JPH01298280A - Production of flame-retardant fabric and flame-retardant fabric - Google Patents

Abstract

PURPOSE:To obtain the title excellent fabric of little smoking, resistant to melt snagging by coating a fabric with a dope prepared by dissolving in a solvent a chlorinated vinyl chloride resin and specific metal-contg. inorganic solid powder followed by solvent removal and gelling the resin component. CONSTITUTION:A dope is prepared by dissolving or dispersing in an organic solvent (e.g., tetrahydrofuran) (A) 100 pts.wt. of a chlorinated vinyl chloride resin, pref. 60-72% in chlorine content and >=0.37 in specific viscosity, (B) a softening agent (e.g., selected from halogen-contg. plasticizers, phosphorus-contg. plasticizers etc.), and (C) >=10 pts.wt. of metal-contg. inorganic solid powder selected from compounds of group II-V metals. This dope is coated on the both surfaces of a base fabric followed by heating and vaporizing said solvent to effect gelling the resin component, thus obtaining the objective flame- retardant fabric. This fabric gives such characteristics as little smoke generation even exposed to sparks or flames, resistance to causing melt snaggings, and prevention of flame spreading.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is flame retardant and flameproof, and generates little smoke even during forced combustion, and prevents melt molding and burnout caused by combustion.
This article relates to a method for manufacturing a flame-retardant fiber cloth that is resistant to fire and the flame-retardant fiber cloth obtained by the method, and is used for construction purposes, fireproof sheets, curtains for welding factories, and other applications requiring flame resistance and flame retardancy. It is used in various fields.

[Conventional technology and its problems]

Textile fabrics used at construction sites, welding factories, shipbuilding factories, etc., such as curtains, wall materials, sheets, etc., are always at risk of being exposed to welding sparks and fire. To prevent this, combustible textiles are laminated with flammable plastic on the surface, or the fibers themselves contain flame retardants. Although it has been made flame retardant by making it 9-coated, it is often insufficient for practical use. For example, if a curtain made of flame-retardant fiber cloth laminated with soft flame-retardant vinyl chloride resin is directly exposed to sparks or fire, it will generate a large amount of black smoke, and the resin part will immediately melt and droop. However, there is a drawback that the function as a flame retardant curtain is lost, such as the parts where sparks are attached are missing. In addition, sheets laminated with flame-retardant synthetic rubber have poor bending resistance and rubber elasticity (although they have poor flame retardancy) and generate a large amount of soot. It produces smoke and easily ashes and burns out when exposed to flames.Additionally, it has the disadvantage that it deteriorates quickly outdoors due to its poor weather resistance, and to improve this, it is made into a thick molded product, which is heavy and difficult to handle. It has the disadvantage of being inconvenient.

In this way, with conventional flame retardant technology for combustible fiber cloth, it is possible to prevent the disadvantage that when exposed to fire for a long time, parts of the fabric become chipped, ash, etc., and the flame retardant function is lost. There wasn't.

Therefore, an object of the present invention is to improve the above-mentioned drawbacks, and to prevent the melt from drooping even when exposed to sparks, molten iron particles, fire, and high temperatures for a long time.
A soft, flame-retardant material that can maintain its function as a flame-retardant curtain, flame-retardant sheet, or fire-proof hole sheet by blocking flames for 1fr, by leaving hard cinders without becoming chipped or burnt to ash even if it is carbonized by forced combustion. An object of the present invention is to provide a low-smoke flame-retardant fiber cloth and a method for producing the same.

[Means for solving problems]

The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result of their intensive research, they have discovered that a) a chlorinated vinyl chloride resin and b) a metal-containing inorganic material containing one or more compounds selected from the compounds belonging to Groups ① to ② of the Periodic Table. This patented flame-retardant fiber cloth is obtained by impregnating or applying a dope prepared by dissolving or dispersing solid powder in a solvent onto fibers or fiber base cloth, and then removing the solvent and gelling the bait components. The inventors have discovered that a manufacturing method and a flame-retardant fiber cloth obtained by the method can achieve the above objects, and have arrived at the present invention.

Hereinafter, the flame-retardant fiber cloth of the present invention will be explained in detail.

The chlorinated vinyl chloride used in the present invention usually has a chlorine content of about 59 to 72% by weight and a specific viscosity (JIS K67
(according to 21) of about 0.2O or more, preferably a chlorine-containing spear of about 60 to 69 weight t% and a specific viscosity of about 0.26 or more, more preferably a chlorine content of about 63 to 6
Chlorinated vinyl vinyl having a specific viscosity of 6% by weight and about 26 or more is suitable because it has excellent burnout resistance, low smoke properties, and rubber elasticity. As a method for producing chlorinated vinyl chloride, for example, 1
It is produced by chlorinating vinyl chloride resin powder in a gas phase, suspended in water, or dissolved in a solvent; for example, Japanese Patent Publication No. 36-888 and Japanese Patent Publication No. 45-30833 The memorial will be left in the manner described in the official bulletin.

