JPH1096170A - Vinyl chloride-based resin-coated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl-chloride based resin-coated sheet having flame retardancy usable in a wide range, excellent in transparency, stain resistance and weather resistance. SOLUTION: This sheet is obtained by coating a woven or knitted fabric composed of a synthetic fiber yarn with a vinyl chloride-based resin paste comprising 100 pts.wt. of a vinyl chloride-based resin, 30-60 pts.wt. of a phthalic acid ester-based compound, 30-60 pts.wt. of a phosphoric ester based compound and 10-30 pts.wt. of an isocyanuric acid compound. Further the sheet is coated with a fluorine-based polymer containing 0.1-20 pts.wt. calculated as solid content of a benzotriazole-based compound, benzophenone-based compound, salicylate- based compound or a combination of the plural these compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a truck cover sheet,
The present invention relates to sheets for construction work, such as tarpaulins and mesh sheets for construction work, open-stacked sheets, and sheets used for tents and the like.

[0002]

2. Description of the Related Art Sheets for truck hoods and sheets for building construction coated with a vinyl chloride resin are well known. These are manufactured by coating a cloth woven or knitted with spun yarn or long fiber yarn of vinylon, polyamide, polyester, aramid or the like with a vinyl chloride resin by a method such as dipping or coating.

[0003] Sheets coated with a vinyl chloride-based resin are widely used because various processing methods can be adopted, the flexibility can be adjusted by adjusting a plasticizer, and the coloring property of the pigment is excellent. That, in addition,
The soft vinyl chloride resin can be sewn by high frequency welding welding. The properties required for these industrial sheets are tensile strength, tear strength, toughness, flame retardancy, abrasion resistance, water resistance, as well as antifouling properties to maintain the aesthetics of the work site. Recently, the color is multicolored, the hue exceeds 50 colors, and fashionability is also required.

However, in a field where flame retardancy is required in terms of hue, a transparent sheet has not been obtained at present because a vinyl chloride resin contains antimony trioxide. This is due to the fact that antimony trioxide does not easily melt even when subjected to thermal processing and is dispersed in the resin, resulting in devitrification of the resin and hindering the transparency of the vinyl chloride resin. It is. Sheets coated with vinyl chloride resin have many advantages, but when used outdoors for long periods of time, the plasticizer in the resin migrates to the surface and becomes tacky. And has the disadvantage that the hue and physical properties are degraded by ultraviolet rays of sunlight.

[0005] Various methods for solving such a problem have been proposed. Typical examples thereof include a method of coating the surface of a vinyl chloride resin with an acrylic resin such as polyacrylate or a urethane resin, and a method of coating with a fluorine elastomer (for example,
No. 321980). However, in the method of coating an acrylate resin or a urethane resin, the persistence of the effect is poor because the plasticizer in the vinyl chloride resin moves to the surface through the resin layer. In addition, the method of coating with a fluoroelastomer has problems that adhesion to a vinyl chloride resin is poor, the feel becomes hard, and furthermore, sufficient durability and antifouling properties cannot be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and provides a vinyl chloride resin-coated sheet having flame retardancy and excellent transparency and weather resistance. It is another object of the present invention to obtain a vinyl chloride resin-coated sheet having antifouling properties.

[0007]

