JPH0742079A - Method for flameproofing of metal-coated textile fabric - Google Patents

Abstract

PURPOSE:To provide a method for imparting textile fabrics with electromagetic wave shielding ability and flameproofness. CONSTITUTION:A metal-coated flame-retardant woven fabric is coated with an urethane resin followed by an organic flameproofing agent (or its mixture with an inorganic flameproofing auxiliary) and then an urethane resin again.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for imparting flameproofness to a metal-coated fiber fabric.

[0002]

2. Description of the Related Art OA equipment is rapidly becoming popular due to the reduction in size and weight of electronic equipment and the availability of word processors, microcomputers, telefaxes and the like at low prices. Furthermore, at home, TVs, microwave ovens, electric blankets, etc. are used daily.

Weak electromagnetic waves are leaked from these electronic devices, and there is concern that malfunctions due to interference between electronic devices or effects on the user may occur.

Therefore, it is necessary to prevent leakage from electronic equipment, but there is also a technically difficult problem.

At present, measures are taken to prevent leakage by applying a metal coating to the casing of electronic equipment, and to cover the electric wire with a metal foil or a copper net.

In addition, for users of OA equipment such as word processors,
Use of an electromagnetic shield apron is recommended.

Further, in order to prevent external noise from being incident on a precision medical instrument, an analytical instrument or the like during measurement to cause a measurement error, the installation of an electromagnetic wave shielded room is also being considered.

In order to cope with such an environment, demands for electromagnetic wave shield curtains, wall materials and the like are increasing in recent years.

Furthermore, the curtain used in an environment close to a closed room such as a hospital, a hotel, a cabaret, a theater, a television broadcasting room is obliged to use a flameproof curtain by the Fire Service Law.

Curtains made of metal fiber woven fabric, metal perforated plates, window glasses having a metal layer formed on the glass surface by sputtering, and the like have electromagnetic wave shielding properties and flameproof properties.

The metal fiber material has a problem that it is weak in bending and easily scratched, and the metal perforated plate lacks comfort and aesthetics.

A window glass having a metal layer formed on the surface by sputtering is expensive and, moreover, lacks the functionality as a curtain.

[0013]

The fiber woven fabric is excellent in flexibility, sewability and the like, and is optimal as a curtain fabric.

However, the fiber is non-conductive and lacks electromagnetic wave shielding performance.

Therefore, the development of a technique for applying a metal coating to the surface of a fiber woven fabric to impart conductivity is under way.

For example, a method of forming a metal film on the surface of a fiber woven fabric by metal plating, sputtering, metal deposition or the like has been put into practical use.

However, since the fiber woven fabric coated with a metal film is flammable and cannot be used as a curtain in places regulated by the Fire Service Law, it is necessary to carry out flameproofing after the metal coating.

On the other hand, Japanese Patent Application Laid-Open No. 62-21870 discloses a method of imparting flameproofness by coating a fiber with a metal by sputtering and then applying a phosphorus compound type flameproof agent and a halogen compound type flameproof agent. Has been done.

According to this method, after forming a metal film on the surface by sputtering, it is immersed in an aqueous solution of a phosphorus-containing cyclic compound, squeezed, dried at 140 ° C. for 5 minutes, and then heat-treated at 190 ° C. for 2 minutes to bring the phosphorus compound into close contact.

Next, there is a method of immersing in a halogen compound flame retardant solution, squeezing, drying at 80 ° C. for 5 minutes, and further heat treating at 140 ° C. for 5 minutes.

In this method, an aqueous solution of a phosphorus compound and a halogen compound is directly applied to a metal film formed by sputtering and heat treatment is performed at 190 ° C. and 140 ° C., so that the conductivity of the metal film may be deteriorated due to corrosion or alteration. However, there is a drawback that desired performance is difficult to obtain.

[0022]

Means for Solving the Problems The present invention has been made as a result of intensive studies based on the above-mentioned circumstances. Has completed the curtain with.

