JP2003147685A - Resin-coated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-coated sheet excellent in flame retardant property, waterproof property, soil-preventing property, endurance and sewing property, without containing a halogen such as chlorine, bromine, and exhibiting less environmental pollution. SOLUTION: This resin-coated sheet is a fibrous cloth whose both surfaces are coated with a thermoplastic resin and only one of the surfaces contains a flame retardant, and is characterized by exhibiting the flame retardant property of exhibiting <=5 sec flame-remaining time, <=20 sec dust-remaining time and <=40 cm carbonized area by a flame retardant test as described in the paragraph 3, article 4 of enforcement regulation of the Fire Services Act, and also exhibiting <=5 sec flame-remaining time, <=1 min dust-remaining time and <=10 cm carbonized length by a flame retardant test regulated in the JIS A 1322.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fat-coated sheet which is lightweight, flexible, excellent in flameproofness / waterproofness, durable, antifouling, and low in environmental pollution.

[0002]

2. Description of the Related Art Conventionally, a waterproof cloth obtained by coating a vinyl cloth with a vinyl chloride resin by a calendering method, an extrusion laminating method, or a coating method or a dipping method has been used as a tarpaulin for industrial materials.
Widely used for various purposes such as tents and truck hoods.

The reason why vinyl chloride resin-coated base fabrics are widely used is that they are derived from the characteristics of vinyl chloride resins, and because they contain halogen elements, they are easily flame retarded. The processability is excellent, various processing methods can be adopted, flexibility can be arbitrarily adjusted with a plasticizer, and high-frequency welder bonding processing and hot air welding processing can be easily performed for the reasons.

As described above, the vinyl chloride resin has many advantages, but since the vinyl chloride resin contains a chlorine element, it is said that toxic gases and smoke containing halogen and residue are generated at the time of waste incineration after use. Since it has serious drawbacks and some of the plasticizers are listed as target substances of environmental hormones (endocrine disruptors), which have recently been regarded as a problem, when used in truck hoods, etc. There is also a growing concern over adverse effects on health through products, and there is a strong demand for the development of products with resin compositions that do not contain halogen elements for the purpose of environmental protection and safety from a global environmental scale.

From this point of view, as a resin other than vinyl chloride resin, an olefin resin, a polyester resin, a polyamide resin, a urethane resin, etc. are being investigated for commercialization, but they are excellent in vinyl chloride resin. Flame retardant,
In the field where sewability and durability are required, for example, in the field of seats such as tents and waterproof cloths, satisfactory products have not been proposed.

In such applications, afterflame time of 5 seconds or less, dust time of 20 seconds or less, carbonized area of 40 cm or less, and JI
Afterflame time 5 according to the flameproof test method specified in SA 1322
It is necessary to have a high degree of flame retardancy such as a second or less, a residual dust time of 1 minute or less, and a carbonization length of 10 cm or less. When a conventional hydrous metal salt is used as a flame retardant, a resin is required to achieve the flame retardancy standard. With respect to 100 parts by weight, it is necessary to add 100 parts or more, which causes a significant decrease in the physical properties of the resin.
Deterioration of antifouling property, weather resistance and durability is inevitable. In addition to the effect of the addition of flame retardant on the physical properties of the resin, the sewability such as high-frequency welder and hot air welding is largely lower than that of the vinyl chloride resin due to the difference in the basic resin properties.

In recent years, in order to improve the above-mentioned drawbacks, a phosphorus compound, especially a phosphoric acid ester compound is used as a flame retardant in place of the hydrous metal salt, which is a liquid at room temperature. Since it is the mainstream and the addition amount can be reduced, when it is mixed with resin, it has relatively little effect on the physical properties of the resin, but since it is liquid, surface bleeding easily occurs, and bleeding causes adhesion to the resin surface. It has a drawback that stains tend to adhere, and that when the sheet is used outdoors, it is very susceptible to stains. Further, since the situation of adding the flame retardant to the resin does not change, deterioration of weather resistance and durability is inevitable.
In addition, there are some phosphoric acid ester compounds that are solid at room temperature, but most of them have low melting points of 150 ° C. or lower,
Since it melts into a liquid during resin molding, it has the same drawbacks.