The present invention achieves the above object and has the following construction. That is, the present invention provides a vinyl chloride resin-coated sheet formed by weaving and knitting a synthetic fiber yarn coated with a vinyl chloride resin paste, or a vinyl chloride resin obtained by coating a woven or knitted fabric made of a synthetic fiber yarn with a vinyl chloride resin paste. In a resin-coated sheet, a film having a thickness of 0.1 mm heat-processed after forming a film with a vinyl chloride resin paste used for coating has a total light transmittance of 80% or more, a diffusion transmission coefficient of 40% or more, and a haze (cloudiness) of 45% or less. Characterized in that the synthetic fiber yarn is a yarn having flame retardancy, or a phthalate compound is used in an amount of 30 to 60 parts by weight based on 100 parts by weight of a vinyl chloride resin. 30 compounds
~ 60 parts and isocyanuric acid ester compound
30 parts by weight, or both, impart flame retardancy, and contain a benzotriazole-based, benzophenone-based, salicylate-based compound or a compound obtained by combining a plurality of these compounds in a solid content of 0.1 to 20% by weight. A fluorine-based polymer, a copolymer composition of the fluorine-based polymer and an acrylate-based polymer, a friend composition, a benzotriazole-based, benzophenone-based, salicylate-based compound or a combination of a plurality of the compounds. A composition having about 90 mol% in the side chain of the acrylate polymer, a copolymer composition or a blend composition of the composition having the side chain of the acrylate polymer and the fluorine polymer Abstract: A vinyl chloride resin-coated sheet coated on at least one side with antifouling properties It is assumed that.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The synthetic fiber yarn used in the present invention may be any of a spun yarn, a monofilament, and a long fiber yarn of a synthetic fiber such as polyamide, polyester, aramid, and vinylon.

As synthetic fiber yarns having flame retardancy,
It may be one produced by adding a flame retardant in the polymerization step or spinning step during fiber production, or one obtained by adding a flame retardant by a yarn treatment, but a yarn produced by adding a flame retardant in the polymerization step Articles are preferred. Examples of the flame retardant used include a phosphorus compound, a halogen compound, a phosphorus-halogen compound, an antimony compound, and an organic sulfur nitrogen compound. These compounds may be used alone or in a composite. If the flame retardant is used in a large amount, the strength and elongation of the fiber are reduced, so the amount of the flame retardant must be appropriately adjusted. If the addition amount is small, the flame retardant effect is not sufficient, and the addition amount is 0.1 to 1
Preferably, it is weight%.

The sheet of the present invention is a woven or knitted fabric woven or knitted with synthetic fiber yarns coated with a vinyl chloride resin paste, or a woven or knitted fabric woven or knitted with synthetic fiber yarns coated with a vinyl chloride resin paste. This is a processed vinyl chloride resin-coated sheet. The vinyl chloride resin refers to a vinyl chloride polymer, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinylidene chloride copolymer or a mixture of the above-mentioned polymers or copolymers. Combustion agents, pigments, aluminum powder, glass beads and other additives are blended and used in paste form. It is preferable that the pigment does not contain a substance having a masking property such as titanium oxide, and it is difficult to obtain transparency with a pigment containing a substance having a masking property.

The vinyl chloride resin paste according to the present invention is such that a film having a thickness of 0.1 mm, which is heat-processed after forming a film with the vinyl chloride resin paste, has a total light transmittance of 80% or more;
It is necessary to have characteristics of a diffusion transmission coefficient of 40% or more and a haze of 45% or less. The thermal processing after forming the film is to apply heat at a temperature higher than the temperature at which the vinyl chloride resin hardens and becomes solid, and the temperature is determined by the blending of the plasticizer and the like. Generally, after drying at a temperature of 50 to 150 ° C, curing is performed at a temperature of 150 to 200 ° C. Taking into account the boiling point of the plasticizer, the surface migration and the state of the film, 90
It is preferable to perform drying at a temperature of 160 ° C to 180 ° C after drying at a temperature of 110 ° C to 110 ° C. Regarding the physical properties of the film, when the total light transmittance is less than 80%, light hardly passes through in a state of being covered with the fiber, and when the diffusion coefficient is 40% or less, a phenomenon occurs that light diffuses and whitens, and Haze is 4
If it is 5% or less, the light transmittance is poor and the sense of transparency is lost.

The vinyl chloride resin paste contains 30 to 60 parts by weight of a phthalic acid ester compound, 30 to 60 parts by weight of a phosphate ester compound and 30 to 60 parts by weight of an isocyanuric acid ester compound per 100 parts by weight of the vinyl chloride resin. 1
It is preferable that the composition contains 0 to 30 parts by weight, and it does not need to contain an inorganic substance which does not melt due to heat applied during processing of a vinyl chloride resin paste such as antimony trioxide or calcium carbonate which may hinder transparency. is there.

