JP4638217B2 - Flame retardant metal coated fabric - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a metal-coated fabric used as an electromagnetic shielding material for shielding electromagnetic waves generated from electronic devices and countermeasures against static electricity. More specifically, the present invention relates to a metal-coated fabric having both high flame retardancy and a flexible texture. About.

  In recent years, with the rapid spread of electronic devices in various fields such as homes and offices, there is a problem of electromagnetic interference that causes the devices to malfunction due to electromagnetic waves leaking from other electronic devices. In order to prevent this, various electromagnetic shielding materials are used.

  In addition, due to the enforcement of the Product Liability Act (PL Law) and the like, not only electronic equipment but also electromagnetic shielding materials have been required to be flame retardant, and in particular, to flame retardant that satisfies FMVSS standards and UL standards. There is a strong demand.

  One example of the electromagnetic wave shielding material is one in which the fiber surface of the fiber fabric is coated with a metal, and such a material often has an increased flammability because the coated metal becomes an oxidation catalyst. The reason for this is thought to be that the metal coating not only prevents the fire extinguishing action due to melting of the fibers but also improves the thermal conductivity of the fibers and promotes the spread of fire. Various studies have been conducted to improve the flame retardancy of such materials.

  For example, Patent Document 1 discloses a metal-attached flameproof fiber having a flameproof property that is synergistically improved by providing a metal-attached fiber in combination with a phosphorus compound-based flameproofing agent and a halogen compound-based flameproofing agent. It is disclosed. However, in recent years, the relationship between halogen compounds and dioxins has attracted attention, and halogen compound flame retardants are too similar in structure to dioxins, or halogen compounds such as copper and iron at temperatures of 300 to 600 ° C. When combusted with metal elements, dioxins may be generated, and it is said that dioxins are generated when the temperature is lowered even if combustion decomposition is performed at a temperature of 800 ° C. or higher for the purpose of complete combustion. . From these points of view, the use of halogenated flame retardants is not preferable from the viewpoint of environmental pollution.

  In Patent Document 2, the surface of a metal-coated fiber fabric is coated with a urethane resin, and the surface is coated with a mixture of an organic compound flameproofing agent such as an organic phosphorus compound and an inorganic compound flameproofing assistant such as an antimony compound. Furthermore, a metal-coated fiber woven fabric having flameproofing and rustproofing effects by covering the surface with a urethane-based resin has been disclosed. However, antimony compounds used as flameproofing aids are not preferred because they are toxic to the human body.

  As described above, in recent years, attention has been paid to safety for the environment and the human body, and development of a flame-retardant metal-coated fabric that does not use a halogen compound or an antimony compound is desired.

  For example, magnesium hydroxide and aluminum hydroxide have been proposed as alternative raw materials for halogen compounds and antimony compounds. However, even if these compounds are applied to the fabric alone, sufficient flame retardancy cannot be obtained, and when a large amount of the compound is applied to improve the flame retardancy, there is a problem that the texture of the fabric is cured. .

  In addition, phosphorus compounds such as red phosphorus and phosphoric acid esters have been proposed, but red phosphorus has a toxic problem of producing phosphine, and phosphoric acid esters generally have a low phosphorus content, resulting in sufficient flame retardancy. There was a problem that it was not possible.

Japanese Patent Laid-Open No. 62-21870 Japanese Patent Laid-Open No. 7-42079

  The present invention has been made in view of such a current situation, and an object of the present invention is to provide a flame retardant having a high degree of flame retardancy without using a halogen compound or an antimony compound and having a flexible texture. It is to provide a conductive metal-coated fabric.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a mixture in which a phosphorus compound, a metal hydroxide, a phosphate ester, and a thermoplastic resin are blended at a specific ratio on at least one surface of a metal-coated fabric. The present inventors have found that a metal-coated fabric having both high flame retardancy and a flexible texture can be obtained by forming a flame retardant coating made of the present invention, and the present invention has been completed based on this finding.

