JPS5813786A - Fire retardant artificial suede like structure - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a human varnished structure having flame retardant properties. More specifically, the present invention relates to a flame-retardant structure made of synthetic fibers containing 9-layer varnished polyurethane.

In recent years, progress has been made in the development of human varnished fabric, which has thermoplastic synthetic fibers containing polyurethane in its pile yarns, and has come to be widely used as a material for clothing.

These human varnished fabrics include nonwoven fabrics made of ultrafine fibers impregnated with a polymeric elastic material as a binder, and knitted fabrics made of raised ultrafine fibers.

＼ There is also active research into applying structures that take advantage of the characteristics of raised artificial leather to applications other than clothing.

Artificial leather made of synthetic fibers containing a polymeric elastomer mainly composed of polyurethane is required to be flame retardant when used for interior applications such as automobile interior materials and upholstery.

A human varnished structure has characteristics in its structure and texture.In particular, reducing the quality of both surface and nape texture means losing its commercial value. There are voids in the nonwoven fabric (or knitted fabric), making it easily flammable.

(2) The flame retardant mechanism of polyurethane thermoplastic synthetic fibers is different.

(3) Flame retardants tend to impair the quality of both surface and nape texture, and also reduce light resistance.

(4) Flame-retardant finishing induces a decrease in color fastness and hardening of the texture.

etc.

A flame-retardant suede-like structure that completely eliminates these problems has not yet been proposed.

In order to solve this problem, the present inventors conducted a study on a flame retardant composition suitable for varnished structures, and found that a specific combination of compounds favorably penetrates into the structure. We have discovered that this product exhibits extremely good flame retardancy without any loss in quality of texture, and have arrived at the present invention! Shita.

That is, the present invention has the following technical configuration.

In the human varnish needle-like structure, a flame retardant composition consisting of an acrylic ester resin, the following compound (A), and at least one compound selected from the group (B) is contained on the back surface of the raised part. A flame-retardant artificial leather-like structure.

(A) O=P÷0CH2CHXCH,X)s or 0'=P+0CH(CH,X)CH,X),
A halogenated phosphate ester represented by (X: C1,Br).

CB) Ammonium polyphosphate, guanidine phosphate, ammonium phosphate, ammonium bromide.

Ammonium chloride, ammonium sulfate, ammonium sulfamate.

The present invention complies with the flame retardant regulations regarding automobile interior materials without changing the surface quality of the surface-puffed artificial leather-like structure made of polyurethane-impregnated thermoplastic synthetic fibers.
The present invention provides a structure that has flame retardancy that passes FMVss-3o2 and FMVSS-3O2 of the American standard, and has less hardening in texture and less deterioration in physical properties.

Of course, the human varnish needle-like structure as used in the present invention may be one having raised portions on both sides of the base layer.

Here, the base layer is composed of a nonwoven fabric-like substrate or a knitted fabric-like substrate containing polyurethane. Further, a backing material such as polyester fiber cloth may be provided on the back side for reinforcement.

The raised portion is formed into a suede-like appearance by raising the surface layer of at least one side of the polyurethane-impregnated substrate or by impregnating the raised trailing curtain with polyurethane.

Examples of thermoplastic synthetic fibers constituting the base of such a varnish-like structure include polyethylene terephthalate or copolymers of this with isophthalic acid, sodium isophthalate, etc., polyesters such as polyoxyethyl benzoate, and polybutylene terephthalate. type fibers, nylon 6, nylon 66, nylon 610.
Examples include polyamide fibers such as nylon 12.

In order to form a suede look more conveniently, it is desirable that the substrate be made of ultrafine fibers of, for example, 0.5 denier or less.

9. The thickness of the base of such a suede-like structure varies depending on the type of structure. Although not particularly limited.

It is usually about 0.3 to 2 mm.