The phthalic acid ester compounds include dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), and di-n-octyl phthalate (nD
OP), butyl lauryl phthalate (BLP), dilauryl phthalate (DLP), butyl benzyl phthalate (BBP), etc., and the amount contained in the paste is 30 to 60 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 30 parts by weight, the dissolving power and the compatibility may be reduced. If the amount is more than 60 parts by weight, the flame retardancy may be poor.

Examples of the phosphoric ester compound include tricresyl phosphate (TCP), trisdichloropropyl phosphate (TDCPP), trixylenyl phosphate (TXP), monooctyl diphenyl phosphate, monobutyl-dixylenyl phosphate and trioctyl phosphate. And the amount contained in the paste is from 30 to 100% by weight of the vinyl chloride resin.
It is 60 parts by weight, and if it is less than 30 parts by weight, the flame retardant effect is reduced, and if it is more than 60 parts by weight, the cold resistance and the compatibility may be poor.

A typical example of the isocyanuric acid ester compound is tris (2,3-dibromopropyl) isocyanurate (TDI). The amount contained in the paste is based on 100 parts by weight of the vinyl chloride resin. 10
If it is less than 10 parts by weight, the flame retardant effect is reduced, and if it is more than 30 parts by weight, the cold resistance and the compatibility may be poor.

The sheet of the present invention is a fluorine-containing sheet containing the above-mentioned vinyl chloride resin-processed sheet containing 0.1 to 20% by weight of a benzotriazole-based, benzophenone-based, salicylate-based compound or a combination thereof in a solid content. -Based polymer, a composition obtained by copolymerizing a fluorine-based polymer and an acrylate-based polymer, and a composition obtained by blending a fluorine-based polymer and an acrylate-based polymer, or a benzotriazole-based or benzophenone-based A composition having a salicylate compound or a combination of a plurality of the compounds in the side chain of the acrylate ester polymer at a ratio of 10 to 90 mol%, and a composition having the side chain of the acrylate polymer. A composition obtained by copolymerization of a fluorine-based polymer and an acrylic ester-based polymer in the side chain 1 to 20 g / m ² on at least one surface of a composition obtained by blending
To obtain a coating.

The fluororesin used in the present invention may be any of tetrafluoroethylene, a fluoroolefin polymer, and a copolymer of the olefin with a synthetic resin such as an acrylic resin, a polyol resin and a urethane resin.
The ratio of copolymerization or blending with the acrylate polymer is not particularly limited, but if it is more than 70 wt%, the properties of the acrylate polymer may be inferior. %.

The acrylate resin used in the present invention is obtained by polymerization or copolymerization of acrylic acid or methacrylic acid ester, and may be combined with melamine, epoxy, acrylamide or the like. . Methyl methacrylate is preferred from the viewpoint of flexibility and cost. In addition, stabilizers, plasticizers, flame retardants, pigments, aluminum powder, and other additives may be blended and used depending on the application and processing method.

The benzotriazole compounds used in the present invention include 2- (2-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'hydroxy3 '
Benzotriazole derivatives such as tert-butyl-5'methylphenol) 5'chlorobenzotriazole and 2- (2'hydroxy3'5'di-tert-butyl-5'methylphenol) 5'chlorobenzotriazole. Benzophenone compounds are 2.4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4methoxy-2'-carboxybenzophenone, 2hydroxy-4methoxy Benzophenone derivatives such as benzophenone-5 sulfonic acid. The salicylate compound is phenyl salicylate, p-octylphenyl salicylate,
Salicylate derivatives such as 4-tert-butyl salicylate. Among the above-mentioned ultraviolet absorbers, 2,4-dihydroxybenzophenone is preferable from the viewpoints of compatibility with vinyl chloride resin, effects and cost.