That is, the present invention provides at least one phosphorus compound (A) selected from an internally added phosphazene compound and melamine polyphosphate , a metal hydroxide (B), and a phosphate ester (C) on at least one surface of the metal-coated fabric. a mixture of a thermoplastic resin (D) (E) Tona is, a halogen compound as a flame retardant, a metal-coated fabric flame retardant coating that does not contain any antimony compounds and thermally expandable graphite has been formed, (a) :( B) :( C ) ratio of :( D) is, in weight ratio 20 to 200: 100 to 950: 10 to 250: 100 der is, the flame retardant to meet the UL94 method VTM-0 test method It is a flame-retardant metal-coated fabric characterized by having a property.

  According to the present invention, it is possible to provide a metal-coated fabric having both high flame retardancy and a flexible texture. The flame-retardant metal-coated fabric of the present invention does not contain an antimony compound that is toxic to the human body, and does not generate toxic halogen gases such as dioxins during combustion. Since the flame-retardant metal-coated fabric of the present invention is imparted with flame retardancy without significantly impairing the inherent flexibility of the fabric, the original conductivity of the metal, and the electromagnetic shielding properties inherent to the metal-coated fabric, It can be used suitably.

Hereinafter, the present invention will be described in detail.
Examples of the fabric used in the present invention include woven fabrics, knitted fabrics, and nonwoven fabrics, and are not particularly limited. The fiber materials used are polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide (nylon 6, nylon 66, etc.), polyolefin (polyethylene, polypropylene, etc.), polyacrylonitrile, polyvinyl alcohol, polyurethane. Synthetic fibers such as cellulose, semi-synthetic fibers such as cellulose (diacetate, triacetate, etc.), protein (promix, etc.), regenerated fibers such as cellulose (rayon, cupra, etc.), protein (casein fibers, etc.), Natural fibers such as cellulose (cotton, hemp, etc.) and protein (wool, silk, etc.) can be mentioned, and two or more of these may be combined. Of these, synthetic fibers are preferable and polyester fibers are more preferable in consideration of processability and durability. From the viewpoint of safety, it is preferable to select a fiber that does not contain a halogen compound, an antimony compound, or red phosphorus.

  The fiber surface of the fabric made of the above fibers can be coated with a metal by a conventionally known method such as vapor deposition, sputtering, electroplating, or electroless plating. Among these, in consideration of the uniformity and productivity of the formed metal film, the electroless plating method or the combined use of the electroless plating method and the electroplating method is preferable. Further, in order to ensure the fixation of the metal, it is preferable to completely remove impurities such as glue, oil, dust and the like adhering to the fiber surface in advance by a scouring process. The scouring treatment can employ a conventionally known method and is not particularly limited.

Examples of the metal used include gold, silver, copper, zinc, nickel, and alloys thereof, but copper and nickel are preferable in consideration of conductivity and manufacturing cost.
The film formed of these metals is preferably one layer or two layers. When the number of layers is three or more, the thickness of the metal coating increases, which is not preferable because the texture of the fabric becomes hard and the manufacturing cost increases. When the metal film is laminated in two layers, the same kind of metal may be laminated in two layers, or different metals may be laminated. These may be appropriately set in consideration of required electromagnetic shielding properties and durability.

  In the flame-retardant metal-coated fabric of the present invention, the phosphorus compound (A), metal hydroxide (B), phosphate ester (C), and thermoplastic resin (D) are specified on at least one side of the metal-coated fabric. The flame retardant coating film composed of the mixture (E) blended at the ratio of is formed. Here, the “film” means a so-called film or sheet.

The phosphorus compound (A) used in the present invention is an internally added phosphazene compound and melamine polyphosphate. Among them, the phosphorus content is 10 to 15% by weight, particularly 12 to 14% by weight, and phosphorus and A nitrogen content ratio of phosphorus: nitrogen = 1: 0.3 to 4, particularly 0.4 to 3.5 is preferably used.