Furthermore, in the composition of the present invention, a blend of 100 M parts of chlorinated vinyl chloride resin and 100 parts by weight or less of vinyl chloride resin can also be used.

Furthermore, as the softener used in the present invention, a plasticizer and/or an elastomer is used. Possible efl uls include dioctyl phthalate (D OP ), dibutyl phthalate (
Phthalic acid plasticizers such as DBP), phosphoric acid plasticizers such as trioctyl phosphate (TOF) and tricresyl phosphate (TCP), chlorinated paraffins, polymer ester plasticizers, epoxy plasticizers, Plasticizers such as mellitic acid ester plasticizers are preferably used.

Furthermore, from the viewpoint of flame retardancy, haloin-containing yarn plasticizers and phosphorus-containing plasticizers are sometimes preferred, and trioctyl phosphate is particularly preferred.

When an elastomer is not used in combination, the amount of plasticizer used is preferably 20 parts by weight or more, particularly preferably 50 parts by weight to 12 parts by weight, per 100 parts by weight of the chlorinated vinyl chloride resin.

Examples of elastomers include chlorinated polyethylene with a price of 30 to 50 yen, chlorinated com, fluorine rubber, chloroprene rubber, nitrile butadiene rubber, nitrile rubber, ethylene-vinegar, vinyl copolymer and its craft polymer polyurethane elastomer, Elastomers such as polyester elastomers, ethylene-propylene-diene terpolymers, polystyrene elastomers, ethylene-propylene copolymers, and crosslinked products of these rubbers are used.

In addition, the amount of the softener used depends on the hardness (
Based on JIS K6301 spring type hardness test method A)
The amount of the softener used is preferably 20 parts by weight or more, particularly preferably 50 to 12 parts by weight, based on 100 parts by weight of the chlorinated vinyl chloride resin.

Further, the metal-containing inorganic solid powder used in the present invention is a powder containing one or more compounds selected from metal compounds belonging to groups ① to ② of the Hajiki Table, including Mg, (:1゜Zn, Ba1Al,
Compounds of metals such as Ti%Zr, Sn%Pb, P, and 8b are suitable. In particular, when the hydroxides and oxides of these metals are present at the same time, they are effective in forming a strong carbonized shell due to the mutual effect with 14-vinyl chloride during forced combustion, and the flame retardant properties are improved. It is suitably used for imparting. For example, hydroxides of these metals include lucium hydroxide, magnesium hydroxide, aluminum hydroxide, and oxides include zinc oxide, lead oxide, antimony trioxide, titanium oxide, and aluminum oxide. In addition, lucium carbonate, tin chloride,
Phosphorus-containing compounds such as phosphorous aluminum, phosphate glass powder, ammonium phosphate, and inorganic glass powders containing these metals are used.

More preferably, the metal-containing inorganic solid powder is a) PgOa
glass powder containing at least 30% by weight of phosphorus,
Alternatively, a mixed powder of a phosphorus compound, b) metal hydroxide, and c) metal oxide is used.

These mixed powders can also be used after being subjected to surface treatment such as silane treatment so as not to reduce the strength of the resin. When the above mixed powder is used, it has particularly excellent flame resistance, and even if small particles of molten metal adhere to it, only the attached part will sinter and harden, forming a hard shell to prevent the spread of fire to other parts. It is difficult to chip or sag, and is highly effective in maintaining its flame retardant function.

Regarding the particle size of the metal-containing inorganic solid powder, the average particle size is 1.
It is preferable that the particle diameter is 00μ or less, and more preferably, if a fine powder with an average particle size of 50 to 2μ is used, it is highly effective in forming a strong carbonized shell due to the mutual effect with chlorinated vinyl chloride during forced combustion. Provides high flame resistance.

C) Each use of metal-containing inorganic solid powder is used in an amount of 10 parts by weight or more per 100 parts by weight of chlorinated vinyl chloride resin, preferably 30 to 250 parts by weight, particularly 50 parts by weight.
~150 parts by weight is preferred.

In the present invention, the composition ratio of a) chlorinated vinyl chloride resin, b) softener, and C) metal-containing inorganic solid powder is a): b
) : c) = 100: 2O~12O: 10~
Used in a ratio of 250.