As for the acrylate polymer, these ultraviolet absorbers are bonded to the side chain of the acrylate polymer by an ester bond or an ether bond. The ratio is 10 to 90 mol%, and if it is less than 10 mol%, it cannot sufficiently serve as an ultraviolet absorber, and if it is more than 90 mol%, the acrylic resin resin has an adverse effect on the inherent antifouling property. give. Preferably 40-60mo
l%.

Further, in the acrylic ester polymer,
In order to three-dimensionally crosslink unsaturated groups and hydroxyl groups contained in the acrylate resin, and to improve durability by improving film strength, an isocyanate can be used in combination with the copolymer. Preferred isocyanates include diphenylmethane diisocyanate, 2,4-toluene diisocyanate and the like. The amount of isocyanate used is 10 to 3 of the mixed resin in terms of solid content.
If the content is less than 10% by weight, the film strength is weak because the crosslinking is insufficient, and if the content is more than 30% by weight, the monomer of isocyanate may remain.

As a method of coating the vinyl chloride resin-coated sheet with the prepared composition, a method such as dipping or coating such as gravure coating or knife coating can be adopted. Regarding the amount of adhesion, if the solid content is more than 1 to 20 g / m ² in order to sufficiently satisfy the performance, cracks occur and it becomes impossible to apply uniformly.

[0023]

According to the present invention, the phthalate compound is 30 to 60 parts by weight, the phosphate compound is 30 to 60 parts, and the isocyanurate compound is 10 to 30 parts by weight, based on 100 parts by weight of the vinyl chloride resin. Physical properties of a 0.1 mm thick film obtained by thermal processing with a total light transmittance of 80% or more, a diffuse transmission coefficient of 40% or more, and a haze of 45% After coating the vinyl chloride resin paste having the following performance on a synthetic fiber yarn or a woven or knitted fabric comprising the synthetic fiber yarn, a benzotriazole-based, benzophenone-based, salicylate-based compound or a compound obtained by combining a plurality of the compounds is used. Containing 0.1 to 20% by weight of solid content, fluorine-based polymer and acrylate-based polymer A composition obtained by copolymerization or a composition obtained by blending a fluorine-based polymer and an acrylate-based polymer, or a benzotriazole-based, benzophenone-based, salicylate-based compound or a combination of a plurality of the compounds, 10 A composition having a side chain of an acrylate-based polymer in a ratio of ~ 90 mol%, a composition obtained by copolymerizing a composition having a side chain of an acrylate-based polymer with a fluorine-based polymer or an acrylate A composition obtained by blending a composition having a side chain of a fluorinated polymer with a composition having a pendant polymer is 1 to 20 g /
By coating with an amount of m ² , a sheet having flame retardancy, excellent transparency and weather resistance, and antifouling properties can be obtained.

[0024]

(Composition of dirt compound)

 ・ Peat moss 38% by weight ・ Cement 17% by weight ・ Kaolin clay 17% by weight ・ Silica gel 17% by weight ・ Carbon black 1.75% by weight ・ Iron oxide 0.50% by weight ・ Mineral oil (Heavy oil A) 8.75% by weight

☆ Evaluation of Film Transparency Using Vinyl Chloride Resin Paste First, in order to evaluate the transparency of the vinyl chloride resin pastes of various formulations used in the examples in Table 1, each of the vinyl chloride resin pastes was separated. A film having a thickness of 0.1 mm is formed on a pattern paper, dried at 100 ° C. for 2 minutes and cured at 180 ° C. for 1 minute, and then subjected to the total light transmittance of the film according to JIS-K-6714,6718. , Diffusion coefficient and haze (cloudiness) were measured, and transparency was evaluated by visual observation.

[0026]

[Table 1]

In the above compounding of the vinyl chloride resin paste, as the vinyl chloride resin, a vinyl chloride resin compound ZEST P21 manufactured by Shin-Daiichi PVC Co., Ltd., and as the stabilizer, KR-69E-1 manufactured by Kyodo Yakuhin Co., Ltd. Using.

