JPH06146174A - Flame retardant synthetic leather - Google Patents

Abstract

PURPOSE:To obtain a flame retardant synthetic leather having high flame retardancy and excellent hand and physical properties as a synthetic leather without stickiness or perspiration, etc., on the surface. CONSTITUTION:This flame retardant synthetic leather 1 is constructed by successively providing a urethane microporous layer 4 and a skin layer 5 on the front surface side of a fiber substrate 2 and a flame retardant layer 3 formed from a flame retardant mixture of a halogenated phosphoric acid ester with a red phosphorus-based flame retardant, antimony oxide and a water-dispersible synthetic resin on the back surface side of the fiber substrate 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a synthetic leather having flame retardancy and used as a material for furniture and a material for vehicle interiors.

[0002]

2. Description of the Related Art In recent years, synthetic leather has been used for furniture and vehicle interiors, and synthetic leather having high flame retardancy is required. For example, in automobile interior materials, F
MVSS-302 (American flame retardant standard) and JIS-D-12
01 (Japanese standard), etc., and it is necessary to pass these standards.

Synthetic leather is, for example, one in which polyurethane resin is laminated on the surface of a fibrous base material via an adhesive, one in which a fibrous base material is applied with a polyurethane solution, or one in which a fibrous base material is applied or impregnated in a polyurethane solution. It is known that after this, polyurethane is coagulated with a non-solvent (wet coagulation) to form a microporous layer on the surface.

A flame-retardant synthetic leather containing a flame-retardant such as tricresyl phosphate or a halogenated phosphoric ester is known as a synthetic leather imparted with flame retardancy.

[0005]

However, since synthetic leather is a composite material in which fibers and resin are laminated, it is different in the combustion mechanism of both (fiber and resin) and satisfies the flame retardancy of both. There was no. Further, in order to impart higher flame retardancy to conventional flame-retardant synthetic leather, it is necessary to add a large amount of flame retardant, in which case the whole becomes hard and the texture and physical properties of the synthetic leather are increased. There was a problem that it decreased.

Addition of a flame retardant to a resin such as polyurethane not only lowers the physical properties of the resin, but also lowers the dyeing fastness, causes the flame retardant to migrate to the surface and causes a sticky feeling, and sweating. However, there is a problem in that the surface quality of the synthetic leather is impaired.

In particular, when the microporous layer is formed by wet coagulation of the resin layer on the surface side of the polyurethane resin, there is a drawback that the wet coagulation property is lowered by incorporating the flame retardant into the resin.

The present invention is intended to solve the above-mentioned drawbacks of the prior art, and it has high flame retardancy and has excellent texture and physical properties as a synthetic leather without stickiness or sweating on the surface. The purpose of the present invention is to provide synthetic leather.

[0009]

The flame-retardant synthetic leather of the present invention is a flame-retardant synthetic leather in which a resin layer is provided on the front surface side of a fiber base material, and a flame-retardant layer is provided on the back surface side. The flame-retardant layer is characterized by being formed of a flame-retardant mixture consisting of a halogenated phosphoric acid ester, a red phosphorus-based flame retardant, antimony oxide and a water-dispersible synthetic resin.

[0010]

Embodiments of the present invention will now be described in detail with reference to the drawings. FIG. 1 is a sectional view of an essential part showing an example of the flame-retardant synthetic leather of the present invention.

In the flame-retardant synthetic leather 1 of the present invention, for example, as shown in FIG. 1, a urethane microporous layer 4 and a skin layer 5 are sequentially provided on the surface side of a fiber base material 2, and the back surface side of the fiber base material 2 is provided. The flame-retardant layer 3 is provided in the structure.

2 to 6 are cross-sectional views of essential parts showing another embodiment of the flame-retardant synthetic leather of the present invention. The flame-retardant synthetic leather of the present invention has a surface state covered with a skin layer of polyurethane or the like as shown in FIG. 1 to form a silver-tone surface, and as shown in FIG. The surface of the microporous layer may be ground to form a nubuck tone having a sponge structure.

