JPS61199945A - Antifouling sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 reduces the occurrence of differences in gloss due to wrinkles formed during use. This is about dirty sheets.

[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 cloth, and an antifouling synthetic resin layer is formed thereon.

For example, JP-A-56-60247. and 59-150
No. 743 discloses an antifouling sheet obtained by forming an intermediate layer made of polyvinyl chloride resin on a base fabric, and forming a surface layer made of fluorine-containing polymer resin on this intermediate layer. .

Also, JP-A-59-165653 and JP-A-58-14
No. 7355 discloses an antifouling sheet in which a polyurethane resin intermediate layer is formed on a base fabric, and a fluorine-containing polymer surface layer is formed thereon.

Furthermore, JP-A-59-146847 and JP-A-59-129
In No. 146, is it on the base fabric? An antifouling sheet is disclosed in which a vinyl chloride resin intermediate layer is formed, and an acrylic polymer resin surface layer is formed thereon.

Furthermore, JP-A-58-147356 and JP-A-59-15
No. 6744 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, in these conventional antifouling sheets, wrinkles that occur when they are bent or folded during use are difficult to recover, and when light hits these wrinkled areas, the gloss becomes uneven. A defect in appearance is recognized, such as the presence of noticeable wrinkles.

The above-mentioned drawbacks can be overcome by forming fine irregularities on the surface of the surface layer made of antifouling synthetic resin. (90) [Problems to be Solved by the Invention] To provide an antifouling sheet in which wrinkles formed during use are not noticeable.

[Means and effects of rounding to solve the problem] The antifouling sheet of the present invention comprises a base fabric made of fiber fabric and at least one of the base fabrics.
The intermediate layer has an intermediate layer made of a soft synthetic resin formed on the surface and a surface layer made of an antifouling synthetic resin formed on the surface of the intermediate layer, and the intermediate layer is bonded to each other. It is characterized in that fine irregularities are formed on at least one bonding surface between the surface layer and the surface layer.

In the antifouling sheet of the present invention, the joining surface of at least one of the intermediate layer and the surface layer having fine irregularities is covered with a synthetic resin having a refractive index lower than that of the soft synthetic resin of the intermediate layer. It may be something that exists.

The base fabric used in the antifouling sheet of the present invention is a fiber fabric. The fibers that make up this fabric are natural fibers,
For example, inorganic fibers such as cotton and hemp; recycled fibers such as glass fiber; e.g. viscose rayon;
semi-synthetic fibers, such as gee and triacetate fibers, and synthetic fibers, such as nylon 6,
Nylon 66, ester Cyle polyethylene tele 7
talates, etc.), aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, and 4-lyolefin fibers. The fibers in the fabric may be in any form, such as short edge fiber spun yarn, long fiber yarn, split yarn, or tape yarn, and the fabric may be woven, woven, nonwoven, or a composite fabric thereof. There may be. 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 resin used in the present invention includes polyvinyl chloride resin, ethylene-vinyl acetate-vinyl chloride copolymer resin, ethylene-vinyl acetate copolymer resin, polyvinylidene chloride resin, other vinyl-based synthetic resins, polyurethane resins, 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 is formed on the base fabric by a conventionally known method such as side light topping, calendering, coating, or tipping using a soft synthetic resin film, (-st, or straight). be able to.

This intermediate layer has a sufficient weight, e.g.
0f/rn! and has a sufficient thickness, e.g. 0.05 m or more, preferably 0.05 to 1.0 tm.
It has a thickness of .

There are no particular limitations on the method for forming fine irregularities in which fine irregularities are formed on the bonding surface of the intermediate layer formed on the base fabric as described above and/or the surface layer formed thereon. Instead, conventionally known surface roughening methods such as the Enges method (particularly the matte Enges method), low temperature plasma treatment method, etching method, square 4 tattering method, and granular physical casting method can be used. There are no particular limitations on the shape, size, etc. of the unevenness formed on at least one bonding surface between the intermediate layer and the surface layer, as long as the object of the present invention is achieved.
For example, the diameter is 5-200 microns, preferably 10-1
A finely textured surface is formed with a large number of depressions having a depth of 0.01 to 5 microns, preferably o, oi 3 to 2 microns, spaced at intervals of 5 to 100 microns, preferably 10 to 50 microns. Preferably formed - A surface layer made of an antifouling synthetic resin may be formed directly on the above-mentioned finely uneven surface. Further, this finely uneven surface may be coated with a synthetic resin having a refractive index lower than that of the intermediate layer soft synthetic resin, and an antifouling synthetic resin surface layer may be formed on this coating layer.