  When the phosphorus content is less than 10% by weight, the effect as a flame retardant is low, and a large amount of phosphorus compound is required to impart sufficient flame retardancy to the metal-coated fabric, which is uneconomical. Further, when the phosphorus content exceeds 15% by weight (such compounds include amide phosphazene, ammonium polyphosphate, etc.), generally, there is a property of corroding the metal film of the metal-coated fabric, In particular, there is a possibility that the conductivity and the electromagnetic wave shielding property are lowered.

  Further, if the nitrogen content is less than 0.3 with respect to phosphorus 1, the carbonized layer formed at the time of combustion becomes brittle, and it becomes difficult to suppress the spread of fire. When the nitrogen content exceeds 4 with respect to phosphorus 1, the effect as a flame retardant is low, and a large amount of phosphorus compound is required to impart sufficient flame retardancy to the metal-coated fabric, which is uneconomical.

As the internally added phosphazene compound of the phosphorus compound (A), it is preferable to use cyclic or linear phenoxyphosphazene.

  The compounding amount of the phosphorus compound (A) is required to be 20 to 200 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the thermoplastic resin (D). When the compounding amount of the phosphorus compound (A) is less than 20 parts by weight relative to 100 parts by weight of the thermoplastic resin (D), sufficient flame retardancy cannot be imparted to the metal-coated fabric, and 200 parts by weight If it exceeds, problems such as bleeding out of the phosphorus compound and hardening of the texture may occur.

  In the present invention, the metal hydroxide (B) is used from the viewpoint of cooling the combustion field when the metal-coated fabric burns. As a metal hydroxide (B) used for such a purpose, aluminum hydroxide, magnesium hydroxide, etc. can be mentioned, for example, These may be combined 2 or more types. Among these, aluminum hydroxide having a large endothermic amount is preferably used.

  The compounding quantity of a metal hydroxide (B) is requested | required that it is 100-950 weight part with respect to 100 weight part of thermoplastic resins (D), More preferably, it is 100-400 weight part. When the blending amount of the metal hydroxide (B) is less than 100 parts by weight relative to 100 parts by weight of the thermoplastic resin (D), sufficient flame retardancy cannot be imparted to the metal-coated fabric, and 950 weights. If it exceeds the part, problems such as poor adhesion between the flame retardant coating composed of the mixture (E) and the metal-coated fabric, and a hardened texture may occur.

  In the present invention, the phosphoric acid ester (C) is mainly used for the purpose of plasticizing the flame retardant film made of the mixture (E). The phosphate ester (C) used for such purposes is not particularly limited, and among them, the normal phosphate ester imparts sufficient plasticity without corroding the metal coating of the metal-coated fabric. preferable. Preferred phosphoric acid esters (C) include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl Conventionally known compounds such as diphenyl phosphate, resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like may be used in combination of two or more.

  The amount of the phosphate ester (C) is required to be 10 to 250 parts by weight, more preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the thermoplastic resin (D). If the blending amount of the phosphoric ester (C) is less than 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin (D), the plasticizing effect is insufficient and the texture may be cured, and it exceeds 250 parts by weight. When the phosphoric acid ester bleeds out or a flame retardant film made of the mixture (E) is formed, problems such as stickiness of the film occur.

  In the present invention, the thermoplastic resin (D) is used for the purpose of fixing the above-described phosphorus compound (A), metal hydroxide (B), and phosphate ester (C) to the metal-coated fabric, that is, as a binder resin. Examples of the thermoplastic resin (D) used for such purposes include ester-based, ether-based, and carbonate-based urethane resins, polymethyl methacrylate, polyethyl methacrylate, ethyl polyacrylate, and polyacrylic acid. Examples thereof include acrylic resins such as butyl, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate-isophthalate copolymer, and two or more of these may be combined. Of these, considering flexibility, urethane resin and acrylic resin are preferable, and urethane resin is more preferable. A urethane resin is particularly preferably used in the present invention because it hardly inhibits flame retardancy and has a soft texture.

