JPH0313356B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a flame-retardant suede-like fabric that satisfies both flame retardancy and flexibility. Conventionally, vinylphosphonate and dialkylphosphonocarboxylic acid amide compounds have been applied to flame retardant cellulose fibers, especially cotton.
However, such flame retardation is achieved by applying a mixed reaction solution system of the above compound or its methylol compound, formaldehyde, a monomer compound containing a reactive functional group, and a reaction catalyst to cotton and causing it to react and fix. Ta. Such flame-retardant fiber products are extremely coarse and hard, and cannot be applied to products that place a high value on soft touch. In addition, in recent years, synthetic resins such as artificial leather and composite materials made of resin have been widely used for clothing, interior materials, industrial materials, etc. For example, for clothing, coats,
It is used for jumpers, suits, etc., and as an interior material for vehicles such as aircraft, ships, trains, and automobiles, and for high-end interiors such as hotels, such as seats, sofa seats, curtains, and wall materials. However, unlike clothing and industrial materials, interior materials are subject to strict legal regulations because of the serious human damage caused by fires, and the reality is that only those that pass these standards can be put to practical use. Various flame-retardant products made of ordinary fibers are known, but flame-retardant products made of composite materials made of synthetic resins and resins have the following problems.
It has not been easy to add flame retardant properties to luxury products without impairing their value. (1) The combustion mechanisms of synthetic fibers and resins are different, and there has been no material that satisfactorily achieves flame retardancy for both. (2) In order to satisfy flame retardancy, it is necessary to mix and contain a large amount, resulting in rough hardening of the texture,
There were drawbacks such as a decrease in color fastness and a sticky feeling. (3) The flame retardant easily migrates, resulting in a sticky feeling and oozing of the dye, which has the disadvantage of impairing the surface quality. As a result of studying these problems, the present inventors have discovered a special flame-retardant compound that also has a softening effect on elastic polymers. That is, as mentioned above, vinylphosphonate compounds and dialkylphosphonocarboxylic acid amide compounds have been conventionally used as components of reactive flame retardants for cellulose fibers such as cotton, but the inventors of the present invention investigated the fact that by allowing the compound to exist alone in an elastic polymer, the elastic polymer can be made extremely flexible and at the same time exhibit sufficient flame retardant performance, and have achieved the present invention. did. That is, the present invention has the following configuration. (1) At least 2% by weight of an elastic polymer and at least 0.8% by weight of at least one flame retardant selected from vinylphosphonate compounds () or dialkylphosphonocarboxylic acid amide compounds () represented by the following general formula. with a sexual compound,
1. A flame-retardant suede-like fabric comprising a suede-like fabric having a raised portion on at least one side. Vinylphosphonate compounds () Here, R, R' = C ₁ to C ₃ alkyl group Y = 2 to 10 dialkylphosphonocarboxylic acid amide compound () Here, R″=alkyl base of C ₁ to _{C 3} By adopting the above configuration, the present invention is compatible with, for example, JIS D-1201, FMVSS-302, and even JIS L
-1091, DOCFF-5-74, and exhibits excellent flame retardant properties.
It has been possible to provide a flame-retardant suede fabric that can achieve a soft feel that has never been seen before. In particular, for products with raised naps, the commercial value can be greatly improved without impairing their high-class image. The present invention uses elastic polymers such as polyurethane resins, acrylic resins, vinyl chloride resins, natural rubber, chloroprene rubber, and SBR, which are usually used as fiber impregnating resins or binder resins. Such polymers may contain additives such as matting agents, pigments, dyes, and stabilizers. Such elastic polymers are important as supports for holding the above-mentioned compounds, flame retardants, etc., and are present in suede-like fabrics at least 2% by weight, preferably 4% by weight.
