JPH08269876A - Leather-like sheetlike material and its production - Google Patents

Abstract

PURPOSE: To obtain a leather-like sheetlike material having excellent air permeability and moisture permeability by dipping and/or coating a polyurethane resin solution on a fiber substrate, forming a porous layer by wet coagulating and placing a surface finishing layer. CONSTITUTION: A nonwoven cloth obtained by entangling and integrating a nylon/polyester dispersion-type conjugate fiber web by needle punching, etc., is used as a base and the base is impregnated and/or coated with a polyurethane resin solution composed of blending 1-30 pts.wt. of a vinyl chloride-ethylene copolymer resin having 800-2200 polymerization degree and an ethylene- containing percentage of 1-10wt.% with 100 pts.wt. of a polyurethane resin, and wet-coagulated by dipping in a non-solvent such as an aqueous solution of dimethylformanide, desolvated, washed and dried to form a polyurethane porous layer having many fine pores on the surface of the substrate. A polyurethane resin containing a colorant is gravure-coated on the porous layer, embossing and rubbing to obtain the objective leather-like sheetlike material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a shoe lining material, a shoe insole material,
The present invention relates to a leather-like sheet material having excellent breathability and moisture permeability, which is preferably used as a material for clothing and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a leather-like sheet material imitating natural leather, that is, a wet porous layer of polyurethane resin and a dry porous layer on a fiber base material as a material for shoe lining, shoe insole, clothing, etc. After forming a quality layer or a dry foam layer, a surface layer corresponding to the silver surface of natural leather is laminated, sprayed,
A leather-like sheet material formed by a method such as a gravure method is often used.

[0003]

However, the above-mentioned leather-like sheet material is inferior in breathability and moisture permeability due to its manufacturing method and structure. Therefore, when such a leather-like sheet material is used as a shoe lining material, a shoe insole material, or the like, there arises a problem that the foot gets damp when worn. The present invention has been made to solve the above-mentioned drawbacks, and provides a leather-like sheet material having not only an appearance and a feeling resembling that of natural leather but also breathability and moisture permeability. That is the purpose.

[0004]

The leather-like sheet material of the present invention made to solve the above-mentioned problems is a leather-like sheet material having a fiber base material, a polyurethane resin layer, and a surface finishing layer. The polyurethane resin layer is formed by impregnating and / or applying a polyurethane resin solution containing 1 to 30 parts by weight of vinyl chloride-ethylene copolymer resin on 100 parts by weight of the polyurethane resin on a fiber base material and wet coagulating The resulting polyurethane resin layer is characterized.

Further, the method for producing a leather-like sheet material of the present invention, which has been made to solve the above-mentioned problems, comprises a fiber base material,
A step of impregnating and / or applying a polyurethane resin solution containing 1 to 30 parts by weight of vinyl chloride-ethylene copolymer resin fine powder to 100 parts by weight of a polyurethane resin,
Polyurethane resin porous with fine pores on the surface by immersing the fibrous base material impregnated and / or coated with the polyurethane resin solution in a non-solvent to wet-coagulate the polyurethane resin, desolvate it, wash it with water, and then dry it Forming layers,
And a surface finishing step.

Examples of the fiber base material used in the present invention include knitted fabrics, woven fabrics and entangled nonwoven fabrics made of fibers having a single yarn fineness of 2 denier or less. The entangled non-woven fabric is a non-woven fabric that has been entangled by needle punching or high-speed fluid flow, and is provided with an elastic polymer such as polyurethane resin or synthetic rubber as necessary. When a knitted fabric or a woven fabric is used as the fiber base material, it is preferable that at least the surface on which the polyurethane resin solution is impregnated and / or applied is napped or napped. Furthermore, the weight of the fiber base material is not particularly limited, and is appropriately selected depending on the application of the leather-like sheet material. For example, when used as a material for shoes, a fiber base material of about 200 to 400 g / m ² is used.

The fibers constituting the fiber base material include, for example, synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyolefin and polyvinyl alcohol,
Natural fibers such as cotton and hemp, regenerated fibers such as rayon, suf, acetate, etc., alone or as a blended fiber thereof, and modified into ultrafine fibers by dissolving and removing at least one component or splitting bicomponent fibers Multicomponent fibers and the like can be used.

For the purpose of improving the texture of the obtained leather-like sheet material, the above-mentioned fiber base material is coated with polyvinyl alcohol, silicone, or a mixture thereof prior to coating and / or impregnation with the polyurethane resin solution. It may be fixed to the. At this time, the amount of polyvinyl alcohol or the like attached is about 1 to 15% by weight based on the fiber base material. The fibrous base material may be a surface-smoothed product for the purpose of improving the surface smoothness of the obtained sheet-like material.

