JPH05163684A - Production of leathery sheet-like product - Google Patents

Abstract

PURPOSE:To provide a leathery sheet-like product excellent in flame retardancy with wet solidifiability, appearance and feeling touch retained. CONSTITUTION:A fibrous base fabric is impregnated and/or coated with a solvent solution of a polyurethane prepared by incorporating (A) 100 pts.wt. of a polycarbonate-based polyurethane with (B) 5-40 pts.wt. of a red phosphorus- based flame retardant followed by treatment with a nonsolvent for the polyurethane to solidify it; and, a polyurethane porous film thus formed on the base fabric is then provided with a surface skin layer either directly or through an adhesive layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a leather-like sheet material, and more particularly, a leather-like sheet material having excellent flame retardancy suitable for furniture materials, vehicle interiors, sheet materials and the like. It relates to a manufacturing method.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand for flame retardancy in furniture materials, vehicle materials, and in particular vehicle interior materials in order to prevent human damage in the event of a fire. For interior materials, FMVS of American flame retardant standard
S-302 and Japanese JIS-D-1201, etc. are specified, and it is required to pass these rules.

Polycarbonate polyurethane is known to be excellent in hydrolysis resistance and light resistance and suitable for the above-mentioned applications as a leather sheet material. Conventionally, as a method of making a leather-like sheet material flame-retardant by a wet coagulation method of the polyurethane, a method of blending a phosphate ester compound such as tricresyl phosphate as a flame retardant is known.

However, the phosphoric acid ester type flame retardant is liable to be dissolved in water during the wet coagulation treatment to reduce its effect.
There is a problem that the film forming performance or the coagulation performance of the polyurethane is remarkably lowered, and further, when obtaining a sponge structure, it is difficult to obtain a uniform sponge structure and only a poor texture is obtained. There is.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a leather-like sheet material excellent in flame retardancy without impairing wet coagulation properties, appearance and texture.

[0006]

According to the present invention, a fiber base material is impregnated with a solvent solution of a polycarbonate polyurethane containing 5 to 40 parts by weight of a red phosphorus flame retardant per 100 parts by weight of a polycarbonate polyurethane, and / or Alternatively, after coating, the polyurethane-like solvent is coagulated with a non-solvent to form a polyurethane porous film on a fiber substrate, and then a skin layer is provided on the surface of the porous film. It is a manufacturing method.

In the present invention, the polycarbonate-based polyurethane means a polymer of a polycarbonate-based polyol, an organic diisocyanate and a chain extender, and the polycarbonate-based polyol means a general formula HO-R- (O-CO-O-R). ) _n -OH [in the _{formula, R = - (CH 2)} m -, m ≧ 2, n =
5 to 200]. Specifically, 1,6-hexane polycarbonate polyol is preferable. Also,
A mixture obtained by substituting a part of the polyalkylene polycarbonate-based polyol with a polyoxyalkylene-modified polycarbonate can also be used.

On the other hand, as the organic diisocyanate, an aliphatic or alicyclic diisocyanate is preferable as the non-yellowing type diisocyanate, for example, tetramethylene diisocyanate, 1,6-hexane diisocyanate,
2,2,4-Trimethyl-1,6-hexanediisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate dicyclohexylmethane, 4,4'-dicyclohexylmethane diisocyanate Is mentioned.

Further, as a yellowing diisocyanate,
Aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate and the like can be used.

The chain extender may be a primary or secondary aliphatic amine or a low molecular weight glycol, such as piperazine, hexamethylenediamine, ethylenediamine, propylene-1,2-diamine, N-methyl-.
Bis- (3-aminopropyl) amine, 1,4-diaminocyclohexane, 1-amino-3-aminomethyl-
3,5,5-Trimethyl-cyclohexane, 1,4-butanediol, ethylene glycol, 1,6-hexanediol, neopentyl glycol, p-xylylene glycol and the like can be used.