Example 1 Polyester multifilament 75 for both warp and weft
0d / 70f, density is 33 / inch, weft 33 /
Weaving a 6 inch 1 inch woven fabric with a complete mosaic structure, dipped with 240 g / m ² of the above-mentioned No. 1 vinyl chloride resin paste, dried at 100 ° C. for 2 minutes,
After curing at 80 ° C. for 1 minute, a vinyl chloride resin-coated sheet of the present invention was obtained.

Comparative Example 1 Polyester multifilament 75 for both warp and weft
0d / 70f, density is 33 / inch, weft 33 /
Weaving a 6-inch inch 1-perfect mosaic fabric, 240 g / m ² of the above-mentioned No. 3 vinyl chloride resin paste was applied by dipping, and dried at 100 ° C. for 2 minutes.
After curing at 80 ° C. for 1 minute, a vinyl chloride resin-coated sheet of the present invention was obtained.

Comparative Example 2 Polyester multifilament 75 for both warp and weft
0d / 70f, density is 33 / inch, weft 33 /
Weaving a 6 inch 1 inch woven fabric with a complete mosaic structure, dipped with 240 g / m ² of the above-mentioned No. 4 vinyl chloride resin paste, dried at 100 ° C. for 2 minutes,
After curing at 80 ° C. for 1 minute, a vinyl chloride resin-coated sheet of the present invention was obtained.

Example 2 Polyester multifilament 75 for both warp and weft
0d / 70f, density is 33 / inch, weft 33 /
Weaving a 6 inch 1 woven fabric with a complete mosaic texture, 240 g / m ² of the above No. 2 vinyl chloride resin paste was applied by dipping, and dried at 100 ° C. for 2 minutes.
After curing at 80 ° C. for 1 minute, a vinyl chloride resin-coated sheet of the present invention was obtained.

Example 3 Polyester multifilament 3000d / 280f
And the above compound N by a dip-nozzle drawing method.
After adding 180% by weight of the o.1 vinyl chloride resin paste, drying was performed at 110 ° C. × 2 minutes, and cured at 150 ° C. × 1 minute using a vinyl chloride resin coated yarn as the warp yarn to give a warp of 1%.
3 / inch, weft 13 / inch plain weave, 150 ° C ×
The tenter treatment was performed for 1 minute, and the contact points of the warp yarns were joined to obtain a vinyl chloride resin-coated sheet of the present invention.

Example 4 Bis β-hydroxy terephthalate obtained by esterifying terephthalic acid and ethylene glycol and 100 parts of a low polymer thereof were mixed with 100 parts of [2- (β-hydroxyethoxycarbonyl) ethyl] methylsulfonic acid as a flame retardant. 5 parts and 0.03 part of antimony trioxide were added and polymerized to obtain a flame-retardant polyester multifilament 750d / 70f obtained by polymer.
Weaving a woven fabric of 33 sq./inch, 6 pcs.
To this, 240 g / m ^{2 of the} vinyl chloride resin base of the above formulation No. 4 was applied by dipping, dried at 100 ° C. × 2 minutes, and cured at 180 ° C. × 1 minute to obtain the vinyl chloride resin of the present invention. A resin-coated sheet was obtained.

Example 5 Bis β-hydroxy terephthalate obtained by esterifying terephthalic acid and ethylene glycol and 100 parts of a low polymer thereof were added with [2- (β-hydroxyethoxycarbonyl) ethyl] methylsulfonic acid as a flame retardant. 5 parts and 0.03 part of antimony trioxide were added and polymerized. A flame-retardant polyester multifilament 3000d / 280f obtained by polymer was used. After applying 180% by weight of resin paste, drying at 110 ° C. for 2 minutes, 15
Using a vinyl chloride resin-coated yarn cured at 0 ° C. for 1 minute as a warp yarn, weave a plain fabric having a density of 13 warps / inch and 13 wefts / inch, and perform a tenter treatment at 150 ° C. for 1 minute. Then, the contact points of the warp yarns were joined to obtain a vinyl chloride resin-coated sheet of the present invention.