Therefore, at the present time, it has both flameproof property, waterproof property, antifouling property, durability and sewability, and chlorine,
The reality is that a resin-coated sheet that does not contain halogen such as bromine and has little environmental pollution has not been proposed yet.

[0009]

In view of such background of the prior art, the present invention is flameproof, waterproof, sewable, stainproof, and
It is intended to provide a resin-coated sheet which has both durability and does not contain halogen such as chlorine and bromine and has little environmental pollution.

[0010]

The present invention employs the following means in order to solve the above problems. That is, the resin-coated sheet of the present invention is a sheet in which both sides of a fiber cloth are coated with a thermoplastic resin, and a flame retardant is contained in only one side thereof, and the flameproof performance thereof is the Fire Defense Law Enforcement Regulations Article 4 Afterflame time 5 seconds or less, afterglow time 20 seconds or less, carbonization area 40 cm or less by the flameproof test method described in 3, and afterflame time 5 seconds or less by the flameproof test method specified in JIS A 1322 Dust time less than 1 minute, carbonization length 10
It is characterized by being less than or equal to cm.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has the above-mentioned problems, namely, flameproofness, waterproofness, antifouling property, durability and sewability, and less environmental pollution that does not contain halogen such as chlorine and bromine elements. As a result of diligent studies on the resin-coated sheet, a sheet in which both sides of the fiber cloth were coated with a thermoplastic resin, and when a flame retardant was included in only one side, it was clarified that these problems could be solved all at once. is there.

In the resin-coated sheet of the present invention, the reason why the durability and antifouling property of the sheet are lowered is that the surface resin layer containing the flame retardant is exposed to light, heat, and wind and rain, so that the stain due to the bleeding of the flame retardant occurs. , And focusing on the fact that the addition of a flame retardant causes the deterioration of the durability due to the deterioration of the resin physical properties, the antifouling property and the flame retardant that causes the deterioration of the durability are removed from the surface resin layer, and it is necessary for flame retardation. By making the amount of the flame retardant unevenly distributed on the back surface which is not exposed to direct light, heat, and wind and rain, the flame retardancy, antifouling property and durability as a sheet are satisfied.

The resin-coated sheet of the present invention has a flameproof performance of 5 seconds or less afterflame, 20 seconds or less afterglow time, and 40 cm or less in carbonization area according to the flameproof test method described in Article 4-3 of the Fire Service Law Enforcement Regulations. In addition, according to the flameproof test method stipulated in JIS A 1322, the afterflame time is 5 seconds or less, the dust time is 1 minute or less, and the carbonization length is 10 cm or less. It is preferably used as a required waterproof cloth, tent, tent warehouse, truck hood, truck seat, container, curing sheet, partition film or curtain.

The use of the resin-coated sheet of the present invention is not particularly limited, including indoor use, but when used outdoors, the resin layer surface containing the flame retardant is directly exposed to feng shui. It is preferable to use the resin layer surface not containing the flame retardant on the indoor surface side which is not exposed and the outdoor surface side.

Examples of the flame retardant used in the present invention include halogen flame retardants such as bromine and chlorine, hydrous metal salts such as aluminum hydroxide and magnesium hydroxide, phosphorus flame retardants, silicon flame retardants and melamine cyanurate. Nitrogen-containing compounds and the like can be used, but phosphorus-based flame retardants are preferably used in consideration of flame retardant effects, environmental aspects, compatibility with resins, and the like. Among such phosphorus-based flame retardants, the compounds shown below are particularly preferably used.

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

Further, in the present invention, one or more kinds of such flame retardants can be used, and the addition amount thereof is based on the total weight of the thermoplastic resin excluding the fiber cloth of the resin coated sheet. Is preferably 15% by weight
The above content is more preferably 20% by weight or more, and particularly preferably 30 to 40% by weight.

However, in order to impart flame retardancy, it is more stable to use a large amount of flame retardant,
On the contrary, if added in excess, it adversely affects the adhesiveness and sewability.
The amount of the flame retardant added is 150 parts by weight or less, further 120 parts by weight or less, relative to 100 parts by weight of the thermoplastic resin,
Particularly, 100 parts by weight or less is preferable.

