JP3389720B2 - Highly transparent flame-retardant film materials, exterior wall materials, roofing materials and agricultural houses - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film material made of a vinyl chloride resin having excellent flame retardancy and translucency, that is, a highly translucent flame retardant film material, an outer wall material, a roof material and an agricultural house. It is a thing.

2. Description of the Prior Art Conventionally, a soft vinyl chloride resin is coated on a fiber base cloth by various methods such as a calendering method, a coating method, and a T-die extrusion method, and is used for various events, warehouse tents, truck hoods and the like. It is used in various applications such as seats, agricultural houses, open-air seats, backlits, and flexible containers. Recently, it has been required to improve the lighting in outdoor sports facilities, to carry out various sports in a bright atmosphere, to reduce temperature control costs, to grow natural grass, and to demand highly translucent film materials. . Vinyl chloride resin has various advantages such as low cost, good handling such as processability, and easy high-frequency welder welding sewing, but due to long-term outdoor use, soot in the atmosphere,
Not only does it impair the aesthetics of film materials such as tents and sheets, because contaminants such as dust are easily attached and contaminated, and they cannot be removed even by wiping, and there is a serious drawback that the light-collecting properties are significantly reduced. The reason for this drawback is
It is said that various plasticizers added to improve the flexibility of the vinyl chloride resin migrate to the surface of the sheet, and the tackiness increases, so that stains are likely to be attached, and it is difficult to remove the stains.

Various methods have been proposed for the purpose of improving such pollution defects. For example, (1) coating with an acrylic or urethane resin dissolved in an organic solvent. (2) A method of laminating a polymethacrylic acid film on a vinyl chloride sheet as described in JP-A-56-167445. (3) A fluorine-based resin on a vinyl chloride sheet as described in JP-A-59-171649. However, the method (1) has almost no antifouling effect because the plasticizer is dissolved in the organic solvent of the coating resin or migrates to the coating resin layer. The method (2) cannot prevent migration of the plasticizer to the film layer, is not sufficient for long-term use, and has a weak welder weldability and is easily wrinkled. Although the method (3) has excellent antifouling properties, it has a serious drawback that it is expensive and cannot be welded or is very difficult.

Further, when various additives such as an ultraviolet absorber and a flame retardant are reduced or reduced in order to improve the daylighting property, the vinyl chloride resin is discolored by the light of ultraviolet rays or the fiber base cloth is deteriorated. In addition, there is a problem that weather resistance and flame retardancy are remarkably deteriorated such that flame retardancy, which is an essential function as an outdoor film material, fails.

However, on the contrary, in order to improve such drawbacks,
When a large amount of an organic weathering agent or flame retardant is added, the organic additive bleeds out on the surface of the vinyl chloride resin, causing a drawback of discoloration. In addition, from the perspective of translucency, the inorganic additives conventionally used for film materials are
It had a drawback that the translucency was significantly lowered.

That is, the vinyl chloride resin sheet which has improved translucency and antifouling property without impairing its properties has not yet been found.

[0006]

DISCLOSURE OF THE INVENTION According to the present invention, various properties of a vinyl chloride resin sheet are maintained and, at the same time, excellent flame retardancy and translucency are satisfied, and further, antifouling property is also excellent. Membrane material, that is, highly translucent flame retardant membrane material, outer wall material, roof material,
Furthermore, it intends to provide an agricultural house.

The present invention has the following constitution in order to achieve such an object.

That is, the highly translucent flame retardant film material of the present invention is
Oxidizing antimony average particle diameter of vinyl chloride resin as a flame retardant is 3 microns or more is contained, and, JIS
The total light transmittance defined by K7105 is 15% or more, and further, a skin having a surface hardness larger than that of the film material is bonded to at least one surface of the film material. It is characterized by. Also,
The outer wall material, the roof material, and the agricultural house of the present invention are characterized by being composed of such a highly translucent flame-retardant film material.

[0008]

The present invention has hitherto been technically considered to be extremely difficult to maintain various advantages of a vinyl chloride resin sheet and to impart excellent flame retardancy and translucency, let alone antifouling property. In view of the background, a thorough investigation has revealed that a film material having a high degree of flame retardancy and translucency at the same time can be obtained by using a specific flame retardant and by selectively using a specific particle size thereof. It has been clarified that excellent antifouling property can also be imparted by providing the surface of the film material with a skin having a surface hardness larger than the surface hardness of the film material. is there.