It is necessary to make it exist. If the amount is less than 2% by weight, the effect as a support is insufficient. The vinylphosphonate compounds and dialkylphosphonocarboxylic acid amide compounds of the present invention are compounds represented by the following general formulas () and (). As a compound of (), Here, R, R' = alkyl group of c ₁ to c ₃ X, Y = 2 to 10 3 The above-mentioned compounds further include those to which an organic phosphorus compound such as a phosphoric acid ester is bonded. For example, as a compound of (), Here, R''=alkyl group of c ₁ to _{c 3} The H of the -NH group of the compounds 1 to 2 above is further -
those substituted with CH ₂ OH groups, as well as −
A condensation of at least one CH ₂ OH group, and an organic phosphorus compound having another -CH ₂ OH group in the -CH ₂ OH group, such as tetrahydroxymethylphosphonium or phosphoric acid ester of methylolated dicyandiamide. Contains combined items. There are two types of flame retardants, carbonized type and self-extinguishing type, and the above-mentioned compound of the present invention has the property of self-extinguishing type. An interesting feature of the above-mentioned compounds is that they effectively exhibit an autoextinguishing action by causing combustion materials to fall out of the combustion zone. Therefore, although the combustion part may fall off and be damaged, it has the effect of reliably preventing damage from the spread of fire. Among the compounds () and () above, the compounds () having a molecular weight of 500 to 2000 and the compounds represented by ()-1 and -2 are excellent in flexibility and flame retardancy. When such a compound is used in a composition with an elastic polymer, its amount in the composition is at least 10% by weight, preferably 20 to 50% by weight. Ten
If the amount is less than % by weight, the plasticizing effect and flame retardancy will not be sufficiently exhibited, and it is rather desirable that the amount be present in a large amount. However, if the amount is too large, the dye tends to ooze out and cause stickiness defects, so it is appropriate to keep it at 50% by weight or less. Note that other flame retardants may be added to this composition in order to further improve the flame retardant performance. The above-mentioned compounds of the present invention are effective because they act synergistically with the performance of such flame retardants and can bring out and utilize the performance to the fullest. Such flame retardants include, but are not particularly limited to,
Examples include phosphorus-containing compounds such as halogenated phosphoric acid esters and ammonium polyphosphates, halogen-containing compounds such as halogenated cycloalkanes and halogenated aromatic compounds, and flame retardants such as antimony trioxide. Such a flame retardant can be added in an amount up to 6 times the amount of the above-mentioned compound of the present invention, but it is preferably added in an amount of 60% by weight or less in the composition due to drawbacks such as flexibility and dye exudation. When such a composition is applied as a binder to be applied to one surface of a suede-like fabric, the ratio of the elastic polymer to the compound is preferably 1.0 or less. The more elastic polymer there is, the more it tends to impede flame retardancy. In other words, the binder in this case has the effect of diffusing and transferring the compound or flame retardant to an area other than the binder and imparting flame retardant performance to that area, but when the amount of elastic polymer increases, It begins to show a tendency to inhibit the above-mentioned diffusion and migration. Furthermore, elastic polymers are flammable materials, and when the amount of such combustible materials increases, a problem arises in that the flame retardant blended to make the polymer flame retardant is consumed. This binder is placed on the back side of the suede fabric.
It can be applied by a method such as an impregnation method, a spray method, or a coating method. The compound and the flame retardant contained in the binder are contained in the interior below the surface of the suede fabric.
Preferably 2/2 of the thickness from the back side of the suede-like fabric.
It is preferable to keep the distribution within the range of up to 3, especially up to 1/2, from the viewpoint of surface quality, color fastness, dye oozing, stickiness, etc. In such a distribution state, the amount of the compound of the present invention contained in the suede fabric is at least
It is 0.8% by weight, preferably 1.5% by weight or more. The higher the content of the compound, the better the flexibility and flame retardancy; however, if the content is too high, the effect will be saturated and the compound will be diffused and migrated, affecting the surface quality, so it is preferably within a range of 20% by weight or less. should be kept below 15% by weight. The suede-like fabric as used in the present invention is composed of a knitted fabric or a non-woven fabric containing an elastic polymer having raised naps on at least one side. Examples of synthetic resins used in such suede-like fabrics include fibers or recycled fibers whose main component is a polymer such as polyester, polyamide, or polyacrylonitrile.
Among them, for example, fibers made of polyethylene terephthalate, polybutylene terephthalate, copolymers of these with isophthalic acid, isophthalic acid sodium sulfonate, etc., polyesters such as polyoxyethyl benzoate, nylon 6, nylon 66, nylon 610, nylon 12, etc. Fibers made of polyamide can be selected from the viewpoint of physical properties. By constructing a suede-like fabric from composite fibers made of such synthetic fibers, for example, polymer components having different physical and chemical properties are selected.
By removing one of the components in post-processing, there is an advantage that a porous suede-like fabric can be easily obtained. When the porous suede-like fabric (base fabric) is in the form of a non-woven fabric, it is preferable from the viewpoint of physical properties that it is interlaced by a needle punching method. The elastic polymer of the present invention and the above-mentioned compounds include those contained in suede-like fabrics made of synthetic fibers, but are not limited to the manner in which they are contained. For example, the compound is contained on the back side of a suede-like fabric impregnated with an elastic polymer, and the composition (binder) containing the compound is contained, or the compound is mixed with the elastic polymer to be impregnated. Alternatively, a combination of these may be adopted. In the suede-like fabric of the present invention, the disadvantages caused by the compound and the flame retardant significantly impair its high-class image, and it is preferable to avoid them as much as possible. It is preferable that the compound be contained in a biased distribution state with a thinner concentration and in a form that is not substantially present on the surface. Next, the method for manufacturing the flame-retardant suede-like fabric of the present invention will be explained by giving one example. For example, a case will be described in which a composition comprising an elastic polymer and the above compound is used to impart flame retardancy. First, typical compositional examples of such compositions are shown below. (Part) Vinylphosphonate compound or/and dialkylphosphonocarboxylic acid amide compound 5-10 Elastic polymer 2-8 Flame retardant 0-30 Dispersant 0.5-3 Thickener 0.5-3 Water x 100.0 Such composition The viscosity is preferably adjusted to 1000 cps or more, more preferably 2000 to 5000 cps.