As the thermoplastic resin of the present invention, a resin containing no halogen compound such as chlorine or bromine is used in order to prevent or suppress environmental pollution. As such a thermoplastic resin, urethane resin, polyester resin, olefin resin, polyamide resin and the like are preferably used in terms of processability, flexibility and the like.

As the urethane resin, for example, polyurethane obtained by reacting an organic diisocyanate, a linear diol and a chain extender is preferably used.

As such an organic diisocyanate, an alicyclic organic diisocyanate, an aliphatic organic diisocyanate, an aromatic organic diisocyanate or the like can be used, and as the linear diol, a polyester diol, a polyether diol or a polyamide can be used. Ester-based diols, polycarbonate-based diols and the like can be used, and as the chain extender, compounds containing two or more active hydrogens such as low-molecular glycols, low-molecular diamines and low-molecular amino alcohols must be used. You can

As the polyurethane, it is also possible to use a mixture or a copolymer of two or more of the above polyurethanes.

Next, as the polyester resin, a copolymer of two or more kinds of aromatic dicarboxylic acids and / or aliphatic carboxylic acids and two or more kinds of alkylene glycols can be used. Also, a mixture of two or more of the above may be used.

As the polyolefin resin,
Polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-alkyl acid alkyl ester copolymer, ethylene-methacrylic acid alkylene ester copolymer, ethylene-vinyl acetate copolymer and the like can be used, as the olefin resin, Mixtures of two or more of the above may also be used.

Examples of the polyamide resin include polyamide 6, polyamide 66, polyamide 11, polyamide 12 and the like, and aliphatic polyamide resins such as copolyamide obtained by copolymerizing these polyamides, aromatic polyamide resins and modified polyamides. Resins, polyamide elastomers, etc. can be used, and as the polyamide resin, a mixture of two or more kinds can be used.

Among these resins, urethane-based resins are preferably used in terms of durability and weldability, and among them, polycarbonate-based polyurethane is used from the viewpoints of weather resistance, hydrolysis resistance, flexibility, weldability and the like. Those mainly composed of are preferably used.

The urethane resin may be used in the form of pellets or dissolved or dispersed in a solvent or water. Among them, the solvent-soluble type is preferable from the viewpoint of water resistance, film-forming property and film strength. Preferably used.

The thermoplastic resin of the present invention may contain at least one selected from ultraviolet absorbers, light stabilizers and colorants. As such a colorant, a commonly used pigment-based colorant is preferable in terms of compatibility and weather resistance. Further, as the ultraviolet absorber and the light stabilizer, those generally used can be used.

As such an ultraviolet absorber, a benzotriazole-based, benzophenone-based or triazine-based one can be used as a mixture of one or more kinds, and preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the resin. Added.

As the light stabilizer of the present invention, a hindered amine type compound or a hindered phenol type compound can be used, and preferably 0.1 to 100 parts by weight of the resin.
Add 3 parts by weight. In addition, an antioxidant, an antibacterial agent, or an antifungal agent may be added if necessary.

In the resin-coated sheet of the present invention, the adhered amount of the thermoplastic resin composition has a great influence on the weather resistance, durability, sewability and flame retardancy of the sheet, and particularly light, heat,
The amount of resin adhered to the surface layer exposed to wind and rain is very important, and in order to impart the weather resistance equivalent to that of vinyl chloride coated products, it is preferably 20 μm or more, more preferably 20 to 10
It is preferable to form a resin coating layer having a thickness of 0 μm or more, particularly preferably 30 to 50 μm. That is, 20μ
If it is thinner than m, the fibers may be deteriorated by ultraviolet rays or the waterproof property may become unstable. The adhesion amount of the resin layer containing the flame retardant on the back surface is determined by the resin type, the flame retardant type, and the surface layer resin adhesion amount, and can be set arbitrarily by a combination thereof.

In the resin-coated sheet of the present invention, at least one of the thermoplastic resin layers may be a film, and when the surface layer, which is a thermoplastic resin layer containing no flame retardant, is a film, The thickness is preferably 2
Those having a range of 0 μm or more, more preferably 20 to 100 μm, and particularly preferably 30 to 50 μm are used.
That is, if the thickness is less than 20 μm, the fibers may be deteriorated by ultraviolet rays and the waterproof property may become unstable.