In the mixture (E), for the purpose of coloring, adjusting the texture, imparting functionality such as insulating properties, and further improving the flame retardancy, other additives can be blended within a range that does not impair the performance. Examples of such additives include silicone rubbers, olefin copolymers, elastomers such as modified nitrile rubbers and modified polybutadiene rubbers, flame retardant aids such as melamine and melamine cyanurate, pigments such as titanium dioxide, and polyethers. Examples thereof include dispersants such as polymers and polycarboxylic acid polymers.

  The raw materials such as the phosphorus compound (A), metal hydroxide (B), phosphate ester (C), thermoplastic resin (D), and additive used in the present invention are not particularly limited and may be commercially available. it can. For example, the thermoplastic resin (D) is commercially available in a state of being dissolved in an organic solvent and can be easily obtained.

  The flame-retardant metal-coated fabric of the present invention has the phosphorus compound (A), metal hydroxide (B), phosphate ester (C) and thermoplastic resin (D) described above as essential components at a specific ratio. It can manufacture by coating a metal-coated cloth with the mixed processing liquid containing, and forming the flame-retardant film which consists of a mixture (E).

  Examples of the solvent for dissolving or dispersing various raw materials include organic solvents such as benzene, toluene, xylene, methyl ethyl ketone, and dimethylformamide. Moreover, you may use mineral oil fractions, such as industrial gasoline, petroleum naphtha, and a turpentine. Further, two or more of these can be combined.

  An appropriate amount of the solvent is added so that the viscosity of the mixed treatment liquid is 3000 to 25000 cps, more preferably 8000 to 20000 cps. If the viscosity of the mixed treatment liquid is less than 3000 cps, the mixed treatment liquid may leak back to the opposite surface of the metal-coated fabric and impair the appearance quality. If the mixed treatment liquid exceeds 25000 cps, the coatability deteriorates.

  As long as various raw materials can be uniformly dispersed and mixed, any method may be used for preparing the mixed treatment liquid. Common methods include dispersion mixing by propeller stirring and dispersion mixing by kneading with a kneader, a roller, or the like.

  Moreover, as a coating method, the normal method using a knife coater, a roll coater, a slit coater, etc. is employable. Also, a laminate method and a bonding method are possible. After coating the metal-coated fabric with the mixed treatment liquid, the solvent is removed by drying or the like to form a flame retardant film composed of the mixture (E).

  The amount of the mixed treatment liquid applied to the metal-coated fabric is preferably 100 to 300% by weight, particularly 150 to 250% by weight, as the weight of the flame retardant coating composed of the mixture (E). If the applied amount is less than 100% by weight, high flame retardancy may not be obtained. If it exceeds 300% by weight, not only the inherent flexibility of the fabric is lost, but further improvement in flame retardancy cannot be expected.

  In addition, in order to prevent back leakage of the mixed processing liquid, a sealing resin such as an acrylic resin, a polyurethane resin, or a polyester resin may be coated in advance. The sealing resin is usually coated so as to fill the gap between the fibers coated with metal. A pigment may be added to the filler resin for the purpose of coloring, or a flame retardant may be added for the purpose of further improving flame retardancy. At this time, it goes without saying that a flame retardant other than the halogen compound or the antimony compound is selected. The surface to be coated with the sealing treatment liquid mainly composed of the sealing resin may be the same surface as the surface to be coated with the mixed processing liquid for forming the flame retardant coating film, or may be the opposite surface. When the same surface is coated, if a resin similar to the thermoplastic resin (D) is used, in addition to the sealing effect, an effect of improving the adhesion between the flame-retardant coating and the metal-coated fabric can be expected. On the other hand, when coating on the opposite surface, using a resin with high film strength, in addition to the sealing effect, has the effect of protecting the surface of the metal-coated fabric and the adhesiveness to the adhesive tape used when attaching to an electronic device. The improvement effect can be expected.