The base of the structure of the present invention is impregnated with a high-molecular elastic polymer such as polyurethane, and if necessary, in addition to this polymer, natural rubber, chloroprene rubber, SBR, acrylic comb-like material, fluorine-based A rubber-like substance such as a rubber-like substance or a silicone-based rubber-like substance may be used in combination, as well as a matting agent and a pigment.

It may also contain additives such as stabilizers.

In the present invention, a flame retardant composition is contained on the back side of the raised portion on the surface of the substrate, and the term "back side" here refers to the casing or lining surface of the substrate itself, and the flame retardant composition is Materials may be applied to any of these back sides.

In the present invention, the non-flame retardant composition is composed of the following specific compounds. That is, with acrylic ester resin.

(A) O, P + OCH, CHXCH, X)s
or 0 =, P +0CH(C1-1,X)CH,X)
, (X: Cj, Br) (B) ammonium polyphosphate, guanidine phosphate, ammonium phosphate, ammonium bromide.

It is a composition consisting of at least one compound selected from ammonium chloride, ammonium sulfate, and ammonium sulfamine.

The above-mentioned acrylic ester resin has excellent adhesion as a binder, has excellent flexibility, does not harden in texture, does not cause dye bleed, and does not reduce color fastness. Yes, this Uoshin binder resin such as ethylene-vinyl acetate copolymer,
There is a marked difference in action from polyvinyl chloride, polyurethane resin, etc. This difference in action makes a significant difference in terms of dye bleed, texture hardening, etc. in thin human varnish needle-like structures.

The shining acrylic ester resin is composed of an alkyl ester of acrylic acid or methacrylic acid,
Acrylic alkyl esters are particularly preferred. As the alkyl group, those having methyl, engineering, thyl, propyl, butyl, and a C1 to C5 alkyl group having a branched chain can be used. In particular, branched alkyl acrylates have excellent flexibility and are suitable for the present invention.

Among such acrylic ester resins, copolymers consisting of two or more, especially three or more, of the above acrylic esters have excellent solvent resistance and moisture fastness9, for example, ether acrylate/butyl acrylate/2-ethylhexyl. Anorylate copolymers and the like are preferably used in the present invention. The proportions of each component in these copolymers are appropriately determined depending on the desired film-forming properties and flexibility. A copolymerization ratio containing ethyl acrylate as a main component (50% by weight or more) is preferred.

Next, the halogenated phosphate ester shown by the above general formula (
A) is a human varnish: □・It has excellent affinity for the polyester fibers and polyamide fibers that make up the needle-like structure, and its permeability becomes even thicker through heat treatment. This compound has the effect of lowering the temperature of the polymer during combustion due to the synergistic action of these compounds.Furthermore, this compound is in the form of an oil.

Since it has the effect of softening the structure, it organically combines with the acrylic acid ester resin and effectively works to improve the feel of the structure.

Such compounds include, for example, tris dichloroisopropyl phosphate, tris 1.3 dichloropropyl phosphate, tris 2,3 dibromopropyl phosphate, tris chlorobromopropyl phosphate, and the like. Among them, tris dichloroinpropyl phosphate is excellent in terms of the above effects.

In addition, compounds of the above group (B) such as ammonium polyphosphate have the effect of promoting the complete carbonization of polyurethane and suppressing the flame propagation. It has a dehydration reaction with respect to polymers such as polyester, and has the effect of forming carbides at lower temperatures.

Furthermore, among these (B) group compounds, ammonium polyphosphate and guanidine phosphate do not corrode metals and are particularly suitable as components of flame-retardant compositions for use in automobiles and building materials.

Such flame retardant compositions are usually blended in the proportions shown in the following composition examples.

(A) 5 to 20 parts of halogenated or phosphoric acid ester compound (B) Group compound 5 to 30 parts.

Flame retardant components other than (A) and (B) 0 to 10 parts Polyacrylic acid ester resin 5 to 20 parts Dispersant,
Thickener 1-5 parts water
Part XIoo: The flame retardant performance of the flame retardant composition of the present invention is influenced by the mixing ratio of each flame retardant compound component and the composition ratio with the acrylic ester resin component, and the appropriate ratio is determined for the purpose of processing. The material of the varnish-like structure.

