyl acrylate to a thickness of 12
Micron Tedlar film (polyvinyl fluoride resin (PVF), manufactured by DuPont) was attached at 160°C.

When the obtained antifouling sheet was subjected to the hand-rubbing treatment described in Example 1 and visually observed, almost no abnormal gloss unevenness due to wrinkles was observed.

For comparison, the same treatment as in Example 2 above was performed. However, embossing and coating were not performed. In the comparison antifouling sheet obtained, uneven gloss due to wrinkles was clearly observed.

Example 3 The same operation as in Example 2 was performed. However, the surface of the intermediate layer was not embossed with a satin finish, but the surface to which the Tedlar film was bonded was embossed with a matte finish. As in Example 2, no uneven gloss was observed.

〔effect〕

The antifouling sheet of the present invention has the same antifouling surface as conventional antifouling sheets, and therefore has the same antifouling effect, less uneven gloss and glare due to wrinkles, and a desirable appearance. It is something.

[Brief explanation of the drawing]

1 and 2 are cross-sectional explanatory views of one embodiment of the antifouling sheet of the present invention, respectively. DESCRIPTION OF SYMBOLS 1... Antifouling sheet, 2... Base fabric, 3... Intermediate layer, 4... Surface layer, 5... Irregularities, 6... Low refractive index synthetic resin layer.

Claims (1)

[Claims for Utility Model Registration] 1. A base fabric made of fiber fabric, and at least one of the base fabrics.
An intermediate layer made of a soft synthetic resin formed on the surface, and an antifouling synthetic material formed on the surface of the intermediate layer and containing at least one selected from a fluorine-containing polymer resin and an acrylic polymer resin. 1. An antifouling sheet having a surface layer made of resin, and having fine irregularities formed on at least one bonding surface between the intermediate layer and the surface layer, which are bonded to each other. 2. The antifouling sheet according to claim 1, wherein the base fabric is a plain woven fabric made of polyester long fibers. 3 The soft synthetic resin is polyvinyl chloride resin,
Utility model registration claim 1 consisting of at least one selected from the group consisting of ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-vinyl chloride copolymer resin, polyvinylidene chloride resin, and polyurethane resin Antifouling sheet as described in section. 4. The antifouling sheet according to claim 1, wherein the intermediate layer has a weight of 30 to 1000 g/ ^m2 . 5. The surface layer has a weight of 1 to 100 g/ ^m2 ,
An antifouling sheet according to claim 1 of the utility model registration claim. 6. The antifouling sheet according to claim 1, wherein fine irregularities are formed on the surface of the intermediate layer or the back surface of the surface layer by a satin finish embossing process. 7 On the surface of the intermediate layer or the back surface of the surface layer, 0.01
The antifouling sheet according to claim 1, wherein a large number of depressions having a depth of 5 to 200 microns are formed at intervals of 5 to 100 microns. 8. The antifouling sheet according to claim 1, wherein the finely uneven surface is covered with a synthetic resin having a refractive index lower than the refractive index of the soft synthetic resin of the intermediate layer.