  Thus, the flame retardant metal coated fabric of the present invention can be obtained. The flame retardant coating composed of the mixture (E) may be formed not only on one side of the fabric but also on both sides. Moreover, after forming a flame-retardant film, you may perform the process which provides other functionality, or special processes, such as a calendar process.

  The thickness of the flame-retardant metal-coated fabric of the present invention is preferably 50 to 500 μm, particularly preferably 100 to 300 μm. If the thickness is less than 50 μm, the strength may decrease, and if it exceeds 500 μm, flexibility is impaired and handling becomes difficult.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited at all by the following examples. In the examples, “parts” and “%” are based on weight. Moreover, the performance of the obtained flame-retardant metal-coated fabric was evaluated by the following method.

(1) Flame retardancy UL94 method VTM-0 test method was followed.
(2) Flexibility According to JIS L 1096 A method (45 ° cantilever method). Here, the smaller the value, the softer the texture.
(3) Surface conductivity Using a Loresta-EP MCP-T360 ESP type resistance value meter manufactured by Mitsubishi Chemical Corporation, the resistance value of the surface on which no flame retardant coating was formed was measured.
(4) Electromagnetic wave shielding property In accordance with the KEC method by the Kansai Electronics Industry Promotion Center, the attenuation of electromagnetic waves at 10 MHz to 1 GHz was measured using a spectrum analyzer HP8591EM with tracking generator manufactured by Hewlett-Packard Japan.
(5) Adhesive strength between flame-retardant coating and metal-coated fabric Using a hot-melt adhesive tape (MELCO tape BW-II 25mm RB) manufactured by Sun Kasei Co., Ltd. Bonding was performed at 150 ° C. for 5 seconds. After leaving at room temperature for 30 minutes, 180 ° peel strength was measured at a tensile speed of 100 mm / min using a tensile compression tester (SV-55C-20H) manufactured by Imada Manufacturing Co., Ltd.
(6) Adhesive strength between pressure-sensitive adhesive tape and flame-retardant metal-coated cloth A double-sided pressure-sensitive adhesive tape (No. 5011N) manufactured by Nitto Denko Corporation was bonded to the surface where no flame-retardant film was formed, A roller with a weight of 2 kg was reciprocated once to make contact. After leaving at room temperature for 30 minutes, 180 ° peel strength was measured at a tensile speed of 100 mm / min using a tensile compression tester (SV-55C-20H) manufactured by Imada Manufacturing Co., Ltd.
(7) Thickness Measured using a thickness measuring device manufactured by Teclock Co., Ltd.

Polyester fiber fabric (warp 56dtex / 36f, weft 56dtex / 36f, warp density 158 / in, weft density 95 / in) is scoured, dried and heat treated, then palladium chloride 0.3g / L, stannous chloride It was immersed in an aqueous solution of 40 ° C. containing 30 g / L and 36% hydrochloric acid 300 ml / L for 2 minutes and then washed with water. Subsequently, it was immersed in borohydric acid having an acid concentration of 0.1 N and 30 ° C. for 5 minutes and then washed with water. Next, it was immersed in an electroless copper plating solution at 30 ° C. containing 7.5 g / L of copper sulfate, 30 ml / L of 37% formalin and 85 g / L of Rochelle salt, and then washed with water. Subsequently, the nickel was immersed in an electric nickel plating solution containing nickel sulfamate 300 g / L, boric acid 30 g / L, nickel chloride 15 g / L, pH 3.7, 35 ° C. for 10 minutes at a current density of 5 A / dm ^2. After laminating, it was washed with water. Copper 10 g / ^{m 2} in the fabric, the nickel is 4g / ^{m 2} Plating. The basis weight of the obtained metal-coated fabric was 64 g / m ² .

One side of the obtained metal-coated woven fabric was coated with a sealing treatment liquid of the following formulation 1 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 4 g / m ² in terms of solid content. Next, the mixed treatment liquid for forming a flame-retardant film of Formula 2 below was coated on the same surface using a knife, and dried at 130 ° C. for 2 minutes. The applied amount was 150 g / m ² in terms of solid content.