The vinyl chloride resin referred to in the present invention is a vinyl chloride polymer, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-acrylic acid ester copolymer, a vinyl chloride-vinylidene chloride copolymer, and the like. These may be used alone or in combination of two or more. Such vinyl chloride resin is mixed with an additive such as a plasticizer, a stabilizer, a filler, an antioxidant, a weatherproofing agent and a flameproofing agent. Among such additives, particles of the inorganic compound are Normally 0.2-1 μm
It was found that the presence of an inorganic compound having this particle size greatly contributes to the diffuse reflection of visible light, and that the light transmissivity is significantly reduced by adding a small amount. One of the features of the present invention is that a specific particle size of the inorganic compound is used. That is, in the present invention, the particle size of the inorganic compound particles blended as an additive is 0.2 μm.
Less than or greater than 1 μm, preferably less than 0.1 μm or 3 μm
It has the above particle size. Regarding such a particle size, there is a preferable particle size for each of the additives, which will be defined in the description below.

In the present invention, an antimony oxide having a specific size, that is, an average particle size of 3 μm or more, more preferably 3 to 7 μm, is used as the flame retardant, and a flame retardant used in combination with this is also preferable. , and it has the characteristics in that it contains at least one the boron zinc and zinc stannate, to compounding. It has been clarified that such a specific flame retardant can impart a high degree of flame retardancy while maintaining the translucency.

First, in order to impart flame retardancy to the antimony oxide while not hindering the light-transmitting property as much as possible, the relationship between the particle size of the antimony oxide and the hiding property is analyzed.
It was determined that the film having a thickness of 2 to 0.8 μm has the highest hiding property and lowers the translucency of the sheet. That is, in antimony oxide, the larger the particle size,
The translucency is improved. That is, by adopting antimony oxide having such a particle size, flame retardancy can be imparted without significantly reducing the transparency of the vinyl chloride resin. As such antimony oxide,
Examples include antimony trioxide, antimony tetroxide, and antimony pentoxide. Such antimony oxide is preferably used in an amount of 6 parts by weight or more, more preferably 7 to 10 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
It is good for achieving the above-mentioned effects of the present invention.

Zinc borate is, for example, 4ZnO.6.
B2 O3 · 7H2 O, 2 ZnO · 2B2 O3 · 3H2 O
Compounds such as the compounds represented by are represented by the above, and the compounds exemplified above are preferably used because of their flame retardancy and heat resistance. In addition, zinc stannate is ZnS
It is a compound represented by nO3.

The compounding amount of such a compound is preferably 2 parts by weight or more, and more preferably 3 to 7 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Such flame retardants can be used in a mixture, and it is preferable to mix them with antimony oxide and at least one of zinc borate and zinc stannate from the viewpoint of the flame retardant effect, and the composition of such a mixture. Is preferably 0.1 to 1 of at least one of zinc borate and zinc stannate with respect to 1 antimony oxide, and more preferably 0.3 to 0.8 of the latter with respect to 1 of the former. .

In the present invention, titanium oxide is contained in order to impart an ultraviolet shielding effect. At that time, the average particle diameter is preferably 0.05 μm or less, more preferably 0.03 μm.
Adopt a specific titanium oxide of m or less. By adopting such a particle size, it is possible to impart an ultraviolet shielding effect without significantly deteriorating the transparency of the vinyl chloride resin, and at the same time, it is possible to prevent coloring of the vinyl chloride resin and deterioration of the physical properties. Achieve the effect. Such titanium oxide is preferably added in an amount of 0.5 to 3 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the ultraviolet absorber of the present invention include triazole type ultraviolet absorbers such as 2- (2'hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole and 2- (. 5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2'hydroxy-3'-t-amino-5'-isobutylphenyl)
-5-chlorobenzotriazole, 2- (3,5-di-
t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2-
(2'hydroxy-5'-methylphenyl) benzotriazole, 2- (2'hydroxy-5'-methylphenyl) 5,6-dichlorobenzotriazole, 2- (2 '
Hydroxy-5'-methylphenyl) 5-ethylsulfone benzotriazole, 2- (2'hydroxy-3'-
Isobutyl-5'-methylphenyl) 5-chlorobenzotriazole, 2- (2'hydroxy-3'-isobutyl-5'-propylphenyl) 5-chlorobenzotriazole, 2- (2'hydroxy-3 ', 5' -Di-t-
Butylphenyl) benzotriazole, 2- (2'hydroxy-5'-1,1,3,3-tetramethylbutylphenyl) benzotriazole and the like can be used, and examples of the benzophenone-based ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4 '
-Dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone, 2,2 ', 4,4'-
Tetrahydroxybenzophenone or the like can be used, and as the hydroquinone ultraviolet absorber,
For example, hydroquinone, hydroquinone disalicylate, acrylate ultraviolet absorbers such as 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, and salicylic acid. As the system ultraviolet absorber, phenyl salicylate, paraoctyl phenyl salicylate, etc. can be used. These ultraviolet absorbers can be used alone or in combination,
In addition, these ultraviolet absorbers are used for the vinyl chloride resin 10
The amount is preferably 0.3 part by weight or more, more preferably 0.5 to 2 parts by weight, based on 0 part by weight.