The textile fabric according to the invention is typically manufactured by hand in the following manner. That is, 1 selected from a) a chlorinated vinyl chloride resin, b) a softening agent, and C) a compound belonging to Groups ■ to ■ of the Old Table of Laws.
A dope prepared by dissolving or dispersing the composition mixture of the present invention containing metal-containing inorganic solid powders in a solvent is impregnated or applied onto the fiber base fabric or fibers.

Next, the solvent is removed by heating or drying to gel the solid content, and the treated fibers are further woven into a cloth using a loom to produce the flame retardant fiber cloth of the present invention.

The solvent used at this time is preferably a solvent that has affinity with the vinyl chloride resin, such as tetrahydrofuran (THF),
Examples include, but are not limited to, ethyl acetate.

Although the ratio of the solvent to the chlorinated vinyl chloride resin can be freely selected, it is preferably 95:5 to 50:50, particularly 80:2O.
~65:35 is suitable.

Further, as the fiber base fabric used in the present invention, a fiber base fabric composed of arbitrary fibers such as natural fibers, synthetic fibers, organic fibers, and inorganic fibers can be used. For example, natural fibers include plant fibers, animal fibers, mineral fibers, etc., and man-made fibers include gold! 14
Fibers, inorganic fibers such as glass fibers, rock fibers, mineral slag fibers, cellulose yarns such as viscose rayon, nitrocellulose, acetate, acetic acid sulphate, etc. tJ1. fibers, polyamide fibers, polyester fibers, polyurethane fibers, polyethylene fibers, polypropylene fibers, polystyrene fibers, IJJM vinyl fibers, polyfluoroethylene fibers, polyacrylic fibers, polyvinyl alcohol fibers, etc. Synthetic fibers, natural rubber, chlorinated rubber, etc., special inorganic fibers such as glass fibers, mica and asbestos fibers,
Teflon fibers in rock fibers and synthetic fibers have excellent flammability,
Preferably used.

Also, the thickness of the fibers that make up the fiber base fabric is 10d to 1000d.
is preferably used, but 100 d to 500 d is suitable for the load, and the number of fiber bundles is 10 × 10 / inch to 100
A ratio of 100 books/inch is suitable.

The composition of the dope used in the present invention further includes conventional dispensing agent components for chlorinated vinyl chloride, such as stabilizers, lubricants, flame retardants, blowing agents, processing aids, antistatic agents, antioxidants, pigments, etc. Can be distributed.

The flame retardant fiber cloth according to the present invention manufactured in this way is
By selecting the types and amounts of the constituent components, it is possible to impart softness and suppleness that suit the intended use.

Examples of the present invention are listed below. In the examples, "part" and "chi" indicate "part by weight" and "% by weight", respectively.

Example 1 a) 100 parts of chlorinated vinyl chloride resin with a chlorine content of 68% and a specific viscosity of 0.30, b) 50 parts of trioctyl phosphate as a softening agent, and c) trioctyl phosphate with an average particle size of 10 μ as a metal-containing inorganic solid powder. 2O parts of antimony oxide, average particle size 10μ
20 parts of aluminum hydroxide and 2 parts of dibutyltin mercaptide as a stabilizer were added, and 50"C x 2
A test dope was prepared by dissolving and dispersing K9/c71 for about 60 minutes.

Next, a polyester base fabric printed at 250 d, 31 x 30 lines/inch was prepared, and the test dope prepared above was applied to both sides of the base fabric. Tetrahydrofuran was volatilized in a dryer adjusted to 150 to 180°C, and a test sheet with a thickness of about 600 μm was prepared by gelling the resin component. Using this sheet, each characteristic was evaluated and the results are shown in the third article.

[Examples 2 to 8] The composition of the test dope was a) 4-corded J soybean vinyl resin;
A test sheet was prepared in the same manner as in Example 1 except for b) a softener and C) a metal-containing inorganic solid powder as shown in Table 1 and Dototel, and each property was evaluated. The results are shown in Table 3.

[Comparative Examples 1 to 4] The composition of the test dope was as follows: a) 4-grade vinyl chloride resin;
A test sheet was prepared in the same manner as in Example 1 except that b) softener and C) metal-containing solid powder were used as shown in Table 2 (j ingredients and amounts shown), and each property was evaluated and the results were Table 4 is shown below.

[Characteristic evaluation method]

One test sheet prepared in Examples and Comparative Examples was used to perform one 1Ff song of each time according to the following test method.