Formula 1
Toacron SA-6218 100 parts (Toepe Co., Ltd., acrylic resin, solid content 18%)
Resamine UD crosslinking agent 1.5 parts (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate crosslinking agent, solid content 75%)
Toluene The viscosity was adjusted to 15000 cps by adjusting the appropriate amount of toluene added.

Formula 2
Melamine polyphosphate 15 parts (phosphorus content 13%, nitrogen content 43%)
Aluminum hydroxide 60 parts Bisphenol A bis (diphenyl phosphate) 22.5 parts Ester urethane resin 30 parts Dimethylformamide 120 parts Methyl ethyl ketone An appropriate amount of methyl ethyl ketone was adjusted to adjust the viscosity to 8000 cps.

One side of the metal-coated woven fabric plated in the same manner as in Example 1 was coated with a sealing solution having the following formulation 3 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 6 g / m ² in terms of solid content. Next, the flame retardant coating forming mixed treatment liquid of the following prescription 4 was coated on the same surface using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 130 g / m ² in solid content.

Formula 3
Toacron SA-6218 100 parts (Toepe Co., Ltd., acrylic resin, solid content 18%)
Resamine UD crosslinking agent 1.5 parts (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate crosslinking agent, solid content 75%)
8.5 parts of cyclic phenoxyphosphazene (phosphorus content 13%, nitrogen content 6%)
Tricresyl phosphate 2.5 parts Toluene Viscosity was adjusted to 18000 cps by adjusting the amount of toluene added.

Formula 4
18 parts of cyclic phenoxyphosphazene (phosphorus content 13%, nitrogen content 6%)
Melamine polyphosphate 15 parts (phosphorus content 13%, nitrogen content 43%)
Aluminum hydroxide 60 parts Tricresyl phosphate 7.5 parts Ester-based urethane resin 30 parts Dimethylformamide 112 parts Methyl ethyl ketone A suitable amount of methyl ethyl ketone was adjusted to adjust the viscosity to 8000 cps.

One side of the metal-coated fabric plated in the same manner as in Example 1 was coated with the sealing treatment solution of Formula 3 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 6 g / m ² in terms of solid content. Next, the mixed treatment liquid for forming a flame-retardant film of Formula 2 was coated on the opposite surface using a knife, and dried at 130 ° C. for 2 minutes. The applied amount was 150 g / m ² in terms of solid content.

One side of the metal-coated woven fabric plated in the same manner as in Example 1 was coated with a sealing solution having the following formulation 5 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 5 g / m ² in terms of solid content. Next, the mixed treatment liquid for forming a flame-retardant film having the following formulation 6 was coated on the same surface using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 120 g / m ² in terms of solid content.

Formula 5
Crisbon 2116EL 100 parts (Dainippon Ink & Chemicals, urethane resin, solid content 30%)
Resamine UD crosslinking agent 1.5 parts (manufactured by Dainichi Seika Kogyo Co., Ltd., isocyanate crosslinking agent, solid content 75%)
Dimethylformamide Viscosity was adjusted to 8000 cps by adjusting an appropriate amount of dimethylformamide.

Formula 6
Melamine polyphosphate 7.5 parts (phosphorus content 13%, nitrogen content 43%)
Aluminum hydroxide 75 parts Titanium dioxide 7.5 parts Bisphenol A bis (diphenyl phosphate) 22.5 parts Ester urethane resin 30 parts Dimethylformamide 110 parts Toluene 10 parts Methyl ethyl ketone Appropriate amount By adjusting the amount of methyl ethyl ketone added, the viscosity can be adjusted. Adjusted to 8000 cps.