Further, in the synthetic leather of the present invention, the resin layer is not particularly limited to the urethane microporous layer 4, and if a leather-like texture can be imparted, the resin layer is impregnated with the solution as shown in FIGS. 3 and 4. The urethane impregnated layer 6 may be formed as a resin layer.

Further, as shown in FIGS. 5 and 6, a resin layer is laminated in the order of a urethane impregnated layer 6 and a urethane microporous layer, and 2
It may be formed from layers. In this case, a skin layer may be provided on the surface to form a silver surface tone (FIG. 5) or unevenness (FIG. 6).

As the resin layer formed on the surface side, other than polyurethane, for example, natural rubber, chloroprene, SB
A high molecular polymer such as R, an acrylic resin, a silicone resin, or vinyl chloride may be used in combination.

If necessary, the urethane microporous layer 4 is mixed with various additives such as a film forming aid, a colorant, a filler, a light stabilizer, an ultraviolet absorber, an antioxidant, a water / oil repellent agent, and the like. can do.

As the polyurethane used for the urethane microporous layer 4, any of polyester type, polyether type, polyester / polyether type, lactone type and polycarbonate type can be used. Polycarbonate-based polyurethane is preferred as the polyurethane of synthetic leather for vehicle interiors, which is required to have durability.

Examples of the fiber base material 2 of the flame-retardant synthetic leather of the present invention include synthetic fibers such as polyester, polyamide and polyacrylonitrile, natural fibers such as cotton and hemp, and recycled fibers such as rayon, suf and acetate. A woven fabric, a knitted fabric, a non-woven fabric or the like, which is used alone or made of a mixed fiber of these, is used.

In the present invention, the flame-retardant layer 3 formed on the back side of the fiber base material 2 is formed of a flame-retardant mixture consisting of a halogenated phosphoric acid ester, a red phosphorus-based flame retardant, antimony oxide and a water-dispersible synthetic resin. It is important to be done. In particular, the above-mentioned red phosphorus flame retardant is excellent in flame retardant effect even if used in a small amount, and is characterized by being used in combination with halogenated phosphate ester and antimony oxide.

The preferred mixing ratio (solid content ratio) of the above-mentioned mixture is as follows. Halogenated phosphoric acid ester 10 to 50 parts by weight Red phosphorus flame retardant 2 to 20 parts by weight Antimony oxide 10 to 30 parts by weight Water-dispersible synthetic resin 5 to 40 parts by weight

Specific examples of the halogenated phosphate ester include tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, and bis (2,3dibromopropyl).
2,3 dichloropropyl phosphate, tris (2,3
Halogenated phosphoric acid esters that are liquid at room temperature, such as dibromopropyl) phosphate and bis (chloropropyl) monooctylphosphate, can be used. The halogenated phosphoric acid ester also acts as a softening agent for the water-dispersible synthetic resin described below, in addition to the flame-retardant combined effect with the red phosphorus compound.

As the above-mentioned red phosphorus flame retardant, a red phosphorus flame retardant which is stabilized by coating the surface of particles with a resin or the like and subjecting it to a surface treatment such as microencapsulation in order to prevent ignition in the kneading operation is used. Is preferred. As such, for example, commercially available products such as Nova Red, Nova Excel, Novaquell, Novazol (all trade names of Rin Kagaku Kogyo Co., Ltd.), Hishigad (trade name of Nippon Kagaku Kogyo Co., Ltd.) and the like can be used. it can.

Specific examples of the above-mentioned antimony oxide include antimony oxides such as antimony trioxide, antimony tetroxide and antimony pentoxide. This compound exerts a high synergistic effect with the above halogenated phosphate ester. Gives good flame retardancy. In particular, antimony trioxide is preferably used because it combines with a halogen compound at the time of combustion and exhibits high flame retardancy.

The water-dispersible synthetic resin is an acrylic resin such as a polyacrylic ester resin, a polyurethane resin,
Polyvinyl chloride resin, polystyrene butadiene resin, polyacrylonitrile butadiene resin, polyester resin and the like can be used. These water-dispersible resins can be applied as an aqueous dispersion (emulsion). The water-dispersible synthetic resin is used as a binder for fixing the flame-retardant compound on the fiber substrate. Among the above resins, a polyacrylic acid ester resin is particularly preferable because it has good uniformity, compatibility, flexibility and the like.