The ultraviolet absorber of the present invention can further improve the weather resistance when used in combination with the above-mentioned titanium oxide. In particular, the ultraviolet absorber plays an extremely important role in the production of a system in which fine particles such as titanium oxide and antimony oxide that reduce the translucency are not added at all, that is, in the case of producing a vinyl chloride resin sheet having excellent transparency. In that case, 2 of the UV absorbers
From-(5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate It is preferable to use at least one selected or a mixture thereof. In particular, a combination of 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2-ethylhexyl-2-cyano-3,3-diphenylacrylate is preferably used. Each of these is preferably used in an amount of 0.5 to 1 part by weight with respect to 100 parts by weight of the vinyl chloride resin, and effectively functions to prevent deterioration and coloring of the vinyl chloride resin.

As the light stabilizer used in the present invention, a hindered amine light stabilizer can be used. Examples of such a light stabilizer include dimethyl succinate.
-(2-hydroxylethyl) -4-hydroxy-2,
2 ', 6,6'-Tetramethylpiperidine polycondensate, poly [(6- (1,1', 3,3'-tetramethylbutyl) amino-1,3,5-triazine-2,4diyl)
(2,2,6,6-Tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], bis (2,2,6,
6-tetramethyl-4-piperidyl) sebacate, 1-
[2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -4- (3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) -2,2,6,6-tetramethylpiperidine and the like can be used. Such a light stabilizer has an effect of capturing radicals and preventing deterioration of the vinyl chloride resin. The light stabilizer is used in an amount of preferably 0.1 part by weight or more, and more preferably 0.2 to 0.5 part by weight, based on 100 parts by weight of the vinyl chloride resin.

The following additives can be used in the vinyl chloride resin of the present invention.

That is, as stabilizers and stabilizing aids, for example, calcium-zinc system, calcium-zinc organic composite system, barium-zinc system, cadmium-barium system,
Cadmium / lead type, epoxy type, organic tin laurate, organic tin mercaptite, organic tin octyl and the like can be used, and these are used alone or in combination. The compounding amount at that time is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-methylenebis (6-t-butyl-4-ethylphenol),
Phenolic antioxidants such as 2,6-di-t-butyl-p-cresol, di-n-dodecyl-thiodipropionate, di-n-octadecyl-thiodipropionate, dilaurylthiodipropionate The thiodipropionic acid ester and the like can be used, and these can be used alone or as a mixture, and these are preferably 0.01 to 100 parts by weight of the vinyl chloride resin.
-2.5 parts by weight are compounded.

Further, the following additives can be used within a range that does not impair the effects of the present invention.

As the flame retardant, inorganic compounds such as titanium phosphate, aluminum hydroxide and magnesium hydroxide, and 2,4,5,6-tetrachloroisophthalonitrile, 10,10 'oxybisphenoxyarsine, etc. The antifungal agent, phthalocyanine blue, phthalocyanine glane, alizarin lake, zinc white, coloring agents such as carbon black and the like can be used. It should be noted that compounds other than those exemplified here may be added if necessary.

The vinyl chloride resin referred to in the present invention is a vinyl chloride polymer, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-acrylic acid ester copolymer, a vinyl chloride-vinylidene chloride copolymer, or the like. These may be used alone or in combination of two or more. The vinyl chloride resin has an average degree of polymerization of preferably 600 to 3500, more preferably 800 to 2500.