If necessary, various additives such as film-forming aids, colorants, fillers, light stabilizers, ultraviolet absorbers, antioxidants, and water / oil repellents may be mixed in the polyurethane. it can.

The red phosphorus-based flame retardant is preferably one whose surface is coated with a resin in order to prevent ignition during kneading, and such red phosphorus-based flame retardant is, for example, NOVA. Red, Nova Excel, Novazol, Novaquell [all are Rin Kagaku Co., Ltd.
Manufactured by Nippon Chemical Industry Co., Ltd., and the like.

The red phosphorus flame retardant is eluted in water during the wet coagulation treatment like conventional phosphoric acid ester flame retardants,
Since it does not adversely affect the coagulation and film-forming properties of polyurethane and has good affinity with polyurethane, it is easy to knead, does not aggregate, maintains a homogeneous dispersed state for a long time, and is unlikely to sediment. It has characteristics. Further, the appearance, texture, and physical properties of the obtained leather-like material are not impaired, and even if it burns, it has lower smoke emission compared to conventional flame retardants and no drip phenomenon is observed.

In the present invention, the flame retardant is 5 to 40 parts by weight based on 100 parts by weight of the polycarbonate polyurethane.
Add parts by weight, preferably 8 to 25 parts by weight. If the amount added is less than 5 parts by weight, the flame retardant effect will not be exhibited, while if it exceeds 40 parts by weight, the flame retardant effect will be saturated and the original coloring of red phosphorus will be remarkable, such being undesirable.

As a solvent for the polycarbonate polyurethane, an organic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and tetrahydrofuran can be used.

In the present invention, a fiber base material is impregnated with a polyurethane solution (hereinafter referred to as "polyurethane composition liquid") obtained by dissolving and dispersing the polycarbonate polyurethane and a specified amount of the red phosphorus flame retardant in the solvent. After coating and / or coating, the polyurethane is solidified with a non-solvent to form a polyurethane porous film on the fiber substrate.

A nonionic surfactant, which is generally considered to be effective, is added to the above-mentioned polyurethane composition liquid as a coagulation regulator for forming fine cells in the wet cells formed in the obtained leather-like sheet. can do.

In the present invention, the fiber base material is cotton,
Natural fibers such as hemp; regenerated fibers such as rayon; semi-synthetic fibers such as acetate; synthetic fibers such as polyamide, polyester, polyacrylonitrile, etc., either alone or as a knitted fabric, woven fabric or non-woven fabric made of a blend of these fibers You can As the fiber base material, it is possible to use a base material that has been subjected to a flame-retardant treatment, or a base material that is made of flame-retarded fiber. By using such a fiber base material, more excellent flame retardancy can be obtained. In addition, it is preferable that at least the surface of the fiber base material, which is impregnated and / or coated with the polyurethane composition liquid, has been raised or napped.

In the present invention, first, the fiber base material is impregnated with and / or coated with a polyurethane composition liquid. The polyurethane composition liquid can be applied by a knife coater, a river roll coater, or the like. The amount of the polyurethane composition liquid impregnated and / or applied is 10 to 200% by weight in terms of polyurethane solid content per weight of fiber,
It is preferably about 20 to 100% by weight.

Next, the polyurethane composition liquid is impregnated and / or
Alternatively, the coated fiber substrate is treated with a nonsolvent for polyurethane to solidify the polyurethane. As the non-solvent for polyurethane, for example, water or a mixed solvent of water and dimethylformamide can be used. The treatment with such a non-solvent can be performed, for example, by immersing the fiber base material impregnated and / or coated with the polyurethane composition liquid in water at 15 to 60 ° C. for 3 to 60 minutes, and further repeating the washing in warm water to repeat the washing. By removing the solvent and dehydrating and drying,
It is possible to form a polyurethane porous film having fine pores on a fiber substrate.

The porous polyurethane membrane preferably has a 100% modulus of 20 to 120 kg / cm ² . When the 100% modulus is less than 20 kg / cm ² , the texture becomes soft, but the physical properties are inferior and not practical. On the other hand, 1
If it exceeds 20 kg / cm ² , the physical properties are improved, but the texture becomes hard, which is not preferable.