The thermoplastic resin film may be formed by extruding the thermoplastic resin into a film with a T-die or a calendar roll and directly thermocompression-bonding it to a cloth.
In addition, after a film is produced by a known method such as T-die, calender roll or coating, the film can be attached via an adhesive.

In the present invention, any means may be adopted, but from the viewpoint of stability of the adhesive force, it is preferable to stack them via an adhesive. As such an adhesive, a solvent-based or water-based adhesive can be used, but a two-component urethane resin-based adhesive is preferably used from the viewpoint of adhesive properties. The amount of such an adhesive used is preferably in the range of 10 to 80 g / m ² , more preferably 40 to 70 g / m ² in terms of resin solid content. That is, when the amount of adhesive is less than 10 / m ² , the adhesive strength is insufficient,
It will also be inferior in durability.

From the viewpoint of improving the adhesiveness of the thermoplastic resin film, the adhesive force between the thermoplastic resin film and the fabric is
Preferably 2 kg / 2 cm or more, more preferably 3 k
It is preferably g / 2 cm or more from the viewpoint of durability of the laminated sheet. That is, if the adhesive force is less than 2 kg / 2 cm, peeling may occur due to external force depending on the intended use.

As the fiber material constituting the cloth of the present invention, synthetic fibers such as polyester fiber, polyamide fiber, polyacrylic fiber, polyethylene fiber, polypropylene fiber, polyvinyl alcohol fiber and natural fibers such as cotton, hemp and wool are used alone. Alternatively, a mixture of two or more kinds can be used, and, of course, in the present invention, a fabric made of a fiber material containing no halogen compound is also preferably used. Further, as the structure of the cloth, woven fabric, knitted fabric, non-woven fabric and the like can be used. Among them, the woven fabric made of polyester fiber is preferably used from the viewpoint of strength, dimensional stability and the like. . Further, such polyester fibers include long fibers,
Short fibers or a mixture of these can be used.

The polyester fiber referred to in the present invention is polyethylene terephthalate, polybutylene terephthalate or a polyester obtained by copolymerizing or blending a third component such as isophthalic acid, isophthalic acid sulfonate, adipic acid or polyethylene glycol. The fiber may be a flame-retardant fiber in advance.

The intrinsic viscosity of the polymer constituting the polyester fiber is preferably 0.65 or more, more preferably 0.8 to 1.0. Further, a high strength fiber having a fiber density of 1.38 g / cm ³ or more and a tensile strength of preferably 6 g / d or more, more preferably 7 to 9 g / d is preferable.

To impart flame retardancy to the polyester fiber, a flame-retardant compound is copolymerized at the time of polymerization of polyester, or a flame-retardant raw yarn blended at the time of polymerization or yarn formation, or after forming polyester fiber. Any of the methods of applying a flame-retardant compound by post-processing may be used, and a known flame-retardant polyester fiber may be used, but a polyester fiber obtained by copolymerizing a flame-retardant compound during polymerization of polyester. Is preferable from the viewpoint of stability of flame retardant performance.

As the polyester fiber, it is also possible to use a fiber which is flame-retarded in advance. In the case of such a flame-retardant polyester fiber, a method of copolymerizing a flame-retardant compound at the time of polymerizing polyester, or a flame-retardant raw yarn in which a flame-retardant compound is blended at the time of polymerization or spinning, or
After forming the polyester fiber, it can be produced by adopting any method of post-processing and adhering the flame-retardant compound. Among them, the polyester fiber obtained by copolymerizing the flame-retardant compound during the polymerization of polyester. Is preferable from the viewpoint of stability of flame retardant performance.

As the flame-retardant polyester fiber, 2
A functional phosphorus compound is copolymerized, and at least 85 mol% of repeating units are polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,
It is a polyester such as 6-naphthalate, and its repeating unit is preferably 0.1 in terms of phosphorus element.
It is a fiber made of a polymer in which a bifunctional phosphorus compound is copolymerized in the range of ˜1 wt%. The flame-retardant polyester may contain a copolymerization component within a range that does not impair flame retardancy. The intrinsic viscosity of the polymer of the flame-retardant polyester fiber is preferably 0.65 or more, more preferably 0.8 or more. More preferably, it is preferable to use a flame-retardant polyester fiber having a density of the flame-retardant fiber itself of 1.38 g / cm ³ or more.