One side of the metal-coated fabric plated in the same manner as in Example 1 was coated with the sealing solution of Formula 5 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 5 g / m ² in terms of solid content. Next, the mixed treatment liquid for forming a flame-retardant film of Formulation 6 was coated on the opposite surface using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 120 g / m ² in terms of solid content.

A polyester fiber fabric (warp 56dtex / 36f, weft 56dtex / 36f, warp density 175 / in, weft density 132 / in) was treated in the same manner as in Example 1, 12 g / m ^{2 for} copper and 5 g for nickel. / ^{m 2} was plated to obtain a metal-coated fabric having a basis weight of 75 g / ^{m 2.} One side of the obtained metal-coated fabric was coated with a mixed treatment liquid for forming a flame-retardant film of the following formulation 7 using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 135 g / m ² in terms of solid content.

Formula 7
Melamine polyphosphate 7.5 parts (phosphorus content 13%, nitrogen content 43%)
Aluminum hydroxide 75 parts Titanium dioxide 7.5 parts Bisphenol A bis (diphenyl phosphate) 22.5 parts Ester urethane resin 30 parts Dimethylformamide 110 parts Toluene 10 parts Methyl ethyl ketone Appropriate amount By adjusting the amount of methyl ethyl ketone added, the viscosity can be adjusted. Adjusted to 20000 cps.

[Comparative Example 1]
One side of the metal-coated fabric plated in the same manner as in Example 1 was coated with the sealing treatment liquid of Formula 1 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 4 g / m ² in terms of solid content. Next, the flame retardant coating forming mixed treatment liquid of the following formulation 8 was coated on the same surface using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 150 g / m ² in terms of solid content.

Formula 8
45 parts melamine polyphosphate (phosphorus content 13%, nitrogen content 43%)
Bisphenol A bis (diphenyl phosphate) 10 parts Ester-based urethane resin 30 parts Dimethylformamide 115 parts Methyl ethyl ketone A suitable amount of methyl ethyl ketone was adjusted to adjust the viscosity to 8000 cps.

[Comparative Example 2]
One side of the metal-coated fabric plated in the same manner as in Example 1 was coated with the sealing treatment liquid of Formula 1 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 4 g / m ² in terms of solid content. Next, the mixed treatment liquid for forming a flame-retardant film having the following formulation 9 was coated on the same surface using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 250 g / m ² in terms of solid content.

Formula 9
Aluminum hydroxide 300 parts Bisphenol A bis (diphenyl phosphate) 10 parts Ester urethane resin 30 parts Dimethylformamide 115 parts Methyl ethyl ketone An appropriate amount of methyl ethyl ketone was adjusted to adjust the viscosity to 8000 cps.

[Comparative Example 3]
One side of the metal-coated fabric plated in the same manner as in Example 1 was coated with the sealing treatment liquid of Formula 1 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 4 g / m ² in terms of solid content. Next, the mixed processing solution for forming a flame-retardant film having the following formulation 10 was coated on the same surface using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 150 g / m ² in terms of solid content.

Formula 10
10 parts of cyclic phenoxyphosphazene (phosphorus content 13%, nitrogen content 6%)
10 parts melamine polyphosphate (phosphorus content 13%, nitrogen content 43%)
Aluminum hydroxide 40 parts Tricresyl phosphate 30 parts Ester-based urethane resin 60 parts Dimethylformamide 100 parts Methyl ethyl ketone A suitable amount of methyl ethyl ketone was adjusted to adjust the viscosity to 8000 cps.

[Comparative Example 4]
One side of the metal-coated fabric plated in the same manner as in Example 1 was coated with the sealing treatment liquid of Formula 1 using a knife and dried at 130 ° C. for 1 minute. The applied amount was 4 g / m ² in terms of solid content. Next, the flame retardant coating forming mixed treatment liquid of the following prescription 11 was coated on the same surface using a knife and dried at 130 ° C. for 2 minutes. The applied amount was 150 g / m ² in terms of solid content.