A metal film is formed on the surface of the flame-retardant fiber woven fabric, and the metal film is coated with a urethane resin, and then an organic compound flame retardant or a mixture of an inorganic compound flame retardant auxiliary agent and an organic compound flame retardant is added. By applying and then coating the surface with a urethane-based resin, it is possible to obtain a metal-coated fiber woven fabric which has neither flame resistance nor deterioration, and has flameproof performance and electromagnetic wave shielding performance.

[0024]

Function As a matter of course, the organic fiber woven fabric often has an increased combustibility as the metal serves as an oxidation catalyst when the flame-retardant fiber woven fabric is coated with a metal and ignited.

For example, when a metal film is formed on a fabric made of polyester fiber, polyamide fiber, flame-retardant polyester fiber, polyclar fiber, polyvinyl chloride fiber, or polyvinylidene chloride fiber by electroless plating, an ignition test is conducted. It was flammable and failed or had a long dusting time, and failed the standards set by the Fire Service Law.

For example, the flame-retardant polyester is burned by ignition, and the portion thereof melts and falls, so that the spread of flame to other parts is prevented and the flame-retardant standard is passed.

However, when the flame-retardant polyester having a metal film formed on its surface is burned by ignition, it cannot be melted and dropped due to the metal film and continues to burn. Further, since the metal has good thermal conductivity, the spread of fire is promoted. To do.

Also, the catalytic action of the metal oxide in the burned portion is involved in the continuation of combustion.

The present invention uses a flame-retardant fiber woven fabric as a base fabric,
Forming a conductive metal film of copper, nickel or the like on the surface of the metal film to prevent the metal film from being corroded or deteriorated by the flameproofing agent, the urethane resin has good adhesion to the metal film and is further flexible. By coating the surface with an organic compound-based flameproofing agent or a mixture of an inorganic compound-based flameproofing aid and an organic compound-based flameproofing agent, and further coating the surface with a urethane-based resin. It is possible to provide a metal-coated fiber woven fabric having an excellent flameproof property and an electromagnetic wave shield property without rust.

As the flame-retardant fiber, various flame-retardant fibers having an LDI value (limit oxygen index) of 26 or more can be used, and a flame-retardant polyester fiber obtained by kneading or copolymerizing a phosphorus compound or a halogen compound, Examples include combustion polyamide fiber, polyclar fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber and the like.

As a flameproofing agent, a search for a water-soluble flameproofing agent revealed that polyphosphoric acid carbamate, which is an organic phosphorus compound, was good.

However, if a large amount is added, the texture becomes hard and the characteristics of the woven fabric are impaired.

Therefore, an inorganic flameproofing aid is blended in order to have excellent flameproofness and not harden the feeling.

The compounding ratio of the organic flameproofing agent and the inorganic auxiliary agent is 100:
The range of 30 to 100 is preferable.

Examples of the inorganic compound-based flameproofing aid include diammonium hydrogen phosphate, antimony trioxide, antimony pentaoxide, borax, tin oxide, molybdenum oxide, zirconium hydroxide and zirconium oxide. Examples of the flame retardant include N.methyloldimethylphosphonopropionamide, amidephosphazene, hexabromocyclododecane, tetrakishydromethylphosphonium sulphate and the like.

The urethane resin is further coated on the flameproof agent to prevent the flameproof agent from falling off, to prevent the absorption of moisture in the air,
A urethane resin was selected because of its flexibility, abrasion resistance, and colorability.

Further, as the urethane type resin, as the isocyanate, aromatic isocyanate such as TDI, HD
Examples of the aliphatic / alicyclic isocyanate such as I and XDI and the polyol include polyester polyols composed of aromatic carboxylic acid or aliphatic carboxylic acid and glycol component, and polyether polyols such as polyoxyethylene glycol and polyoxypropylene glycol as raw materials. The self-emulsifying type colloidal dispersion type aqueous urethane resin can be preferably used.