As the above-mentioned bifunctional phosphorus compound, a phosphonate represented by the following formula (9), a phosphinate represented by the formula (10) or a phosphine oxide represented by the formula (11) is preferably used.

[0046]

[Chemical 9]

[0047]

[Chemical 10]

[0048]

[Chemical 11]

As the phosphorus compound represented by the formula (9),
Dimethyl phenylphosphonate, diphenyl phenylphosphonate and the like are preferably used.

As the phosphorus compound represented by the formula (10), (2-carboxyethyl) methylphosphinic acid,
Methyl (2-methoxycarbonylethyl) methylphosphinate, (2-carboxyethyl) phenylphosphinic acid, methyl (2-methoxycarbonylethyl) phenylphosphinate, (4-methoxycarbonylphenyl)
Methyl phenylphosphinate and ethylene glycol ester of [2- (β-hydroxyethoxycarbonyl) ethyl] methylphosphinic acid are preferably used.
Examples of the phosphorus compound of the formula (11) include (1,2-dicarboxylethyl) dimethylphosphine oxide and (2,3
-Dicarboxypropyl) dimethylphosphine oxide, (1,2-dimethoxycarbonylethyl) dimethylphosphine oxide, (2.3-dimethoxycarbonylethyl) dimethylphosphine oxide, [1,2di (β
-Hydroxyethoxycarbonyl) ethyl] dimethylphosphine oxide, [2,3 di (β-hydroxyethoxycarbonyl) ethyl] dimethylphosphine oxide and the like are preferably used.

Among these compounds, the compound of formula (3) has particularly good copolymerization reactivity with polyester,
Also, it is preferably used because of less scattering during the polymerization reaction.

The above-mentioned phosphorus compound is preferably 0.2 to 1.5 in terms of phosphorus element in the polyester polymer.
%, Particularly preferably 0.4 to 1.3% by weight. That is, if less than 0.2% by weight,
It is not preferable because the flame retardancy of the obtained fiber cloth decreases. On the other hand, if the amount of elemental phosphorus exceeds 1.5% by weight, defects such as physical properties of the raw yarn, particularly strength reduction, increase in shrinkage properties, and increase in manufacturing cost will appear.

The fiber cloth may be treated with a water repellent material, depending on the purpose.
An adhesive treatment, an antistatic agent treatment, a weathering agent, an antibacterial agent, an antifungal agent, etc. can be applied as a pretreatment.

In the flame-retardant fiber structure of the present invention, the surface of the resin-coated sheet can be subjected to a surface treatment such as a top coat or embossing in order to improve the antifouling property and scratch resistance.

The resin used for the top coat is not particularly limited as long as it does not contain a halogen element, but from the viewpoint of antifouling property and scratch resistance, it has a modulus higher than that of the thermoplastic resin used for the film. A high resin is preferable, and among them, a resin similar to the thermoplastic resin used for the film is preferable in terms of adhesiveness and sewing property.

Further, the thermoplastic resin has adhesiveness,
Additives such as silicon oxide, calcium carbonate, silicon, and cellulose can be contained within a range that does not impair the sewability.

The resin coating method in the present invention is not particularly limited, but the surface of the thermoplastic resin layer which requires weather resistance and stain resistance can be uniformly coated with a fiber cloth and has a smooth surface. A film laminate is preferable from the viewpoint of imparting properties, and a coating processing method is preferable on the back surface because a liquid flame retardant is added and the amount and composition thereof are changed.

As the coating method, a generally used processing method can be adopted. The resin solution is applied by a known processing method such as knife coating, kiss coating, comma coating, gravure coating, and the temperature is 100 to 160 ° C. The method of drying in the temperature range of is preferable.

Next, an example of a method for producing such a resin-coated sheet will be described.

First, a cloth is made by weaving a polyester fiber with a flat structure, and a urethane resin solution consisting of polyurethane, a phosphate ester flame retardant and a pigment is coated on the cloth with a knife coater and then dried. A flame retardant-containing resin layer is applied to the cloth.