Example 6 Bis β-hydroxy terephthalate obtained by esterifying terephthalic acid and ethylene glycol and 100 parts of a low polymer thereof were mixed with 100 parts of [2- (β-hydroxyethoxycarbonyl) ethyl] methylsulfonic acid as a flame retardant. 5 parts and 0.03 part of antimony trioxide were added and polymerized to obtain a flame-retardant polyester multifilament 750d / 70f obtained by polymer.
Weaving a 33-inch / inch, 6-piece, 1-perfect mosaic fabric,
To this, 240 g / m ² of the above-mentioned No. 1 vinyl chloride-based resin paste was applied by dipping, dried at 100 ° C. for 2 minutes, and cured at 180 ° C. for 1 minute to obtain the vinyl chloride-based resin of the present invention. A resin-coated sheet was obtained.

Table 2 also shows the evaluation results of the sheets obtained in Examples 1 to 6 and Comparative Examples 1 and 2.

[0037]

[Table 2]

As is clear from Table 2, Examples 1 to 6
Was a vinyl chloride resin-coated sheet having flame retardancy and excellent transparency. On the other hand, Comparative Example 1 using a vinyl chloride resin paste having flame retardancy by adding antimony trioxide has flame retardancy, but is inferior in transparency. The sheet of Comparative Example 2 using a vinyl chloride resin paste containing neither antimony trioxide nor a phosphate compound and an isocyanurate compound was inferior in flame retardancy.

Example 7 The vinyl chloride resin-coated sheet obtained in Example 1 was dipped in a processing solution having the following composition 1, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was carried out to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 1] Fluorotop FT-1030 100 parts by weight (fluoroolefin and alkyl vinyl ether copolymer, active ingredient 50%, manufactured by Asahi Glass Co., Ltd.) Fluorotop curing agent 20 parts by weight (isocyanate, active ingredient 67.6 %, Manufactured by Asahi Glass Co., Ltd.)-Biosorb 110 1 part by weight (2-hydroxy-4-methoxybenzophenone, manufactured by Kyodo Yakuhin Co., Ltd.)-Ethyl acetate / toluene (= 5/5) 400 parts by weight

Example 8 The vinyl chloride resin-coated sheet obtained in Example 1 was dipped in a processing solution having the following composition 2, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was carried out to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 2] 100 parts by weight of Zeffle LC-962 (-CH ₂ -CF _2- , -CF ₂ -CF _2- , -CF ₂ -CFCl- and a copolymer of fluoroolefin and thermoplastic acrylic Blend with resin, active ingredient 50%, manufactured by Daikin Industries, Ltd. ・ Biosorb 110 1 part by weight (2-hydroxy-4-methoxybenzophenone, manufactured by Kyodo Yakuhin Co., Ltd.) ・ Ethyl acetate / toluene (= 5/5) 400 parts by weight

Example 9 The vinyl chloride resin-coated sheet obtained in Example 1 was dipped in a processing solution having the following composition 3, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was performed to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 3] 50 parts by weight of UVA-935LH type F <[2-hydroxy-4- (methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer]
/ [Fluoroolefin] copolymer, active ingredient 30%,
BASF Japan Co., Ltd.> ・ 50 parts by weight of ethyl acetate

Example 10 The vinyl chloride resin-coated sheet obtained in Example 1 was dipped in a processing solution having the following composition 4, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was carried out to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 4] 50 parts by weight of UVA-935 LH <2-hydroxy-4- (methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer, active ingredient 30%, manufactured by BASF Japan Ltd.> Ethyl acetate 50 Parts by weight