In the present invention, a leather-like sheet material is then obtained by providing a surface skin layer on the surface of the porous polyurethane membrane formed on the fiber base material. As the skin layer, a film made of polyurethane resin and having a thickness of 5 to 100 μm is preferable. As the polyurethane resin for the skin layer, polyester-based polyurethane, polyether-based polyurethane,
Any of polycaprolactone-based polyurethane, polymethylvalerolactone-based polyurethane, polycarbonate-based polyurethane and the like can be used. Among them, polycarbonate-based polyurethane is preferable because it has excellent durability and heat resistance.

The polyurethane resin film forming the skin layer has a 100% modulus of 30 to 200 kg /
cm ² is preferable. 100% modulus is 30k
If it is less than g / cm ² , the texture will be soft, but the surface strength will be poor, while if it exceeds 200 kg / cm ² , the texture will be hard, which is not preferable.

In the present invention, the skin layer is formed by, for example, applying a skin layer-forming resin to a release paper and drying the release paper, and then applying the release paper to the surface of a porous polyurethane membrane formed on a fiber substrate. It can be carried out by heat laminating, and then laminating by a transfer method in which the release paper is peeled off. Alternatively, a method in which a solvent solution of polyurethane for forming the skin layer is directly applied to the surface of the porous membrane can be used. The skin layer is formed with or without an adhesive.

When an adhesive is used, in order to improve the flame retardancy of the obtained leather-like sheet material, the adhesive contains a red phosphorus flame retardant therein, and for the same reason as above, 100 parts by weight of polyurethane. However, it is preferable to contain 5 to 40 parts by weight. The amount of flame retardant is more preferably 8 to 25 parts by weight.

Examples of the adhesive used include polyester polyurethane, polyether polyurethane,
Two-component polyurethane resins such as polycaprolactone-based polyurethane, polymethylvalerolactone-based polyurethane and polycarbonate-based polyurethane can be mentioned. Among them, a polycarbonate polyurethane two-component adhesive is preferable from the viewpoint of durability and heat resistance.

The layer structure of the leather-like sheet material obtained by the present invention will be described with reference to a schematic sectional view in which the steps are taken into consideration. For example, as shown in FIG. 1, a fiber base material is impregnated with a polyurethane composition liquid and solidified. The surface of the polyurethane porous membrane 21 thus formed is provided with the skin layer 40 via the adhesive layer 30, and is formed by impregnating and solidifying a polyurethane composition liquid into a fiber base material as shown in FIG. A surface layer 40 is provided on the surface of a polyurethane porous film 22 formed by coating the same composition liquid in contact with the polyurethane porous film 21 and then solidifying the same, as shown in FIG. A structure in which the skin layer 40 is provided on the surface of the polyurethane porous film 22 formed on the surface of the fiber base material by coating and coagulating the polyurethane composition liquid on the fiber base material 10 with the adhesive layer 30 interposed therebetween. It can be mentioned.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, a part represents a weight part in an Example. Example 1 16% of a non-yellowing type polyurethane [Product name: Crisbon MP-120, manufactured by Dainippon Ink and Chemicals, Inc.] containing 1,6-hexane carbonate polyol as a main component and having a 100% modulus of 35 kg / cm ^2. To 100 parts of polyurethane solid content in dimethylformamide solution, 4 parts of sodium salt of di-2-ethylhexyl sulfosuccinate, 7 parts of polyether modified silicone oil, 5 parts of black colorant and red phosphorus flame retardant [Product name: Novazol R
-20, manufactured by Rin Kagaku Kogyo Co., Ltd.] 23 parts was added to prepare a polyurethane composition liquid.