The amount of adhesion to the fabric is 5 to 15% of the plating metal, 0.5 to 2% of the first layer urethane resin, 0.5 to 2% of the organic flameproof agent, and 0.5 to the second layer of the urethane resin. 2%,
Is preferred.

[0039]

EXAMPLES The present invention will be described below with reference to specific examples.

[0040]

Example 1 A flame-retardant polyester fiber woven fabric (warp 150 denier multifilament, 80 filaments / inch, 150 denier multifilament, 80 filaments / inch) was used as a scouring agent 2 g / l (Daiichi Kogyo Seiyaku: WS-20). 8 in aqueous solution
Scouring and degreasing at 0 ° C for 30 minutes, then sodium hydroxide 2g
/ L aqueous solution (bath ratio 1:30) at 85 ° C for 60 minutes.

Then, it was dipped in an electroless copper plating solution adjusted to 40 ° C. for 3 minutes to form a uniform copper film of 0.3 Ω / cm on the surface of the woven fabric.

The woven fabric coated with copper is made of urethane resin 10
g / l aqueous solution (Dainippon Ink: Hydran AP6
It was immersed in 0), squeezed, dried and then heat-treated at 120 ° C. for 2 minutes.

Then, diammonium hydrogen phosphate 50 g
/ L and an organic compound flameproofing agent 40 g / l (manufactured by Nikka: Nikka Phinon P-100) were immersed in an aqueous solution, squeezed and dried.

Furthermore, the woven fabric treated as described above was treated with an aqueous solution of 8 g / l of urethane resin (Dainippon Ink: Hydran AP
After immersing in −40), squeezing and drying, it was heat treated at 120 ° C. for 2 minutes.

The woven fabric thus obtained was tested for rust-preventing performance and flameproofing under the following conditions.

The results are shown in Tables 1 and 2, and the rust prevention effect and flameproof performance were good.

Composition of copper plating solution Copper sulfate 15 g / l Sodium hydrogencarbonate 10 g / l Tartrate 30 g / l 38% formalin solution 100 ml / l PH 11.5

(Evaluation of Anticorrosion Property) (1) 5 in a room adjusted to room temperature of 25 ° C. and humidity of 55% RH
Store for 00 days and check for rust and discoloration. (2) Store in a room at room temperature of 40 ° C. and humidity of 40% RH for 500 days to check for rust and discoloration. (3) A desiccator having a humidity of 100% RH is prepared in a room at a room temperature of 25 ° C., and left in the desiccator for 500 days to examine rusting and discoloration.

(Evaluation of Flameproofness) In order to evaluate the flameproofness of the sample obtained by the flameproofing treatment as described above, a 45 degree method combustion tester defined by JIS was used. A 45 degree method combustion test is carried out. 3 for each test
It is carried out once.

The 45-degree method combustion test is a test in which a sample placed at an angle of 45 degrees is ignited from the lower side of the sample with a flame of a burner of 45 mm to check flame resistance.
For one second, if the flame does not reach, heat it for 1 minute,
The residual dust time, carbonization area and carbonization length are measured to evaluate the flameproof property.

The evaluation criteria for each evaluation item in the 45-degree method combustion test are as follows.

(Items) (Pass criteria) (Pass value) Afterflame time Elapsed time from removal of the burner after burning to raising the flame and stopping from burning (within 3 seconds) Afterglow time Burner after burning Elapsed time from removal to stop burning without raising flame (within 3 seconds) Carbonized area Carbonized area within time until burning stops after burning (within 30 cm ² ) Long carbonization Burning after burning Carbonization length (within 20 cm) within the time it takes to stop

[0053]

[Comparative Example 1] A flame-retardant polyester woven fabric having the same structure as that of Example 1 was subjected to scouring / defatting and weight reduction treatment under the same conditions as in Example 1,
A copper film was applied by electroless plating.