Next, with respect to the film to be the thermoplastic resin layer, a polyurethane resin solution containing a polyurethane resin and a pigment is coated on a release paper with a comma coater and dried.

Next, the film described below is laminated on the cloth surface of the cloth provided with the above-mentioned flame retardant-containing resin layer. In such lamination, it is preferable that these films are laminated with an adhesive agent. Good in terms of durability and durability.

As such an adhesive, for example, a two-pack type adhesive whose main component is polyester polyurethane can be used. When applying this adhesive to each thermoplastic dendrite film, gravure coating,
Dry until surface is tacky. The laminating film thus treated with the adhesive is laminated on the cloth, and
The resin-coated sheet of the present invention is manufactured by pressing and rolling between 0 ° C. metal rolls, and then aging at 50 ° C. for 48 hours.

In such a manufacturing method, a coating means or an impregnating means may be adopted instead of the means for containing the laminating film.

[0065]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Various evaluations in the examples were measured by the following methods. (Flame retardancy A) Afterflame time, afterglow time, and carbonization area were measured by the flameproof test method described in Article 4-3 of the Fire Service Law Enforcement Regulations, afterflame time was 5 seconds or less, afterglow time was 20 seconds or less, carbonization. Those having an area of 40 cm or less and satisfying the passing level were marked with ◯, and those not satisfying the level were marked with x. The flame retardance was measured by immersing the work cloth in hot water at 50 ° C. for 30 minutes, drying it at 50 ° C. for 24 hours, and leaving it in a desiccator containing silica gel for 2 hours or more. (Flame retardancy B) Afterflame time, afterglow time, and carbonization length were measured by the flameproof test method specified in JIS A 1322. Afterflame time was 5 seconds or less, afterglow time was 1 minute or less, and carbonization length was 10 cm or less. Those that meet the second flameproof standard are indicated by ◯, and those that do not meet are indicated by x.

The flame retardancy was measured by pretreatment B method by immersing the work cloth in hot water at 50 ° C. for 30 minutes, leaving it in a dryer at 50 ° C. for 48 hours, and then in a desiccator containing silica gel for 2 hours. It carried out about what was left as above. (Waterproof property) Measured according to JIS L 1092 (A method a). (Anti-fouling property) A stain test was conducted for 180 days by the 45 degree outdoor exposure method specified in JIS A-1410, and the surface before and after contamination was measured with a digital colorimetric color difference meter (manufactured by Suga Test Instruments Co., Ltd.) The value was measured and the degree of contamination was calculated by the following calculation formula.

Contamination degree (%) = A / B × 100 Here, A is the L value after the contamination and B is the L value before the contamination, and the smaller the value of the contamination degree is, the more significant the contamination is. (Adhesive force) Using a high frequency welder welding machine (YF-7000A type manufactured by Yamamoto Vinita Co., Ltd.), 2 cm width × 65
After heating a metal mold having a length of cm to 105 ° C. and welding at an output of 7 KW, a current value of 1.5 A, a pneumatic pressure of 4 kg / cm ² , a welding time of 6 seconds and a cooling time of 2 seconds, JIS K-6328 (5 ．
Adhesive strength (kg / 2cm) based on the peel test method of 3.7)
The width) was measured. (Creep resistance) A sample was prepared by welding under the same conditions as the adhesive strength measurement.

Temperature: 60 ° C. Load: 13 kg / 3 cm Time: 24 hours Judgment: (No problem) O, (Break) X. (Weather resistance) An accelerated exposure test was carried out under the following conditions using a metal weather resistance tester (manufactured by Die Plow Intes Co., Ltd.).

Irradiation cycle Constant temperature irradiation treatment → Rainfall → Constant temperature and high humidity treatment Constant temperature irradiation treatment (8 hours) Illuminance: 80 mW / m ² (295 to 780 nm) Temperature: 63 ° C Humidity: 50% Rainfall (10 seconds) Constant temperature and high humidity treatment (4 hours) Temperature: 30 ° C. Humidity: 98% Irradiation time 192 hours (16 cycles) Sheets before and after such exposure are JIS L 1096 (6.
The tensile strength was measured based on 12.1 A method), and the strength retention was determined by the following calculation formula.