This polyurethane composition liquid was twilled and woven by mixing polyester fibers and rayon fibers in a thickness of 0.
On a brushed surface with a water content of 70% of a 8 mm single-sided brushed cloth, a coating amount of 110 g / polyurethane solid content was applied with a knife coater.
m ² was applied, and then the substrate was immersed in an 11% aqueous solution of dimethylformamide (liquid temperature 20 ° C.) to solidify. The obtained polyurethane substrate was further desolvated in warm water of 60 ° C., washed, and dried to obtain a sheet-shaped product having a polyurethane porous membrane. The sheet-like material had a thickness of 0.95 mm, had a sponge structure with uniform and fine pores on the surface, and was flexible and excellent in surface smoothness.

Next, on the surface of the embossed release paper, a yellowing-free type polycarbonate-based polyurethane resin film containing 20 parts of a black colorant, a polycarbonate-based two-component polyurethane adhesive [crosslinking agent: 10 parts, red phosphorus-based flame retardant: Novazole R-2
0, manufactured by Rin Kagaku Kogyo Co., Ltd., containing 20 parts] is laminated by a transfer method on the surface of a sheet-like material having a polyurethane porous film through the adhesive layer by a transfer method. Then, a non-yellowing type polycarbonate-based polyurethane resin film was laminated to form a skin layer having a thickness of 20 μm to obtain a silver-tone leather-like sheet. The leather-like sheet obtained had natural fine folds and wrinkles, had a silver-like appearance that was very similar to natural leather, and had a soft and voluminous texture. Moreover, this leather-like sheet was excellent in hydrolysis resistance, light resistance, and flame retardancy, and could be used as a material for furniture and vehicles.

The leather-like sheet material has a temperature of 70.
Changes in physical properties such as appearance, texture, surface abrasion and peel strength after jungle test for 10 weeks in an atmosphere of ℃ and 95% humidity and after 200 hours of irradiation with a fade meter (black panel temperature 83 ℃) There were few. The flame retardancy (combustion rate) according to the FMVSS-302 standard was 42 mm / min.

Example 2 A non-yellowing type polyurethane [Product name: Resamine Cu-9430NL, manufactured by Dainichiseika Kogyo Co., Ltd.] containing 100% 1,30-hexane carbonate polyol as a main component and having a 100% modulus of 30 kg / cm ² . 3% sulfosuccinic acid di-2-ethylhexyl ester sodium salt per 100 parts of polyurethane solid content in a 10% dimethylformamide solution
Part, polyethylene oxide modified polysiloxane 4 parts,
A polyurethane composition liquid was prepared by adding 10 parts of a black colorant and 18 parts of a red phosphorus flame retardant [Product name: Nova Red 120UF, manufactured by Rin Kagaku Kogyo KK].

A weight per unit area of 250 denier of polyester resin and nylon fiber was applied to this polyurethane composition liquid.
75 g of polyurethane solid content in g / m ² entangled nonwoven fabric
It was impregnated so that it would be / m ^2, and it was filled up. Further, on the fiber substrate, a yellowing-resistant polyurethane [Product name: Resamine Cu-9450N] containing 100% modulus 50 kg / cm ² containing 1,6-hexane carbonate polyol as a main component.
L, manufactured by Dainichiseika Kogyo Co., Ltd.] in 17% dimethylformamide solution per 100 parts of polyurethane solid content.
5 parts sulfosuccinic acid di-2-ethylhexyl ester sodium salt, 4 parts sorbitan oleic acid ester,
10 parts of black colorant and 20 parts of red phosphorus flame retardant [Product name: Nova Red 120UF, manufactured by Rin Kagaku Kogyo Co., Ltd.]
The polyurethane composition liquid prepared by adding the above was coated with a knife coater at a coating amount of 100 g / m ^{2 in} terms of polyurethane solid content.
And then the substrate was dipped in a 13% dimethylformamide solution (liquid temperature 20 ° C.) to solidify the polyurethane to obtain a polyurethane substrate.

The resulting polyurethane substrate is further treated with 60
The solvent was removed in warm water of ℃, washed, and dried to obtain a sheet-like material having a polyurethane porous membrane. The sheet is
It had a thickness of 1.1 mm, had a sponge structure with uniform and fine pores on the surface, and was flexible and had excellent surface smoothness.