As the plasticizer used for the vinyl chloride resin, those generally used can be used. For example, as the phthalate ester, dibutyl phthalate, diethyl phthalate, dihebutyl phthalate, Di-2-ethylhexyl phthalate, di-n
-Octyl phthalate, dinonyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate and the like, and as the aliphatic dibasic acid ester, dimethyl adipate, diisobutyl adipate, dibutyl adipate, di-2-ethylhexyl adipate, diisodecyl adipate. , Dibutyl diglycol adipate, di-2-ethylhexyl azelate, dimethyl sebacate, dibutyl sebacate, di-2-ethylhexyl sebacate, methyl acetylricinoleate, etc., and as the epoxy type, epoxidized soybean oil, octyl epoxy Examples of the phosphoric acid ester-based compound include stearate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, and the like. Riboxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc. As the polyester type, adipic acid and esterified glycols such as 2-methyl-1,8-octanediol, 1,2-propanediol, 1,3-butanediol, 2-ethylhexanol and n-octanol are esterified. The trimellitic acid type is tri-2-ethylhexyl trimellilate, triisodecyl trimellilate, etc., and the other is pyromellitic acid type such as 2-ethylhexylpyromellilate, biphenyl tetracarboxylic acid ester type, etc. Exemplify Bets can be, these those singly or in combination are used.

In the case of a soft vinyl chloride resin, such a plasticizer is preferably used in an amount of 30 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. In addition, an ethylene-vinyl acetate copolymer used as a so-called non-plasticizer,
Ethylene-acrylic acid ester copolymers and ELVALOY (manufactured by Mitsui DuPont Polychemical Co., Ltd.) into which carbon monoxide is introduced can also be used,
In this case, it is preferably used in an amount of 50 to 120 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

The highly translucent flame-retardant film material of the present invention is usually called a soft type, and as a plasticizer, di-2-ethylhexyl phthalate (DO) which is generally used is used.
In the example of P), the blending amount is 10% vinyl chloride resin.
It is preferably 40 to 100 parts by weight, more preferably 50 to 70 parts by weight, based on 0 parts by weight.

The soft vinyl chloride resin is extremely prone to soiling due to various contaminants adhering to the surface thereof, especially when it is used outdoors for a long period of time. It is considered that pollutants are likely to adhere and the adhered contaminants are hard to be removed because they exude and increase in tackiness. For example, conventionally, for flame retardation of vinyl chloride, it is common to use a flame retardant, for example, antimony oxide, in combination with a flame retardant plasticizer such as tricresyl phosphate. In order to impart stain resistance, a method of joining the epidermis as described later is adopted. However, in order to maintain the antifouling property of the epidermis for a long period of time, it is preferable to prevent softening due to migration of the plasticizer from the film material as much as possible. That is, conventionally used flame retardant plasticizers have a violent migration property and impair the translucency and antifouling properties. Further, the flame retardant plasticizer has a drawback that when it is used in combination with a polyester-based plasticizer, a trimellitic acid ester-based plasticizer, or a pyromellitic acid ester-based plasticizer, migration is further increased.

In view of the above-mentioned cause, therefore, in the present invention, there is a difference in the degree of stain between the types of plasticizers having different bleeding degrees and the non-plastic type that uses solid plasticizers without bleeding. In consideration of this, various experiments were conducted with the surface hardness of the sheet almost the same, and the fact that there was almost no difference in the stain resistance between the plasticizer type and the non-plasticizer type was confirmed, and the seepage of the plasticizer was not the main factor. As a result of further investigation, it was discovered that the surface hardness of the sheet remarkably affects the antifouling property, that the hard surface is hard to stain, and the adhered stain is easily removed by wiping.

The present invention has a surface hardness higher than that of a vinyl chloride resin in which the film material is used on the surface of a highly transparent flame-retardant film material (hereinafter simply referred to as a film material) made of a soft vinyl chloride resin. The present invention completes a laminated sheet excellent in antifouling property with a vinyl chloride resin 100% system, which is characterized by joining a skin (hereinafter, simply referred to as a skin) made of a vinyl chloride resin having a large size.

According to the present invention, the surface hardness of the film material and the surface skin is DUH, a Shimadzu dynamic micro hardness tester manufactured by Shimadzu Corporation.
-200 type, using triangular pyramid indenter 115 °, temperature 25
The dynamic hardness value measured under the conditions of a load of 0.1 mg, an indentation rate constant of 10 and a holding time of 5 seconds under an atmosphere of ℃ and a humidity of 65% RH is preferably 0.2 or less for the film material, and the skin is preferable. Is more than 0.2. The film material is a conventional soft vinyl chloride resin, and is generally used as a plasticizer for di-2-ethylhexyl phthalate (DO).
In the example of P), the addition of 40 parts by weight to 100 parts by weight of vinyl chloride resin is about 0.2, and the hardness is 0.15 or less in consideration of the flexibility required for the film material. . The hardness of the skin, which obviously improves the antifouling property, is preferably 0.2 or more, more preferably 0.35 or more, higher than that of the film material with respect to the contamination property of the film material. Further, when the hardness of the surface skin is preferably 0.5 or more, more preferably 0.6 or more, an extremely excellent antifouling function is exhibited. The present invention can use a sheet composed only of a resin having a surface hardness of 0.5 or more, but since such a sheet has low flexibility, it is difficult to use for a tent, a truck hood, etc. Will be extremely limited. In the field of application utilizing the flexibility of vinyl chloride resin, it is preferable to use a conventional soft sheet having a high hardness film laminated on the surface thereof.