The flame retardant mixture has excellent flame retardancy by combining the above-mentioned compounds (1) to (4) and can satisfy the flame retardancy of both the fiber and the resin with a small amount of use. That is, in the present invention, it is necessary to use the flame retardants of the above-mentioned (1), which acts as a main flame retardant, and brings a synergistic effect with a halogenated flame retardant as a flame retardant aid. Further, the compound (2) plays a role as a binder having flexibility, and reliably holds the flame retardant.

The amount of the above-mentioned mixed composition attached to the synthetic leather is 10 to 70% by weight based on the synthetic leather. If the amount of the adhering agent is less than 10% by weight, the flame retardant effect is insufficient, and if it exceeds 70% by weight, the flame retardant effect is not so improved and the texture tends to be hard. Particularly preferably, it is 20 to 50% by weight. The flame-retardant layer can be formed by coating the mixture on the back side of the fiber base material and drying.

To produce the flame-retardant synthetic leather of the present invention,
It is preferable to form the resin layer such as the urethane microporous layer 4 on the front surface side of the fibrous base material 2, and then coat and dry the flame retardant layer 3 on the back surface side. Although the resin layer 4 may be formed on the front surface side after the flame-retardant layer 3 is formed on the rear surface side of the fibrous base material 2, when a urethane wet porous layer is formed as the resin layer as in the above embodiment, In order to prevent the flame retardant from flowing out into solvent insects or water during impregnation into a resin solution or immersion in water, it is necessary to form the flame retardant layer 3 after forming the resin layer 4 as in the latter case. preferable.

The resin layer 4 is not limited to being formed by directly coating the surface of the fibrous base material 2, but the resin layer 4, the adhesive layer, etc. are sequentially laminated on the surface of the release paper in advance. It is also possible to manufacture the formed transfer sheet and transfer the resin layer of the transfer sheet to the surface of the fibrous base material 2 to form the transfer sheet.

Specific examples of the method of the present invention will be shown below. Example 1 A water-dispersed flame retardant mixture comprising the following mixed composition was prepared. -Tris (2,3 dibromopropyl) phosphate (manufactured by Daihachi Chemical Co., Ltd.) 20 parts by weight-Novaquel ST-100 (manufactured by Rin Kagaku Kogyo Co., Ltd.) 5 parts by weight-Antimony trioxide (manufactured by Suzuyu Chemical Co., Ltd.) 15 parts by weight-Acrylic resin [ Boncoat 350 (solid content concentration 60%): Dainippon Ink and Chemicals] 10 parts by weight Thickener (Boncoat V: Dainippon Ink and Chemicals) 1.5 parts by weight Dispersant (Demol P: Kao) 2 parts by weight Part-water 46.5 parts by weight

Next, this mixture was applied by a knife coater to the fiber surface of a silver-faced synthetic leather having a microporous structure coated with a polycarbonate urethane resin having a thickness of 1.0 mm, and then dried at 120 ° C. for 10 minutes. . The amount of the composition deposited was 28% by weight. Although this, FMVSS-3
The flame retardancy (combustion rate) according to the 02 standard was 19 mm / min, and the synthetic leather of the present invention had high flame retardancy, which was a value that sufficiently passed the flame retardancy standard for vehicles. In addition, the flame-retardant synthetic leather had a soft texture and was not much different from the unprocessed one.

Example 2 A water-dispersed flame retardant mixture comprising the following mixture composition was prepared. 25 parts by weight of tris (dichloropropyl) phosphate (made by NOF Corporation) 7 parts by weight of Novarred 120UF (made by Rin Kagaku Kogyo Co., Ltd.) 13 parts by weight of antimony trioxide (made by Suzu Yu Chemical) Acrylic resin [Boncoat AB-407 ( Solid content concentration 45%): Dainippon Ink and Chemicals] 15 parts by weight-Thickener (Boncoat V: Dainippon Ink and Chemicals) 1.5 parts by weight-Dispersant (Demol P: Kao) 2 parts by weight-Water 36 parts by weight