The woven fabric obtained above was examined under the same conditions as in Example 1 for rust resistance and flameproof performance. As a result, rust was generated as shown in Tables 1 and 2, and flameproof performance was It was a failure.

[0055]

Comparative Example 2 On the woven fabric obtained in Comparative Example 1 on which a copper film was applied by electroless plating, 50 g / l of the same diammonium hydrogen phosphate as in Example 1 and 40 g / l of an organic compound flame retardant (Nikka: Nikka) It was immersed in an aqueous solution of a mixture with Phinon P-100), squeezed and dried.

The obtained fabric was examined under the same conditions as in Example 1 for rust-preventing performance and flameproofing performance. The results show that the flameproofing performance passed as shown in Table 2, but the rustproofing was as shown in Table 1. , And discoloration were observed, and it was confirmed that the copper film was corroded.

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

Example 2 Polyvinylidene chloride mesh (300 denier monofilament, warp, weft, 60 / in) in an aqueous solution of a scouring agent 2 g / l (Daiichi Kogyo Seiyaku Co., Ltd .: WS-20) at 60 ° C. for 60 minutes. After scouring and degreasing, urethane resin aqueous solution 20g / l (Dainippon Ink: Hydran HW-3
It was immersed in 33), squeezed and dried.

Then, it was immersed in an electroless nickel plating solution adjusted to 40 ° C. for 7 minutes to form a uniform nickel film of 1.2 Ω / cm on the surface of the polyvinylidene chloride mesh.

A nickel-coated mesh was used to prepare a urethane resin aqueous solution 20 g / l (manufactured by Dainippon Ink and Co., Ltd .: Hydran H
W-350), soaked, squeezed and dried.

Next, the organic compound flame retardant was immersed in an aqueous solution of 60 g / l (manufactured by Nikka: Nikka Phinon P-100), squeezed and dried.

Further, it was dipped in an aqueous solution of 30 g / l of urethane resin (Dainippon Ink: Hydran HW-311), squeezed and dried.

With respect to the obtained mesh, the results of examining the rust-preventing performance and the flameproofing performance under the conditions of Example 1 were good as shown in Tables 3 and 4.

Composition of nickel plating solution nickel hypophosphite 28 g / l boric acid 12 g / l ammonium sulfate 3 g / l sodium acetate 5 g / l PH 6.0

[0066]

[Comparative Example 3] After a nickel plating film was formed on the mesh surface by the same method as in Example 2, the results of examining the rust-preventing property and the flame-proofing property were as shown in Tables 3 and 4, and rust occurred and the residual dust time Only failed.

[0067]

Comparative Example 4 A nickel plating film was formed on the mesh surface in the same manner as in Example 2, and then an organic compound flameproofing agent 60 g / l was used.
(Nikka: Nikka Phynon P-100) was dipped in an aqueous solution, squeezed and dried.

The results of examining the rustproofing property and flameproofing property of the obtained mesh are shown in Tables 3 and 4, and rust was generated and discoloration occurred.
However, as shown in Table 4, the flameproof performance was acceptable.

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

As described above, according to the present invention, a metal film is formed on the surface of a fiber made of flame-retardant fiber, and the surface is coated with a urethane resin.

Then, it is treated with an organic compound flameproofing agent or a mixture of an inorganic compound flameproofing aid and an organic compound flameproofing agent,
Further, by coating the surface thereof with a urethane-based resin, a metal-coated flame-retardant woven fabric having excellent flameproof performance and rustproof effect can be obtained and provided as an electromagnetic wave shielding material.

Claims (1)

[Claims] 1. A surface of a metal-coated flame-retardant fiber woven fabric is coated with a urethane resin, and the surface thereof is treated with an organic compound flame retardant or a mixture of an inorganic compound flame retardant aid and an organic compound flame retardant. A flameproofing method for a metal-coated fiber woven fabric, which comprises coating and further coating the surface thereof with a urethane resin.