The amount of plasticizer of the laminated sheet of the present invention is such that the skin is smaller than that of the film material. For example, when the amount of plasticizer is 100 parts by weight of vinyl chloride resin, when the plasticizer is the same, Di-2-ethylhexyl phthalate (D
In OP), when the film material is 50 parts by weight, the skin is preferably 35 parts by weight or less, more preferably 30 parts by weight or less. When the plasticizer is tetraoctylpyromellimate, the skin is preferably 4 parts by weight when the film material is 65 parts by weight.
It is 5 parts by weight or less, more preferably 40 parts by weight or less.

In the present invention, the types of plasticizers for the film material and the epidermis may be different. In this case, when a pyromellitic acid ester type, a trimellitic acid ester type, or a polyester type is used for the film material, it is preferable to use a phthalic acid ester type for the epidermis. For example, tetraoctylpyromellimate is used for the film material. A sheet is used when the amount of di-2-ethylhexyl phthalate (DOP) in the skin is 65 parts by weight, preferably 35 parts by weight or less, more preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less. With such a sheet, it is possible to exert excellent antifouling property without being easily influenced by environment such as temperature and humidity.

In the present invention, instead of the above-mentioned plasticizer, ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer as a plasticizing component, and ELVALOY (DuPont Mitsui Polychemical Co., Ltd.) in which carbon monoxide is introduced into these copolymers. Polymers for plastics such as chlorinated paraffin can be used. If the non-plasticizing polymer is used, there is no need to worry about the migration of the plasticizer described above. For example, when ELVALOY-HP533 (ethylene-alkyl acrylate copolymer system) is used, when 100 parts by weight of the non-plasticizing polymer is mixed with 100 parts by weight of vinyl chloride resin in the film material, On the epidermis,
The amount is less than that of the membrane material, preferably 70 parts by weight or less, more preferably 50 parts by weight or less. By adopting such a constitution, it is possible to exert the advantages that there is no migration of the plasticizer and the excellent antifouling property can be maintained.

In the present invention, the average degree of polymerization of the vinyl chloride resin of the film material is different from that of the vinyl chloride resin of the skin, and it is particularly preferable to use the one having a high polymerization degree for the skin. Originally, the higher the degree of polymerization, the higher the hardness, and the plasticizer has the property of migrating from the high degree of polymerization side to the low degree of polymerization side. It becomes easy to maintain hardness. The difference in the degree of polymerization between the two is preferably 300 or more, more preferably 500 or more.

The thickness of the epidermis of the present invention is preferably 5 to 3.
00μ, more preferably 10 to 100μ, and particularly preferably 30 to 50μ. Such a thickness can be determined according to the intended flexibility of the sheet of the product.

The film material of the present invention has a total transmittance value of 15 measured by a "direct reading haze computer apparatus" manufactured by Suga Test Instruments Co., Ltd. by the method specified in JIS K 7105.
% Or more, preferably 20% or more. Membrane materials commonly used in agricultural houses, sports facilities, and even event halls have too low a total transmission, eg 10% or less in the latter case, and a total transmission of 25% required for a natural lawn to grow. It is said that the total transmittance is 25 to 35% when playing sports such as tennis.

The value of the total transmittance is determined by the constitution of the laminated structure of the fiber base cloth, the membrane material and the skin, and the kind and the amount of the additive used for the membrane material and the skin. When calendered sheets are thermocompressed on both sides to make tarpaulin, and when the surface (the surface exposed to the outside air) is joined to the skin for imparting antifouling properties, the tarpaulin's front and back surfaces (inside the room) are chlorinated. A vinyl resin having different translucency may be used, or a completely transparent or semitransparent vinyl chloride resin having the same translucency may be used. The epidermis may be completely transparent or semi-transparent, and can be set according to the intended product. According to the invention 50 to 6
A film material having an extremely high transmittance of 0% is also possible.