Example 11 The vinyl chloride resin-coated sheet obtained in Example 6 was dipped in a processing solution having the following composition 5, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was carried out to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 5] Fluorotop FT-1030 100 parts by weight (fluoroolefin and alkyl vinyl ether copolymer, active ingredient 50%, manufactured by Asahi Glass Co., Ltd.) Fluorotop curing agent 20 parts by weight (isocyanate, active ingredient 67.6 %, Manufactured by Asahi Glass Co., Ltd.)-Biosorb 110 1 part by weight (2-hydroxy-4-methoxybenzophenone, manufactured by Kyodo Yakuhin Co., Ltd.)-Ethyl acetate / toluene (= 5/5) 400 parts by weight

Example 12 The vinyl chloride resin-coated sheet obtained in Example 6 was dipped in a processing solution having the following composition 6, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was carried out to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 6] 100 parts by weight of Zeffle LC-962 (-CH ₂ -CF _2- , -CF ₂ -CF _2- , -CF ₂ -CFCl- and a copolymer of fluoroolefin and thermoplastic acrylic Blend with resin, active ingredient 50%, manufactured by Daikin Industries, Ltd. ・ Biosorb 110 1 part by weight (2-hydroxy-4-methoxybenzophenone, manufactured by Kyodo Yakuhin Co., Ltd.) ・ Ethyl acetate / toluene (= 5/5) 400 parts by weight

Example 13 The vinyl chloride resin-coated sheet obtained in Example 6 was dipped in a processing solution having the following composition 7, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was carried out to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 7] 50 parts by weight of UVA-935LH type F <[2-hydroxy-4- (methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer]
/ [Fluoroolefin] copolymer, active ingredient 30%,
BASF Japan Co., Ltd.> ・ 50 parts by weight of ethyl acetate

Example 14 The vinyl chloride resin-coated sheet obtained in Example 6 was dipped in a processing solution having the following composition 8, squeezed with a mangle at a squeezing ratio of 20%, dried at 100 ° C., and then heat-treated at 150 ° C. × 1 minute. Was carried out to obtain a vinyl chloride resin-coated sheet provided with the antifouling property of the present invention.

[Composition 8] UVA-935 LH 50 parts by weight <2-hydroxy-4- (methacryloyloxyethoxy) benzophenone / methyl methacrylate copolymer, active ingredient 30%, manufactured by BASF Japan Ltd.> Ethyl acetate 50 Part by weight Table 3 shows the results of the evaluation tests of the obtained sheets of Examples 7 to 14.

[0055]

[Table 3]

As is clear from Table 3, Examples 7-14
The sheet having even better antifouling property and weather resistance.

[0057]

According to the present invention, a vinyl chloride resin-coated sheet having flame retardancy and excellent transparency can be provided, and a vinyl chloride resin sheet excellent in antifouling property and weather resistance can be provided. A resin-coated sheet can be provided.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/3477 C08K 5/3477 5/521 5/521 C08L 27/06 C08L 27/06 27/12 27/12 33/08 33/08 D03D 1/00 D03D 1/00 Z D06M 15/277 D06M 15/277

Claims (11)