When the surface layer is formed directly on the intermediate layer as described above, the adhesion between the intermediate layer and the surface layer is caused by a large number of points (
If this is done at the convex portion, the adhesive strength between the two may be unsatisfactory. 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 has a refractive index of 1.3 or more, so the low refractive index synthetic resin is one that has a lower refractive index than the intermediate layer synthetic resin used. Generally, it is selected from those having a refractive index of 1.1 to 1.5, preferably 1.2 to 1.4.

Such low refractive index synthetic resins include /su)lifluoroethyl methacrylate, polytrifluorochloroethylene, /lidrifluoroethyl acrylate, polytetrafluoroethylene, polypentadecafluorooctyl acrylate, and tetrafluoroethylene-hexafluoropropylene. Fluorine-containing compounds such as copolymers, silicon compounds such as I-ridimethylsiloxane and polydimethylsilane, polyvinyl acetate, polyvinyl form)
, /9 vinyl acetal, vinyl polymers such as /vinyl alcohol, polytert-butyl methacrylate, polyisobutyl methacrylate, poly n-propyl methacrylate.

I ethyl methacrylate, methacrylic acid ester polymers such as polymethyl methacrylate, /rich acrylate, / ethyl acrylate.

Acrylic acid esters such as polymethyl acrylate! Examples include vinyl ether polymers such as /vinyl 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 to fill the dents in the finely uneven surface.
/m2.

The finely textured surface of the intermediate layer and/or the surface layer 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-hexafluoroprogylene copolymer resin (FFP), tetrafluoroethylene-hexafluoroprogylene copolymer resin (FFP),
/JP-fluoroalkyl copolymer resin (PFA), /
Lichlorotrifluoroethylene resin (PCTFE), polyvinylidene fluoride resin 11 (PVDF), polyvinyl fluoride resin (PVF), /lichlorodifluoroethylene resin, and chlorotrifluoroethylene-ethylene copolymer resin (ECTFE), etc. You can choose from.

The acrylic polymer resin used in the present invention is preferably one mainly composed of polyalkyl methacrylate.
/As the realkyl methacrylate resin, a single polymer of methyl methacrylate, ethyl methacrylate, brol methacrylate, and butyl methacrylate, or a copolymer of two or more of these is preferable. In the acrylic resin, a small amount of a monopolymer such as alkyl acrylate, vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylate trile, or a copolymer of two or more of these may be mixed. It may be copolymerized with the above alkyl methacrylate.

The above-mentioned fluorine-containing polymer resins and acrylic polymer resins have extremely good weather resistance, but in order to protect the intermediate layer, ultraviolet absorbance and other functional agents are added to these resins. For example, a coloring agent, etc. may be added.

The surface layer is generally manufactured by pasting a film of antifouling synthetic resin on the surface of the intermediate layer, but a paste or straight antifouling synthetic resin may be applied by a conventionally known coating method. ) It can also be formed by coating.

The surface layer generally has a weight of 1 to 100 f/m", preferably 3 to 50 g/m2). The thickness of the surface layer should be in the range of 1 to 50 microns. is preferred, and more preferably within 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. , it has the advantage of being easy to store and having a long-lasting effect.

〔Example〕

The method of the present invention will be explained below using examples.

Example 1 The following textile structure: Polyester spun yarn basis weight: 195 f/ln2 Structure: A plain weave polyester spun yarn fabric was scoured and dried in a conventional manner to be used as a base fabric.

Separately, the following composition: I vinyl chloride (PVC) too parts by weight D,
O, P, (Plasticizer) 75 parts by weight Zinc stearate 3 Color pigment
2 Knead the resin composition in a calendar,
A sheet with a thickness of 0.1 m was produced.

The PvC sheet was heated and adhered to the surface of the base fabric at 180° C. to produce an intermediate laminated sheet having a thickness of 0.58 sheets. Both sides of this intermediate laminate sheet were preheated to a temperature of 100°C, and then rolled using a water-cooled Enges roll at a pressure of 3.5 kg/
cm, satin embossed, diameter 50 microns, g
A finely textured surface was formed in which a large number of depressions each having a diameter of 2 microns were formed at intervals of 10 to 50 microns.