The membrane material referred to in the present invention is often used as being reinforced with a fiber base cloth. Such a fiber base cloth is a knitted or woven fabric in which synthetic fibers such as polyester, polyamide and vinylon, and natural fibers such as cotton and hemp are used alone or in combination, and the fibers may be long fibers or short fibers. The fiber base cloth is subjected to a water repellent treatment and an adhesive treatment, if necessary.

The membrane material of the present invention is produced by bonding a vinyl chloride resin to at least one side of a fibrous base fabric to form a membrane material, and then joining the skin, or by joining the membrane material and the skin. It may be laminated on a fiber base cloth and is not particularly limited. In the production of the laminate, an adhesive method, a thermocompression bonding method, a laminator method, an extrusion laminator method and the like can be used, but the method is not limited to these. It is preferable to laminate a surface skin. Further, the surface of the laminated sheet may be treated with a pressured body having irregularities to shape the surface.

The present invention does not bond different types of polymer substances such as acrylic type and fluorine type to the surface of vinyl chloride resin as in the conventional improvement technique, but uses 100% vinyl chloride resin. Since a laminated sheet can be used, properties such as high-frequency weldability inherent in vinyl chloride resin are not impaired, and sewability and strength of the sewn part do not change, so handling and construction can be performed in the same manner as in the past.

The film material of the present invention can be effectively used not only as an outer wall material and a roof material, but also as an agricultural house using them.

[0043]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

The performance values shown in Examples and Comparative Examples were measured by the following method. "Outdoor exposure pollution test" The method was stipulated in JIS A 1410 and carried out for 360 days. "Stain-removing property" Those exposed outdoors were wiped off with a cotton cloth. "Staining property evaluation" The L value was measured by a digital colorimetric color difference calculator (manufactured by Suga Test Instruments Co., Ltd.) on the surface of the sheet before the contamination, the sheet after the exposure, and the sheet after the stain after the exposure was wiped off with a cotton cloth, and the following values were measured. Degree of contamination Deterioration of dirt was obtained by a calculation formula.

Contamination degree X = (A−B) / A × 100 Contamination removal property Y = (A−C) / A × 100 where A: L value of the sheet before the contamination test B: Sheet after the outdoor exposure L value of C: L value after wiping off the stain on the sheet after outdoor exposure with a cotton cloth. The larger the X value is, the more severe the stain is, and the smaller the Y value is, the easier the stain is to be removed. Shows up. "Surface hardness" The surface of the sheet is made by Shimadzu Corporation Shimadzu dynamic ultra-fine hardness meter DUH-200 type triangular pyramid indenter 115
At 25 ° C. and 65% RH, and a load of 0.
The measurement was performed under the conditions of 1 mg, indentation rate constant 10 and holding time 5 seconds. The higher the number, the harder it is. “High-frequency adhesive strength” Based on JIS K 6328, it was measured with a width of 3 cm by a method defined by the Membrane Structure Association of Japan, and displayed as a numerical value per 3 cm width (Kg). The welding process was performed using a KM4000TA type device manufactured by Seidensha Denshi Kogyo Co., Ltd., with a 4 KW output and a pressure of 2 Kg / cm @ 2 for a processing time of 6 seconds. “Creep resistance” Based on JIS K 6859, evaluation was carried out after treatment at 60 ° C. for 6 hours according to the method specified by the Membrane Structure Association.

The one that has no change is defined as "abnormal", and the one in which the joint is partially or completely peeled off is "abnormal"
And "Transmittance" Based on JIS K 7107, the total transmittance was measured by a "direct reading haze computer device" manufactured by Suga Test Instruments Co., Ltd.

Total transmittance (%) = (amount of transmitted light / amount of incident light) × 100 “flame retardancy” Measured by “45 ° Meckel burner method” of JIS A 1322, and the performance was displayed as a grade. Membrane materials for construction specified by the Membrane Structure Association are "flameproof class 2" or higher,
Those that pass it will be displayed as "first grade" and "second grade",
Those that failed were classified as "out of grade". "Weather resistance" According to the regulations of the Membrane Structure Association of Japan, after treating it with a sunshine weatherometer at 63 ° C for 2000 hours, measure the tensile strength by the method specified in JIS K 6730, and hold it strong against those not irradiated. The rate was calculated. The membrane material for construction, which is defined by the Membrane Structure Association, has a strength retention of 80% or more and is passed. In addition, the degree of coloring was visually judged, and those with no coloring were marked with ◯, those with some coloring were marked with Δ, and those with significant coloring were marked with x. Examples 1 to 19 and Comparative Examples 1 to 8 Plain woven fabrics using polyethylene terephthalate fiber (made by Toray Industries, Inc.) of 96 denier and 96 filaments as warp and weft were scoured, dried and heat set by a conventional method. The total transmittance of this woven fabric was 61%.