It varies depending on the tissue and thickness. It is also affected by the permeability of the flame retardant composition component applied to the back surface of the structure. According to the studies of the present inventors, the preferred composition ratio of the flame retardant composition is such that the total weight of the flame retardant compounds (A) and CB) is the sum of the weight of substances other than the flame retardant compound components such as acrylic acid ester resin. It is more than its weight. More preferably, the flame retardant compound component is preferably contained in an amount of 180 to 250% by weight based on the acrylic acid ester resin.

When coated, the acrylic ester resin content is higher than the flame retardant compound content.

As the flame retardant compound component increases, the amount of the acrylic acid ester resin component also increases, and therefore, in order to obtain high flame retardant performance, it is necessary to apply a large amount of the flame retardant composition.
As a result, only materials that are coarse and hard and have poor physical properties are obtained. On the other hand, if the acrylic ester resin component is small, it is necessary to fix the flame retardant compound component to the human varnish needle-like structure.
Defects such as falling off occur.

The flame retardant composition of the present invention contains a flame retardant compound (A
), (B) in a total amount of 15 to 30% by weight, and the acrylic acid ester resin is preferably contained in a proportion of 8 to 20% by weight.

In addition, in the composition of the present invention, other flame retardant compounds can be added if necessary, but in that case, the content of the flame retardant compound component is not more than 50% by weight, preferably not more than 30% by weight. It should be kept within a range that does not impede the purpose of the present invention. Note that the compound added here should avoid inorganic metal compounds and reactive flame retardant compounds.
Preferable in terms of texture and flexibility.

Further, in order to improve the adhesion of the composition, a crosslinking agent such as a halogenated cycloalkashi, a halogenated core compound, thiourea, etc. may be added to the extent that it does not impede the texture and flexibility.

As a method for applying such a flame retardant composition to the structure, a conventional coating method such as a doctor knife method-roller printing method can be applied.

In that case, the viscosity of the composition is adjusted to between 1000 and 8000 centipoise, preferably between 2000 and 4000 centipoise. For such viscosity adjustment, common thickeners such as polyvinyl alcohol, carboxymethyl cellulose, and starch paste can be used.

In the present invention, such a flame retardant composition is applied to the back surface of the structure, that is, to the base surface on the back side of the front and front raised portions, or to the backing material surface that reinforces the base surface. In this case, the viscosity of the composition is adjusted so that the components of the composition are distributed in the inner layer below the surface of the base layer, preferably within a thickness of V3 from the back surface, and more preferably within a thickness of V2. is preferable.

In addition to the viscosity of the composition, the amount of adhesion is important as a requirement for regulating such distribution. The amount of adhesion is 8 to 30% by weight (solid content) of the entire structure.

For example 1. In the case of a structure with a thickness of 2 mm and a basis weight of 400 g/m, 16 to 24% by weight (solid content) of the composition having a viscosity of 3000 centivoids is deposited.Of the above deposited amount, only the amount that permeates into the base layer of the structure is deposited. The amount contained is at least 2% by weight (solid content) and at most 4 to 10% by weight.
It is. If the amount of this adhesion is less than 2 tqb, the flame retardant effect will be poor, and if it exceeds 10 tqb, the flame retardant compound will seep out onto the surface of the base layer, causing raised pilings.

The following disadvantages are given to the section.

In other words, when a flame-retardant compound penetrates or adheres to, for example, a raised part, it causes dye bleeding in the raised part, and also causes a decrease in appearance, wind resistance, color fastness, and physical properties.

This results in a decline in commercial value. That is, in the human varnish needle-like structure of the present invention, the composition components are distributed at least within the base layer constituting the structure, below the surface of the base.