In the same manner as in Example 1, a polycarbonate-based two-component polyurethane adhesive (10 parts of a cross-linking agent, 10 parts of a black colorant, and 20 parts of a red phosphorus flame retardant: Novarred 120UF) was applied to the surface of this sheet-like material. A non-yellowing type polycarbonate-based polyurethane resin film containing 20 parts of a black colorant by a transfer method using a textured release paper to form a skin layer, and a silver-finished leather-like sheet material. Finished. The leather-like sheet thus obtained had natural fine folds and wrinkles, had a silver-like appearance that was very similar to natural leather, and had a highly flexible texture. Further, this leather-like sheet was excellent in hydrolysis resistance, light resistance and flame retardancy, and could be used as a material for furniture and vehicles.

The appearance of this sheet-like material after a jungle test for 10 weeks in an atmosphere at a temperature of 70 ° C. and a humidity of 95% and after irradiation for 200 hours with a fade meter (black panel temperature 83 ° C.) , Texture,
There were few changes in physical properties such as surface wear and peel strength.
The flame retardancy (combustion rate) according to the FMVSS-302 standard was 38 mm / min.

Comparative Example 1 As a flame retardant, 20 parts of a red phosphorus flame retardant was used in place of 23 parts of a phosphoric acid ester flame retardant [Product name: TCP, manufactured by Daihachi Chemical Industry Co., Ltd.]. Polyurethane was coagulated in the same manner as in 1, desolventized and dried to obtain a sheet-like material having a polyurethane porous membrane. The sheet-like material had a thickness of 0.8 mm and had a smooth surface during wet coagulation, but after drying, it had a settled surface such as insufficient desolvation, many surface irregularities, and lacked in volume. It was a thing.

A skin layer was provided on the surface of this sheet material in the same manner as in Example 1 to produce a leather-like sheet material. Although this leather-like sheet had good hydrolysis resistance,
The light resistance was poor, and the flame retardancy (combustion rate) according to the FMVSS-302 standard was 93 mm / min.

[0039]

EFFECTS OF THE INVENTION According to the present invention, a leather-like sheet material having excellent flame retardancy can be obtained without impairing the wet coagulation property, appearance and texture.

[Brief description of drawings]

FIG. 1 is a schematic sectional view showing an example of the layer structure of a leather-like sheet material obtained by the present invention.

FIG. 2 is a schematic cross-sectional view showing an example of the layer structure of a leather-like sheet material obtained by the present invention.

FIG. 3 is a schematic cross-sectional view showing an example of the layer structure of a leather-like sheet material obtained by the present invention.

[Explanation of symbols]

10 Fiber Substrate Layer 21 Polyurethane Porous Membrane Layer Formed by Impregnation into Fiber Substrate 22 Polyurethane Porous Membrane Layer Formed by Coagulation After Application 30 Adhesive Layer 40 Skin Layer

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B32B 27/40 7016-4F C08K 3/32 C08L 75/04 NFY 8620-4J D06N 3/18 7141- 4F

Claims (3)

[Claims] 1. A polycarbonate-based polyurethane 100
A fiber base material is obtained by impregnating and / or applying a solvent solution of a polycarbonate-based polyurethane containing 5 to 40 parts by weight of a red phosphorus flame retardant with respect to parts by weight, and then coagulating with a non-solvent of the polyurethane. A method for producing a leather-like sheet, comprising forming a polyurethane porous film on the surface and then providing a skin layer on the surface of the porous film. 2. The method for producing a leather-like sheet material according to claim 1, wherein the skin layer is provided via an adhesive layer containing 5 to 40 parts by weight of a red phosphorus flame retardant with respect to 100 parts by weight of polyurethane. .. 3. The method for producing a leather-like sheet material according to claim 1, wherein the adhesive layer and / or the skin layer is made of durable polyurethane.