Vinyl chloride resin layers having a thickness of 0.2 mm were formed on both sides of the woven fabric, and the resin compositions on the surface of the film material in Table 1 and on the back surface of the film material in Table 2 were subjected to a calendar method at a temperature of 180 ° C. A coating was applied to produce a membrane material. Here, the surface exposed to the outside air is the front surface, and the indoor side is the rear surface.

Next, a film made of the skin resin composition shown in Table 3 was thermally laminated at the temperature of 170 ° C. on the surface side of the film material.

The breakdown of each component used for each resin composition is shown below. (A) Vinyl chloride resin average degree of polymerization a. 1000 a. 1650 (B) Plasticizer c. Di-2-ethylhexyl phthalate d. Adeka Sizer PN1430 (polyester plasticizer manufactured by Asahi Denka Kogyo Co., Ltd.) e. Adeka Sizer UL80 (Pyromellitic acid plasticizer manufactured by Asahi Denka Kogyo Co., Ltd.) Ka. ELVALOY-HP533 (Olefin plasticizer manufactured by Mitsui Dupont Polychemical Co., Ltd.) (C) Antimony oxide a. Antimony trioxide (average particle size 0.5 μm). Antimony trioxide (average particle size 3 μm). Antimony trioxide (average particle size 7 μm) (D) Titanium oxide? The average particle size is 0.2 μm. Average particle diameter 0.03 μm (E) UV absorber a. Tinuvin P (benzotriazole type manufactured by Japan Ciba-Geigy Co., Ltd.) b. Tinuvin 320 (benzotriazole-based Ciba-Gaigy Co., Ltd.) c. Ubinal N539 (cyanoacrylate-based BAS F Japan Co., Ltd.) (F) Light stabilizer d. Kimasorb 944 (manufactured by Nippon Ciba-Geigy Co., Ltd.) (G) Flame retardant e. Zinc stannate 4ZnO.6B2 O3 .7H2 O f. Zinc borate ZnSnO3 Further, the following various stabilizers were added to all vinyl chloride resins.

Epoxidized soybean oil 2.0 parts by weight Ba / Zn-based stabilizer 2.5 parts by weight Dibutyltin dilaurate-based stabilizer 0.2 parts by weight Here, parts by weight means 100 parts by weight of vinyl chloride resin. Represents the amount added.

The contents of the display in Tables 1 to 3 are as follows.

Degree of Polymerization: Those used are indicated by A and B.

Plasticizer: The type used is indicated by C, D, E, and C, and the addition weight part to 100 parts by weight of the vinyl chloride resin is shown numerically.

Sb: represents antimony oxide, and the types used are (a), (i), and (u), and the vinyl chloride resin 1
Numerical values are shown for the added weight parts relative to 00 weight parts.

ZB: Zinc borate, which is a numerical value indicating the added weight part to 100 weight parts of vinyl chloride resin.

ZS: Zinc stannate, which is a numerical value indicating the added weight part to 100 weight parts of vinyl chloride resin.

Ti: Titanium oxide, the type of which is
In (i), the added weight part is shown numerically with respect to 100 weight part of vinyl chloride resin.

UV absorber: The type used is a, b, c
The added weight parts are shown numerically with respect to 100 weight parts of the vinyl chloride resin.

Light stabilizer: Numerical values show the added parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

Thickness: The thickness of the film is shown numerically. The unit is μm.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

Table 4 shows the results of evaluating various performances. As a comparative example of the skin layer, a vinylidene fluoride film having a thickness of 20 μm was adhered with an adhesive.

[0066]

[Table 4]

From Table 4, the examples are capable of maintaining the high-frequency welding characteristics of the vinyl chloride resin, achieving both flame retardancy and translucency, and also having excellent antifouling properties and weather resistance. It can be seen that the film material is made of vinyl chloride resin.

Example 20 When the highly translucent flame-retardant film material made of the vinyl chloride resin of Examples 1 to 19 was used as an outer wall material and a roof material, respectively, the translucency shown in Examples 1 to 19 was obtained. It had flame retardancy and antifouling properties, and had excellent characteristics that its effects did not change in a durable manner. In addition, the agricultural house using these film materials as the outer wall material and the roof material, respectively, was extremely effective in cultivating plants and was excellent in durability.