It is important that it is not distributed to the surface of the surface and the surface of the base layer. In order to achieve such a configuration, the present invention regulates the above-mentioned viscosity and adhesion amount, as well as the subsequent heat treatment.

That is, the structure coated with the flame retardant composition has a
Heat treatment is performed under a temperature condition of 200° C. to fix the composition and at the same time control the penetration of the composition components. Heat treatment temperature is 1
9. If the temperature is below 00°C, the flame retardant composition will not penetrate sufficiently into the varnish-like structure or substrate. The coating surface is sticky due to poor solidification. On the other hand, if the temperature exceeds 200°C, the penetration of the flame-retardant compound becomes excessive, resulting in a decrease in the color fastness and texture of the front raised areas. Preferably 110-1130
Penetration control is performed by heat treatment at ℃ for 10 to 15 minutes.

Thus, the flame-retardant composition of the present invention is contained in the base layer of the human varnish-like structure in a specific distribution.

In the flame-retardant artificial suede-like structure of the present invention, the flame-retardant compound rapidly penetrates into the napped part and other fiber parts due to the heat of the flame, and has the effect of lowering the decomposition temperature of the fiber and at the same time carbonizing the polyurethane. Due to the synergistic effect with the promoting action, it has an extremely excellent flame retardant effect.On the other hand, the ordinary structure has an excellent raised texture and appearance, and is highly flexible. It also has excellent color fastness and light resistance.

The flame-retardant varnished structure of the present invention can be usefully applied to interior materials such as automobile interior materials, chair upholstery, and wall coverings.

The present invention will be further explained below with reference to Examples.

Example 1.

As a human varnished structure made of polyurethane-impregnated thermoplastic synthetic fiber, Toshi ■ 1 Ecsaine''T type (
A polyester fiber fabric (warp, filament) '150D-48F, weft, spun yarn 30S, weaving density 52 x 43 pieces/i, n 4 was made using a low melting point polyamide resin adhesive on the back side of the 1.2 mm (thickness) The material used was one in which sheets of satin (sheet satin texture) were laminated together by heat fusion. How was the flame retardancy of the varnished structure obtained using FMVSS-Q3?
When evaluated according to the 02 standard, the burning rate is 150-18'Omm/
It was found to be extremely flammable.

On the other hand, 12 parts of tris dichloroisopropyl phosphate,
8 parts ammonium polyphosphate, 4 parts guanidine phosphate,
Acrylic acid ester resin (ethyl acrylate/butyl acrylate/2-ethylhexyl acrylate) −
8415/11. 10 parts by weight of a copolymer), 8 parts of cMco, and 0.0 parts of a nonionic surfactant.
Viscosity of flame retardant composition consisting of 2 parts water, 65 inches of water 3000
Centipoise (measured at 20°C, B-type viscometer, 60' r-ps m with a No. 4 rotor) was coated with a round-blade knife coater over the backing fabric on the back side of the varnished structure. and dried at 115° C. for 15 minutes.

The adhesion amount (solid content) of the flame retardant composition was calculated based on the weight change before and after processing. When the flame retardant rate is evaluated using the gFMVss-302 standard, as shown in Table 1, when the amount of adhesion is 8% by weight or more, it is less than the standard value of 700 mm/win, and the amount of adhesion is 20 mm/win or less.
It becomes self-extinguishing at a weight percent, and becomes almost nonflammable when it exceeds 30 weight percent.

It became clear that the texture became rough and hard. Therefore, the adhesion amount is preferably in the range of 8 to 30% by weight.

Table 1* Burning speed (FMvss-302 standard)
Hardness was determined by feeling the material against an unprocessed product.

○...Good (same as unprocessed product).

X... It's a little hard since it's an unprocessed product. ×...Hard.

Example 2 Flame retardant compositions having different content ratios of the flame retardant compound component and the acrylic ester resin component were applied to the human varnish needle-like structure used in Example 1 from the back side.