Strength retention rate (%) = A / B × 100 Here, A represents tensile strength after exposure, and B represents tensile strength before exposure.

Examples 1 to 15 and Comparative Examples 6 to 9 Polyester spun yarn No. 20 twin yarn (manufactured by Toray Industries, Inc.)
Weaving a plain weave with a warp / weft density of 54/48 yarns / inch by using the warp yarn and the 10th single yarn as the weft yarn (weight 220 g
/ M ² ), the woven fabric is a wax-based water repellent (Daiguard D-
A pad (80% squeezing ratio) was applied to a treatment liquid of 23D manufactured by Daikyo Kagaku Co., Ltd. (solid content: 40%) and dried at 120 ° C. for 2 minutes to obtain a treated cloth. The treated cloth is resin-coated in the following steps. The results of performance evaluation are shown in Tables 1 and 2. (Backside resin layer) After coating the following resin composition solution with a knife coater, it was dried at 160 ° C for 2 minutes to form a flame-retardant resin layer.

Resin Resin A: Polycarbonate polyurethane (solid content 25
% DMF solvent solution) Resin B: Aliphatic copolymer polyester resin (solid content 20)
% Anone-based solvent solution) Pigment: Solid content 40% White pigment added with 20 parts of resin solid content Flame retardant Flame retardant a: The following compounds were used.

[0074]

[Chemical 12]

Flame retardant b: The following compounds were used.

[0076]

[Chemical 13]

Flame retardant c: The following compounds were used.

[0078]

[Chemical 14]

Flame retardant d: The following compounds were used

[0080]

[Chemical 15]

(Surface Resin Layer) Preparation of Film A resin solution having the following composition was prepared, coated on a release paper with a comma coater, dried at 110 ° C., and heat-treated at 160 ° C. to produce a film.

Resin A: Polycarbonate polyurethane (solid content 25% DMF solvent solution) Resin B: Aliphatic copolymer polyester resin (solid content 20)
% Anone-based solvent solution) Pigment: Solid content 40% White pigment is added in a resin solid content ratio of 20 parts Resin film laminating method A laminating film stuck to release paper is coated with an adhesive having the following composition by gravure. After the adhesive is dried until it becomes tacky, it is superposed on the fiber cloth surface of the cloth on which the flame-retardant resin layer has been formed, and the pressure is kept between the metal rolls at 80 ° C. with a pressure of ² kg / cm ² , and then it is wound. Then, it was aged in the atmosphere at 50 ° C. for 48 hours.

Adhesive: Polyester polyurethane (solid content 50% ethyl acetate solvent solution) 100 parts, trifunctional isocyanate (solid content 75% ethyl acetate solvent solution) 15 parts, catalyst (chain extender solid content 75)
% Ethyl acetate solvent solution) was used.

Examples 16 to 23, Comparative Examples 1 to 5 Polyester spun yarn No. 20 yarn (manufactured by Toray Industries, Inc.)
Weaving a plain weave with a warp / weft density of 54/48 yarns / inch by using the warp yarn and the 10th single yarn as the weft yarn (weight 220 g
/ M ² ), the woven fabric is a wax-based water repellent (Daiguard D-
A pad (80% squeezing ratio) was applied to a treatment liquid of 23D manufactured by Daikyo Kagaku Co., Ltd. (solid content: 40%) and dried at 120 ° C. for 2 minutes to obtain a treated cloth.

Both sides of the treated cloth were coated with the resin composition shown below. The results of performance evaluation are shown in Table 1.
2 shows.

Resin Resin A: Polycarbonate type polyurethane (solid content 25
% DMF solvent solution,) Resin B: Aliphatic copolymer polyester resin (solid content 20)
% Anone-based solvent solution) Resin C: Polycarbonate-based polyurethane aqueous dispersion (solid content 35%) Resin D: Ethylene-vinyl acetate aqueous dispersion (solid content 40%) Resin E: Aliphatic copolymer polyester aqueous dispersion (25 %) Pigment: 20 parts of a white pigment having a solid content of 40% is added to 100 parts by weight of the resin solid content.

The flame-retardant solvent-dissolved solution was added as it was, but it was added as an emulsion of 40% to the aqueous dispersion.

Flame retardant a: The following compounds were used.