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EFFECTS OF THE INVENTION According to the present invention, while maintaining various characteristics of the vinyl chloride resin sheet, excellent transparency, flame retardancy, and
Further, since a film material having excellent antifouling property can be provided, it is possible to provide a material suitable for various applications, particularly an outer wall material or a roof material, and particularly an excellent agricultural house.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI D06M 11/45 D06M 15/248 11/46 11/00 Z 11/47 // D06M 15/248 (56) References 6-1862 (JP, A) JP 5-331338 (JP, A) JP 6-279639 (JP, A) JP 59-152944 (JP, A) JP 63-89569 (JP, A) Actual development Sho 50-142787 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 5/00-5/24 B32B 1/00-35/00 C08L 1/00- 101/16

Claims (18)

(57) [Claims] 1. A oxide antimony average particle diameter as a flame retardant vinyl chloride resin is 3 microns or more is contained, and the total light transmittance defined in JIS K 7105 is not less than 15% Characteristic high translucent flame retardant film material. 2. The average particle size of the antimony oxide is 3 to.
The highly transparent flame-retardant film material according to claim 1, which has a thickness of 7 microns. Wherein said content of oxidizing antimony is at 6 parts by weight or more is based on 100 parts by weight of the vinyl chloride resin according to claim 1 or 2 high light flame-retardant film material according. As claimed in claim 4, wherein said flame retardant, at least one zinc borate and zinc stannate are contained, and the content of the claims 1-3 for at least 2 parts by weight per 100 parts by weight of a vinyl chloride resin The highly transparent flame-retardant film material according to any one of claims. 5. A said antimony oxide, the mixing ratio of the at least one selected from zinc borate and zinc stannate are 1 /
The highly translucent flame-retardant film material according to claim 4, which is 0.1 to 1/1. On at least one surface according to claim 6 wherein said high light flame-retardant film material, according to claim 1 epidermis consisting of larger vinyl chloride resin surface hardness than the membrane material, characterized in that it is joined ~
7. A highly translucent flame-retardant film material according to any one of 7 . 7. A surface hardness of the skin is 115 ° of a triangular pyramid indenter of Shimadzu dynamic ultra-fine hardness meter DUH-200 manufactured by Shimadzu Corporation, and the load is 0 at an temperature of 25 ° C. and a humidity of 65% RH. 1 mg, indentation speed constant 10, holding time 5
Sec and a dynamic hardness of 0.5 or more as measured under the conditions of claim is greater than 0.2 relative to the film material 6
The highly transparent flame-retardant film material described. 8. The vinyl chloride resin constituting the film material and the surface skin contains a plasticizer, and the amount of the plasticizer is 5 parts by weight or less in the surface skin than in the film material.
7. The highly transparent flame-retardant film material according to 7 . 9. The plasticizer blended in the film material and the epidermis,
Different types, the plasticizer blended in the film material is at least one selected from polyester plasticizers, pyromellitic ester plasticizers and trimellitic acid ester plasticizers, and is blended in the skin. The highly translucent flame-retardant film material according to claim 8 , wherein the plasticizer is a phthalate ester plasticizer. 10. A plasticizer formulated in the membrane material and epidermis is, et styrene - vinyl acetate copolymer, ethylene - acrylic acid ester copolymer and made by introducing them into carbon monoxide copolymer The highly translucent flame-retardant film material according to claim 8, which is at least one selected from the group consisting of: 11. The average degree of polymerization of the vinyl chloride resin of the skin is 300 or more higher than that of the film material .
10. The highly translucent flame-retardant film material according to any one of 10 . 12. The method according to any one of claims 1 to 11 ,
A highly transparent flame-retardant film material containing 0.5 to 3 parts by weight of titanium oxide having an average particle diameter of 0.05 μm or less based on 100 parts by weight of a vinyl chloride resin. 13. The method according to any one of claims 1 to 12 ,
A highly transparent flame-retardant film material containing an ultraviolet absorber in an amount of 0.3 parts by weight or more based on 100 parts by weight of a vinyl chloride resin. 14. The method according to any one of claims 1 to 13 ,
Vinyl chloride resin 100 with hindered amine light stabilizer
A highly translucent flame-retardant film material containing 0.1 part by weight or more based on parts by weight. 15. membrane material, high light-transmissive flame-retardant film material according to any one of claims 1 to 14 which is a laminate of a fiber base fabric. 16. An outer wall material comprising the highly translucent flame retardant film material according to any one of claims 1 to 15 . 17. A roofing material comprising the highly translucent flame-retardant film material according to any one of claims 1 to 15 . 18. An outer wall material according to claim 16 and a claim.
An agricultural house comprising the roofing material according to item 17 .