The KFC sheet (/vinylidene fluoride resin layer (
thickness 2-3 microns) / acrylic polymer resin layer (thickness 2
~ 4 microns) / polyvinyl chloride, resin (45 micron thick) laminated sheet, manufactured by Kenbetsu Kagaku Kogyo Co., Ltd.) by heating the polyvinyl chloride resin layer side and applying it to fill in the dents on the surface of the fine irregularities mentioned above. It was pressure bonded to.

A test piece with dimensions LO x 1ocff1 was taken from the obtained antifouling sheet and subjected to a hand-rubbing process to form wrinkles in the sheet. When the wrinkled antifouling sheet was observed with the naked eye under light, it was found that the uneven gloss caused by the wrinkles was clear and had a good appearance.

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

Vinylon spun yarn canvas (plain weave) with the following structure: Weight:
It was boiled at 360 f/m2 and dried to obtain a base fabric.

Processing liquid with the following composition: Polyvinyl chloride resin (80 parts by weight butyl pendyl phthalate) 68-weight Ti epoxidized soybean oil 7 Calcium carbonate
20 Cadmium barium stabilizer
3 Pigment 8 Toluene (solvent) 130 Immerse in #
Squeeze with a roller to reduce the amount of adhered liquid to 100% of the weight of the base fabric.
% IIC was prepared, dried at 90° C. for 1 minute, and then heat-treated at 180° C. for 1 minute to solidify the PvC and pressurized with a roll with a smooth surface.

The refractive index Fi of the formed intermediate layer was 1.62. Moreover, both surfaces of the obtained intermediate layer were smooth. One side of this smooth surface is given a matte finish finish at a temperature of 100℃,
A large number of depressions similar to those in Example 1 were formed.

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.

Next, a 12 micron thick teller film (polyvinyl fluoride resin) is applied on the polybutyl acrylate coating layer.
PVF (manufactured by DuPont) was attached at 160°C.

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

For comparison, the same treatment as in Example 2 above was performed. However, no engraving or coating treatment was 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 matte embossing was not applied to the surface of the intermediate layer, but the matte embossing was applied to the bonded surface of the Tetra film. As in Example 2, occurrence of uneven gloss was observed.

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

Claims (1)

[Claims] 1. A base fabric made of fiber fabric, an intermediate layer made of a soft synthetic resin formed on at least one surface of the base fabric, and an antifouling property formed on the surface of this intermediate layer. and a surface layer made of a synthetic resin, and fine irregularities are formed on at least one bonding surface between the intermediate layer and the surface layer, which are bonded to each other.
Antifouling sheet. 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, ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate-
The antifouling sheet according to claim 1, comprising at least one selected from the group consisting of vinyl chloride copolymer resin, polyvinylidene chloride resin, and polyurethane resin. 4. The antifouling sheet according to claim 1, wherein the antifouling synthetic resin is made of at least one selected from fluorine-containing polymer resins and acrylic polymer resins. 5. The antifouling sheet according to claim 1, wherein the intermediate layer has a weight of 30 to 1000 g/m^2. 6. The antifouling sheet according to claim 1, wherein the surface layer has a polymerization rate of 1 to 100 g/m^2. 7. The antifouling sheet according to claim 1, wherein fine irregularities are formed on the surface of the intermediate layer by a matte embossing process. 8. A claim in which a large number of depressions having a depth of 0.01 to 5 microns and a diameter of 5 to 200 microns are formed on the surface of the intermediate layer at intervals of 5 to 100 microns. The antifouling sheet described in item 1. 9. A base fabric made of fiber fabric, an intermediate layer made of a soft synthetic resin formed on at least one surface of the base fabric, and a surface layer made of an antifouling synthetic resin formed on the surface of this intermediate layer. The intermediate layer and the surface layer have fine irregularities formed on at least one joint surface of the intermediate layer and the surface layer, and the fine irregular surface is formed on the soft synthetic resin of the intermediate layer. An antifouling sheet coated with a synthetic resin that has a refractive index lower than the refractive index. 10. The antifouling sheet according to claim 1, wherein the low refractive index synthetic resin has a refractive index of 1.1 to 1.5.