It is preferable in terms of ease of coating, distribution of the compound, etc. This composition is applied (impregnated) on the back side of the suede-like fabric by coating, etc.
It is heated and fixed at a temperature preferably in the range of 110 to 130°C. The treatment time is determined while controlling the state of permeation and distribution of the compound, but is usually about 10 to 15 minutes. The suede-like fabric may have a backing material such as a fiber cloth as a reinforcing material on the back surface in practical use in order to stabilize physical properties and dimensions. The above-mentioned composition has the effect of causing combustible materials to fall off and away from the combustion area, is self-extinguishing, and also has the characteristic of plasticizing and softening elastic polymers such as impregnated polymers and binder resins, such as vehicles (aircrafts, Suede-style fabrics are ideal for use in luxury interiors such as trains, automobiles, ships, etc.) and hotels, such as seats, sofas, walls, and curtains. The present invention will be further explained below with reference to Examples. Example 1 Artificial suede made of polyurethane-impregnated thermoplastic synthetic fiber with a thickness of 1.2 mm (“Ecsaine” manufactured by Toray Industries)
A polyester fabric having a basis weight of 80 g/m ² was heat-sealed to the back side of the fabric as a backing fabric using a low melting point polyamide resin adhesive. Next, a vinylphosphonate compound represented by the general formula below is 10 parts, tris dichloropropyl phosphate 10
part, 8 parts of ammonium polyphosphate to acrylic resin (Nippon Reichhold, Boncoat WP-
210) Mix 6 parts with 65 parts of water as a thickener.
One part of CMC was added to create a binder resin composition with a viscosity of 3000 cps. This binder resin composition was applied to the backing cloth surface of the artificial suede using a round-blade knife coater, and then heat-treated at 110° C. for 15 minutes. The amount of the composition deposited was 16% by weight. For comparison, a binder resin composition with the same solid content was prepared by adding 5 parts of each of the other two components in place of the vinyl phosphonate compound of the general formula in the above binder resin composition. Similarly, it was applied to the same artificial suede backing fabric surface, and a coating amount of 16% by weight was obtained. Regarding these, flame retardancy (burning rate) was measured according to the FMVSS-302 standard, and flexibility was measured according to the JIS-L1079 standard.

【table】

[Table] Example 2 Artificial suede made of polyurethane-impregnated thermoplastic synthetic fiber with a thickness of 0.8 mm (“Ecsaine” manufactured by Toray)
20 parts of methylolated dimethylphosphonopropionic acid amide (Pyrobatex CP manufactured by Ciba Geigy) and decabromodiphenyl ether on the back side of the
Mix 15 parts of antimony trioxide and 5 parts of antimony trioxide with 6 parts of acrylic resin (Ultrasol 2635 manufactured by Takeda Pharmaceutical Co., Ltd.) and 53 parts of water, and add 1 part of CMC as a thickener to make a binder resin composition with a viscosity of 2800 cps. Ivy. After applying this binder resin composition to the back side of the artificial suede using a round blade knife coater,
Heat treatment was performed at 110°C for 15 minutes. The amount of the composition applied is
It was 28% by weight. As a comparative example, in place of dimethylphosphonopropionic acid amide in the above binder resin composition, 15 parts of decabromodiphenyl ether and 5 parts of antimony trioxide were added to make a binder resin with the same solid content, and this was prepared as described above. Same as the example, applied to the back side of the same artificial suede, 28% by weight
I got one with a lot of adhesion. Regarding these, FMVSS-302 standard, JIS-
Microburner method of L1091 and DOC-FF-5-
Flame retardancy was measured according to the 74 standard. Also JIS-
Flexibility was measured according to the L1091 standard, and the state of adhesion of the binder resin composition was judged visually. The results are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1. At least 2% by weight of an elastic polymer and at least 0.8% by weight of at least one selected from vinylphosphonate compounds () or dialkylphosphonocarboxylic acid amide compounds () represented by the following general formula. 1. A flame-retardant suede-like fabric comprising a flame-retardant compound containing a flame-retardant compound in a suede-like fabric having a napped portion on at least one side. Vinylphosphonate compounds () Here, R, R' = C ₁ to C ₃ alkyl group Y = 2 to 10 dialkylphosphonocarboxylic acid amide compound () Here, R″=C ₁ to C ₃ alkyl group