[Claims] 1. A vinyl chloride resin-coated sheet formed by weaving and weaving a synthetic fiber yarn coated with a vinyl chloride resin paste, wherein the vinyl chloride resin paste used for coating is:
30 to 60 parts by weight of a phthalate compound, 30 to 60 parts of a phosphate compound and 10 to 30 parts by weight of an isocyanurate compound are added to 100 parts by weight of a vinyl chloride resin. A film having a thickness of 0.1 mm heat-processed after forming a film with a vinyl resin paste has a total light transmittance of 80% or more and a diffusion transmittance of
%, Having a haze of not more than 45%. 2. A vinyl chloride resin-coated sheet in which a woven or knitted fabric composed of synthetic fiber yarns is coated with a vinyl chloride resin paste, wherein the vinyl chloride resin paste used for coating is based on 100 parts by weight of the vinyl chloride resin. 30 to 60 parts by weight of a phthalate compound, 30 to 60 parts of a phosphate compound, and 10 to 30 parts by weight of an isocyanurate compound were subjected to heat processing after forming a film with the vinyl chloride resin paste. A 0.1 mm thick film has a total light transmittance of 80% or more and a diffuse transmittance of 4
A vinyl chloride resin-coated sheet characterized by having a property of 0% or more and a haze of 45% or less. 3. A vinyl chloride resin-coated sheet formed by weaving and weaving synthetic fiber yarns coated with a vinyl chloride resin paste, wherein the synthetic fiber yarns are yarns having flame retardancy and are used for coating. The resin paste was heat-processed after forming a film with the vinyl chloride resin paste.
A vinyl chloride resin-coated sheet, characterized in that a film having a thickness of m has a characteristic of a total light transmittance of 80% or more, a diffusion transmission coefficient of 40% or more, and a haze of 45% or less. 4. A vinyl chloride resin-coated sheet in which a woven or knitted fabric composed of synthetic fiber yarns is coated with a vinyl chloride resin paste, wherein the synthetic fiber yarns are yarns having flame retardancy, and The vinyl resin paste was heat-processed after forming a film with the vinyl chloride resin paste.
A vinyl chloride resin-coated sheet, characterized in that a film having a thickness of 1 mm has characteristics of a total light transmittance of 80% or more, a diffusion transmission coefficient of 40% or more, and a haze of 45% or less. 5. The vinyl chloride resin-coated sheet according to claim 1, wherein the synthetic fiber yarn is a yarn having flame retardancy. 6. A fluorine-based polymer containing a benzotriazole-based compound, a benzophenone-based compound, a salicylate-based compound or a compound obtained by combining a plurality of these compounds in a solid content of 0.1 to 20% by weight, at least 1 to 20 g / m ^{2 on} one surface. 6. The vinyl chloride resin-coated sheet according to claim 1, which is coated with the vinyl chloride resin sheet. 7. A copolymer of a fluorine-based polymer and an acrylate-based polymer containing a benzotriazole-based, benzophenone-based, salicylate-based compound or a compound obtained by combining a plurality of these compounds in a solid content of 0.1 to 20% by weight. The polymer composition is coated on at least one side in an amount of 1 to ²⁰ g / m ^2.
Or the vinyl chloride resin-coated sheet according to claim 4. 8. A blend of a fluorinated polymer and an acrylate polymer containing a benzotriazole-based compound, a benzophenone-based compound, a salicylate-based compound or a combination of a plurality of these compounds in a solid content of 0.1 to 20% by weight. The vinyl chloride resin-coated sheet according to claim 1, wherein the composition is coated on at least one surface in an amount of 1 to ²⁰ g / m2. 9. A composition having a benzotriazole-based, benzophenone-based, salicylate-based compound or a combination thereof in a side chain of an acrylate polymer at a ratio of 10 to 90 mol% on at least one surface. The vinyl chloride resin-coated sheet according to claim 1, which is coated in an amount of 1 to ²⁰ g / m2. 10. A composition comprising a benzotriazole-based compound, a benzophenone-based compound, a salicylate-based compound or a combination thereof in a ratio of 10 to 90 mol% in a side chain of an acrylate-based polymer, and a fluorine-based polymer. 1-20 g / m ^{2 on} at least one side of the copolymer composition
Claim 1, Claim 2, Claim 3, which is coated in an amount of
The vinyl chloride resin-coated sheet according to claim 4 or 5. 11. A composition comprising a benzotriazole-based compound, a benzophenone-based compound, a salicylate-based compound or a combination of a plurality of such compounds in a ratio of 10 to 90 mol% in a side chain of an acrylate-based polymer, and a fluorine-based polymer. 1 to 20 g /
Claim 1 is coated in an amount comprising of m ^2, claim 2, claim 3, claim 4 or vinyl-based resin-coated sheet chloride according to claim 5, wherein.