Next, this mixture was applied by a knife coater to the back surface (fiber surface) of suede-like synthetic leather whose surface was buffed by impregnating a polyester knitted cloth having a thickness of 0.9 mm with a polycarbonate-based urethane resin, and then applied at 120 ° C. And dried for 7 minutes. The amount of the water-dispersed flame retardant mixture adhering to the synthetic leather was 32% by weight. Although this, FMVSS
The flame retardancy (combustion rate) according to the -302 standard is self-extinguishing, and the synthetic leather of the present invention has high flame retardancy, which is a value that sufficiently passes the flame retardancy standard for vehicles. In addition, the flame-retardant synthetic leather had a soft texture and was not much different from the unprocessed one.

Comparative Example 1 (when no red phosphorus flame retardant was used) A water-dispersed flame retardant mixture comprising the following mixture composition was prepared.・ Tris (dichloropropyl) phosphate (manufactured by NOF Corporation) 25 parts by weight ・ antimony trioxide (manufactured by Suzuyu Chemical Co., Ltd.) 15 parts by weight ・ Acrylic resin [Boncoat 350 (solid content concentration 60%): manufactured by Dainippon Ink] 10 parts by weight・ Thickener (Boncoat V: manufactured by Dainippon Ink) 1 part by weight ・ Dispersant (Demoll P: manufactured by Kao) 2 parts by weight ・ Water 47 parts by weight

Next, this mixture was applied with a knife coater to the fiber side of a silver-faced synthetic leather having a microporous structure coated with a polycarbonate-based urethane resin having a thickness of 1.0 mm, and then dried at 120 ° C. for 10 minutes. The amount of the composition deposited was 28% by weight. This product is made of flame retardant according to FMVS-302 standard
The (combustion speed) was 102 mm / min, and it was not possible to pass the flame-retardant standard for vehicles. Table 1 shows the test results of Examples and leather examples.

[0035]

【table 1 】

[0036]

As described above, in the flame-retardant synthetic leather of the present invention, the flame-retardant mixed composition comprising halogenated phosphoric acid ester, red phosphorus-based flame retardant, antimony oxide and water-dispersible synthetic resin has a fibrous base. By adopting the configuration provided on the back surface side of the material, the flame retardant of the above composition has a very excellent flame retardant effect, so a sufficient flame retardant effect can be obtained with a small amount of use, and the basis weight is small. Flame-retardant synthetic leather with excellent texture can be obtained.

Further, since the flame retardant is not directly mixed with the resin layer, there is no possibility that the flame retardant bleeds on the surface of the synthetic leather and the surface becomes sticky, and the physical properties of the resin layer are not deteriorated. Furthermore, when the resin layer is formed by wet coagulation of polyurethane, it has an effect of not lowering the coagulability and film-forming property of the polyurethane resin.

[Brief description of drawings]

FIG. 1 is a sectional view of an essential part showing one embodiment of a flame-retardant synthetic leather of the present invention.

FIG. 2 is a cross-sectional view of essential parts showing another embodiment of the flame-retardant synthetic leather.

FIG. 3 is a cross-sectional view of an essential part showing another aspect of the flame-retardant synthetic leather.

FIG. 4 is a cross-sectional view of essential parts showing another embodiment of the flame-retardant synthetic leather.

FIG. 5 is a cross-sectional view of essential parts showing another embodiment of the flame-retardant synthetic leather.

FIG. 6 is a cross-sectional view of essential parts showing another embodiment of the flame-retardant synthetic leather.

[Explanation of symbols]

 1: Flame-retardant synthetic leather 2: Fibrous base material 3: Flame-retardant layer 4: Urethane microporous layer 6: Urethane impregnated layer

Claims (1)

[Claims] 1. A flame-retardant synthetic leather having a resin layer provided on the front side of a fiber substrate and a flame-retardant layer provided on the back side, wherein the flame-retardant layer is a halogenated phosphoric acid ester or red phosphorus-based flame-retardant material. A flame-retardant synthetic leather, which is formed from a flame-retardant mixture comprising a flame retardant, antimony oxide and a water-dispersible synthetic resin.