Heat treatment was performed at 110°C for 15 minutes. As a result, as shown in Table 2, samples with a small content of acrylic ester resin (Sample I
a1.2,) had poor storage stability of the flame retardant composition, and although it was possible to apply it by remixing it before application, it fell off frequently, and the coated surface of the processed product developed stickiness. On the other hand, if the content of acrylic ester resin is large, the flame retardant compound component will be consumed as much as necessary to make the acrylic ester resin flame retardant.9. High flame retardancy could not be obtained. The composition of the flame retardant composition used is as shown below, and the acrylic acid ester resin contains 57/11732% by weight of ethyl acrylate/butyl acrylate/2-ethylhexyl acrylate, respectively.
An emulsion of a copolymer consisting of

Flame retardant composition acrylic ester resin variable (part) ammonium polyphosphate (B) 5 guanidine phosphate (B) in ammonium bromide (B) 3 0 MC (thickener) 1 alkyl phenol EO additive (dispersion) agent) 0.500 The amount of the above flame retardant composition attached (solid, min.) is 18~
The content was adjusted to 19% by weight.

Stability in Table 2: After adjusting the flame retardant composition by uniformly dispersing it, the state of separation after being allowed to stand for 24 hours was determined.

○: Not separated.

×: Separate.

Example 3 The amount of acrylic acid ester resin and the mixing ratio of the flame retardant compound component in the flame retardant composition were kept constant, and flame retardant compositions containing different types of the compound were prepared as trial samples.

This flame retardant composition was applied to the back side of the same human varnish needle-like structure as used in Example 1 at two levels of adhesion amount: 15% by weight and 25% by weight, and then heated at 110°C.

Flame retardancy was examined for those heat-treated for 15 minutes.

Regarding flame retardancy, the burning rate was evaluated according to the FMVSS-302 standard and compared with the product of the present invention (Table 3).

The flame retardant composition of the present invention was found to have extremely superior flame retardant performance compared to comparative examples containing other flame retardant compound components. The composition of the flame retardant composition used is as follows.

Flame retardant compound component 24 parts CMC1 00 Table 3 *sFuel speed i (FMVSS-302) ◎Extinguish the fire by the nister line.

○: Burning speed 100 mm/min or less.

×: Burning speed exceeds 1'00 mm/min.

Example 4 In order to investigate resin performance as a binder, the presence or absence of dye bleed, the texture after application, and the flame retardant speed of 9 different resins with a certain amount of the same flame retardant compound component were determined using the human varnish needle of Example 1. The amount of adhesion on the back side of the shaped structure is 15! ``Amount (solid content) was coated and evaluated. The results are shown in Table 4.

Flame retardant compound component 1.3-dike 60-biruphosphate 10 parts Ammonium polyphosphate Guanidine heptaphosphate
7 Thickener CMC1 Resin [Solid content] 10 Water 6
500 Table 4 *Flame retardant rate: Based on Example 3.

**Dye bleed: Place the processed structure in an atmosphere of 40℃ x 80% RH with 4Bh.
(r) Dye staining on the resin layer when left standing.

The presence or absence of leads was observed.

O: No bleeding into the resin layer and no change in color tone of the resin.

Δ: Slight bleeding into the resin layer, resin strength; light color tone.

×: Bleed into the resin layer is large, and the color changes to a deep resin crab color.

**SBR had poor miscibility with flame retardant compounds and gelled, making it impossible to apply.

Patent applicant: Toshi Co., Ltd.

Claims (1)

[Claims] In a human varnish needle-like structure, an acrylic ester resin and the following compound (A) are added to the back surface of the raised surface. A flame-retardant varnished structure comprising a flame-retardant composition comprising at least one compound selected from the group (b). (A) 'O=P+OCH,CHXCH,X)
. or 0 = P (-,0CH(CH,X)CH,X
], (, X: , C7, Br). (B) Ammonium polyphosphate, guanidine phosphate, ammonium phosphate, ammonium bromide, ammonium chloride, ammonium sulfate, ammonium sulfamate.