1) Appearance/Feel Test Observe the smoothness of the sheet surface, the presence or absence of IJ-de such as plasticity, stickiness, texture, etc., and those with problems are marked as "defective", and those without problems are marked as "defective". It was rated as "good".

2) Hardness: Use a spring-type hardness test type A specified in 5 of JIS K6301. A test piece of approximately 25 x 70 mm and 12 mm thick made by stacking test sheets is used. Hold the hardness tester horizontally on the test piece, and lightly touch the pressure surface so that the indenter is perpendicular to the test piece measurement surface. The hardness was determined by reading the scale within 1 second after contact.

3)! The oxygen index was measured using a flammability test sheet according to the method specified in JIS K72O1.

4) A flame-resistant test piece (300 x 300 mm laminate sheet) set horizontally on propane is supported at a position 150 degrees from the burner outlet so that the flame of the sburner is vertically concentrated, and the propane gas is placed in the center of the test piece. A burner flame (flame length 2O0 ++n) was applied directly to the sheet, and the smoke generation status, the time required for the flame to penetrate the sheet, and the degree of deformation of the sheet were evaluated.

5) Melt the tip of an iron rod with a blast resistance of approximately 3 mm with a gas burner, and
As the molten iron grains of the Tomo ball, the thickness is about 600μ, the width is 300X3
Five drops were dropped scattered on a 00 mm test sheet, and the amount of smoke, combustibility, and missing area were evaluated. The evaluation method was as follows.

Smoke amount: The amount of smoke generated was determined with the naked eye.

Flammability: Molten iron particles were dropped onto a test sheet, and the average time (see) from when a flame was generated until it disappeared was measured.

Missing area: When the test sheet was melted and burned by dripping molten iron particles, the area (-) of the resulting missing penetration part was measured. Compared to conventional fiber AH, it generates less smoke even when exposed to sparks, molten iron particles, flame, and high temperatures, and causes melt droop and apertures.

In addition, even if it is carbonized by forced combustion, it is difficult to break off or burn to ash, leaving hard cinders that can cause flames and prevent the spread of fire, which is a characteristic that could not be achieved with conventional technology. There is.

Therefore, it can be seen that the present invention provides flame-retardant and fire-retardant fibers and fiber cloths that have extremely excellent functions for use in flame-retardant curtains, flame-retardant sheets, and the like.

Claims (10)

[Claims] (1) a) Chlorinated vinyl chloride resin and b) Periodic Table I
A dope prepared by dissolving or dispersing a metal-containing inorganic solid powder containing one or more compounds selected from Groups I to V in a solvent is impregnated or applied onto fibers or fiber base fabric, and then the solvent is removed and the resin component is removed. A method for producing a flame-retardant fiber cloth, characterized in that it is obtained by gelation. (2) Claim 1, wherein the a) chlorinated vinyl chloride resin is c) a resin composition containing a softener.
A method for producing a flame-retardant fiber cloth as described in Section 1. (3) The chlorine content (Cl%) of the chlorinated vinyl chloride resin
60 to 72%, and a specific viscosity (ηsp) of 0.37 or more. (4) The softening agent (c) includes at least one selected from the group consisting of a halogen-containing plasticizer, a phosphorus-containing plasticizer, and a silicone oil-based plasticizer.
A method for producing a flame-retardant fiber cloth as described in Section 1. (5) The softening agent c) is chlorinated polyethylene, ethylene vinyl acetate copolymer and its graft copolymer, nitrile rubber,
polyurethane elastomer, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer,
2. The method for producing a flame-retardant fiber cloth according to claim 1, which comprises one type of elastomer selected from the group consisting of fluororubber, chloroprene rubber, and silicone rubber. (6) Claim 1, wherein the metal-containing inorganic solid powder (c) contains a metal hydroxide and a metal oxide.
A method for producing a flame-retardant fiber cloth as described in Section 1. (7) The flame-retardant fiber fabric according to claim 1, wherein the metal-containing inorganic solid powder c) contains at least 30% by weight of phosphorus in terms of P_2O_5. (8) The average particle size of said c) metal-containing solid powder is 50μ to 0
．． 2μ. The method for producing a flame retardant fiber cloth according to claim 1. (9) A tent, canvas, and construction sheet made of the flame-retardant fiber cloth according to claim 1. (10) a) Chlorinated vinyl chloride resin and b) Weekly table number
A dope in which a metal-containing inorganic solid powder containing one or more compounds selected from Groups II to V is dissolved or dispersed in a solvent is impregnated or applied onto fibers or fiber base fabric, and then the solvent is removed and the resin component is removed. A flame-retardant fiber cloth characterized by being obtained by gelation.