[0089]

[Chemical 16]

Flame retardant b: The following compounds were used.

[0091]

[Chemical 17]

Flame retardant c: The following compounds were used.

[0093]

[Chemical 18]

Flame retardant e: The following compounds were used

[0095]

[Chemical 19]

Example 24 A fiber cloth was treated in the same manner as in Comparative Example 1, and a resin composition containing a flame retardant a was coated on the surface resin layer in the same manner, and a 40 μ film of a polycarbonate polyurethane elastomer resin was formed on the back surface resin layer. A resin-processed cloth that was pressure-bonded while forming a film was prepared.

Comparative Example 10 A fiber cloth made of the above polyester spun yarn was mixed with vinyl chloride resin, dioctyl phthalate plasticizer, titanium oxide, heat stabilizer, antimony trioxide flame retardant, tricresyl phosphate flame retardant plasticizer, and UV absorption. Soak the cloth in a resin solution consisting of a chemical agent and mineral terpene and squeeze it with a mangle 180
Heat treatment was performed at 0 ° C. to prepare a resin-processed cloth having a resin adhesion amount of 320 g / m ² .

[0098]

[Table 1]

[0099]

[Table 2]

From the results of Tables 1 and 2, Examples 1 to 24 have smaller surface tackiness and excellent antifouling property than Comparative Examples 1 to 5 containing a flame retardant in the surface layer, and are coated with a conventional vinyl chloride resin. It can be confirmed that the antifouling property is also excellent in comparison with Comparative Example 10 described above.

Further, in Comparative Example 10, since the vinyl chloride resin is used and the halogen substance is contained in the resin, a harmful gas residue is generated at the time of disposal and incineration.

[0102]

According to the present invention, it is possible to stably provide a resin-coated sheet which is extremely useful as a waterproof cloth, a tent, a tent warehouse, a truck hood, a truck sheet, a container, a curing sheet, a partition film, and a curtain. .

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 13/292 D06M 13/292 E04H 15/54 E04H 15/54 F term (reference) 2E141 EE03 4H028 AA23 AA29 AA35 AA36 AA38 AA44 AA46 AA48 BA04 4J038 CB001 DD001 DG001 DH001 HA186 HA386 JA07 JC21 NA05 NA07 NA15 PB02 PB03 PC10 4L033 AA05 AA07 AA08 AB04 AB05 AC05 AC15 BA39 CA50

Claims (9)

[Claims] 1. A sheet in which both sides of a fiber cloth are coated with a thermoplastic resin, and a flame retardant is contained only in one side,
Its flameproof performance is 5 seconds or less afterflame time, 20 seconds or less afterglow time, 40 cm or less in carbonization area according to the flameproof test method described in Article 4-3 of the Fire Service Law Enforcement Regulations, and the fire protection specified in JIS A 1322. Flame test method: afterflame time 5 seconds or less, dust time 1
A resin-coated sheet having a carbonization length of 10 minutes or less and a length of 10 minutes or less. 2. The resin-coated sheet according to claim 1, wherein the flame retardant is at least one kind of a phosphorus compound represented by the following general formula. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] 3. The content of the flame retardant is 15 with respect to the total weight of the thermoplastic resin excluding the fiber cloth of the resin-coated sheet.
The resin-coated sheet according to any one of claims 1 to 2, wherein the resin-coated sheet has a weight% or more. 4. The thermoplastic resin is at least one selected from urethane resins, polyester resins, olefin resins and polyamide resins.
The resin-coated sheet described. 5. The resin-coated sheet according to claim 1, wherein the thermoplastic resin layer has a thickness of 30 μm or more. 6. The resin-coated sheet according to any one of claims 1 to 5, wherein at least one of the thermoplastic resin layers is formed into a film, and the fiber cloth is laminated and coated. 7. The resin-coated sheet according to claim 1, wherein the fiber cloth is treated with a water repellent agent. 8. The resin-coated sheet according to claim 1, wherein the fiber cloth is previously treated with a halogen-free flame retardant. 9. The resin-coated sheet according to claim 1, which is used as a waterproof cloth, tent, tent warehouse, truck hood, truck sheet, container, curing sheet, partition film or curtain. Resin coated sheet.