Formula 11
Decabromodiphenyl oxide 45 parts Antimony trioxide 25 parts Tricresyl phosphate 15 parts Ester-based urethane resin 30 parts Dimethylformamide 85 parts Methyl ethyl ketone An appropriate amount of methyl ethyl ketone was adjusted to adjust the viscosity to 8000 cps.

  The results of evaluating the performance of the above Examples and Comparative Examples are shown in Table 1.

  As is apparent from Table 1, according to Examples 1 to 6, it is possible to obtain a flame-retardant metal-coated woven fabric having both high flame retardancy and a flexible texture without using a halogen compound or an antimony compound. did it. In Example 2, by adding a flame retardant to the sealing resin, even if the weight of the flame retardant coating formed on the resin is small, the target flame retardancy can be satisfied, and flexibility It was excellent in properties. In Example 4, it was possible to improve the adhesion between the flame retardant film formed on the resin and the metal-coated fabric by using a urethane resin as the sealing resin. This is considered to be because compatibility is improved by using a thermoplastic resin (urethane resin) contained in the flame-retardant coating and a similar sealing resin. In Example 5, the adhesive resin coated on the opposite surface of the flame-retardant film is made of urethane resin having high film strength, so that the adhesive tape is more adhesive than that coated with acrylic resin having low film strength in Example 3. And the flame-retardant metal-coated woven fabric were improved, which was preferable for use as an electromagnetic shielding material attached to electronic equipment. In Example 6, by using a high-density fabric and increasing the viscosity of the mixed treatment liquid for forming the flame-retardant coating, a flame-retardant metal-coated fabric can be obtained without coating the sealing resin. It was.

  On the other hand, Comparative Example 1 lacking metal hydroxide and Comparative Example 3 in which the ratio of the phosphorus compound, metal hydroxide, phosphate ester, and thermoplastic resin is outside the specific range can satisfy the flame retardancy. There wasn't. Further, Comparative Example 2, which lacks a phosphorus compound and contains a large amount of metal hydroxide, was satisfactory in flame retardancy, but the texture was extremely hardened, was difficult to handle, and was not practical. Although Comparative Example 4 using a halogen compound or an antimony compound satisfies flame retardancy and flexibility, it is not preferable in view of safety to the environment and the human body.

Claims (7)

On at least one surface of the metal-coated fabric, at least one phosphorus compound (A) selected from an internally added phosphazene compound and melamine polyphosphate , a metal hydroxide (B), a phosphate ester (C), and a thermoplastic resin ( mixture of D) (E) Tona is, a halogen compound as a flame retardant, a metal-coated fabric flame retardant coating that does not contain any antimony compounds and thermally expandable graphite has been formed, (a) :( B) :( C) ratio of :( D) is, in weight ratio 20 to 200: 100 to 950: 10 to 250: 100 der is, to have a flame retardancy satisfying the UL94 method VTM-0 test method A flame-retardant metal-coated fabric characterized. The phosphorus content of the phosphorus compound (A) is 10 to 15% by weight, and the ratio of the phosphorus and nitrogen content is phosphorus: nitrogen = 1: 0.3-4 by weight ratio The flame-retardant metal-coated cloth according to claim 1. The flame retardant metal-coated fabric according to claim 1 or 2, wherein the metal hydroxide (B) is at least one selected from aluminum hydroxide and magnesium hydroxide. The flame-retardant metal-coated fabric according to any one of claims 1 to 3 , wherein the phosphate ester (C) is a regular phosphate ester. The flame-retardant metal-coated cloth according to any one of claims 1 to 4 , wherein the thermoplastic resin (D) is at least one selected from a urethane resin, an acrylic resin, and a polyester resin. The flame-retardant metal-coated fabric according to any one of claims 1 to 5 , wherein the weight of the flame-retardant coating comprising the mixture (E) is 100 to 300% by weight based on the metal-coated fabric. . The flame-retardant metal-coated fabric according to any one of claims 1 to 6 , wherein the flame-retardant metal-coated fabric has a thickness of 50 to 500 µm.