The polyurethane resin used in the present invention is
One or more polyol components selected from polyols having an average molecular weight of 500 to 3000, such as polyester-based polyols, polyether-based polyols, polyester-ether-based polyols, polycaprolactone-based polyols, polymethylvalerolactone-based polyols, polycarbonate-based polyols; One or more isocyanate components selected from aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, aliphatic diisocyanates having a cyclic group, and the like; and low-molecular compounds having at least two active hydrogen atoms, such as aliphatic diols and alicyclics It is obtained by reacting with one or more chain extenders selected from group diols, aliphatic diamines, alicyclic diamines, hydrazine derivatives and the like. Further, these polyurethane resins include, for example, amino acids, silicones,
It may be a modified polyurethane resin obtained by reacting with fluorine or the like. The composition of the polyurethane resin can be appropriately selected depending on the intended use and purpose of the leather-like sheet material.

The above polyurethane resin preferably has a 100% modulus of 10 to 120 kg / cm ² .
If the 100% modulus is too small, the mechanical strength of the obtained leather-like sheet will decrease, and conversely if the 100% modulus is too large, the texture of the obtained leather-like sheet will be hard.

If necessary, various additives such as coagulation regulators (surfactants), colorants, fillers, antioxidants, water / oil repellents, etc. are added to the above polyurethane resin, and dimethylformamide, It is dissolved in a solvent such as dimethylacetamide, N-methylpyrrolidone or dimethylsulfoxide to give a polyurethane resin solution having an appropriate concentration. Also,
Of the above solvents, dimethylformamide is particularly preferable.

In the leather-like sheet of the present invention, a vinyl chloride-ethylene copolymer resin is added to the above polyurethane resin solution in order to impart air permeability and moisture permeability. This vinyl chloride-ethylene copolymer resin is insoluble in solvents such as methanol, acetone, toluene, and methyl ethyl ketone but does not dissolve to the extent that it swells, but it is a polar solvent used as a solvent for the polyurethane resin solution, specifically, Is soluble in solvents such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide. Moreover, the vinyl chloride-ethylene copolymer resin is
In the polyurethane solution, although dissolved in the solvent,
In the solution state, the polyurethane resin is phase-separated without being mixed uniformly. As a result, pores having an appropriate size, specifically pores having a diameter of 5 to 80 μm, are formed on the surface of the polyurethane resin layer obtained by wet coagulating the polyurethane resin, and air permeability and moisture permeability are imparted.

The degree of polymerization of the vinyl chloride-ethylene copolymer resin used in the leather-like sheet of the present invention is 800 to 2200.
Is preferred. If the degree of polymerization is too low, the compatibility with the polyurethane resin solution will be too good, and the problems that the pores on the surface of the polyurethane resin layer will not be sufficiently expressed and the texture of the obtained leather-like sheet will be hard On the contrary, if the degree of polymerization is too high, the compatibility with the polyurethane resin solution decreases, and the stability of the polyurethane resin solution to which the vinyl chloride-ethylene copolymer resin is added is lacking. The ethylene content of the vinyl chloride-ethylene copolymer resin is preferably in the range of 1 to 10% by weight. If the ethylene content is too low, the compatibility with the polyurethane resin solution will be too good and the pores on the polyurethane resin layer surface will not be sufficiently expressed, and conversely if the ethylene content will be too high,
The compatibility with the polyurethane resin solution is lowered, and the stability of the polyurethane resin solution to which the vinyl chloride-ethylene copolymer resin is added is lacking.

The vinyl chloride-ethylene copolymer resin is added in an amount of 1 to 100 parts by weight of the polyurethane resin.
It is 30 parts by weight, preferably 3 to 15 parts by weight. If the added amount of vinyl chloride-ethylene copolymer resin is too small, there is a problem that air permeability and moisture permeability are not sufficiently imparted, conversely if the added amount of polyethylene fine powder is too large, the mechanical strength of the polyurethane resin layer Getting worse.

The surface finishing layer formed on the surface of the polyurethane resin layer is the same as in the case of the conventional leather-like sheet, using a gravure roll coater and the like, a polyurethane resin solution containing a colorant and various additives, a polyamide resin solution, an acrylic resin. It is formed by applying a surface treatment agent such as a system resin solution, a polyamino acid resin solution, or a mixed solution thereof. Needless to say, as the solvent used for the surface treatment agent used at this time, a solvent that dissolves the polyurethane resin layer and does not close the pores formed on the surface is selected and used.

As with the conventional leather-like sheet, the leather-like sheet material of the present invention can be subjected to secondary processing such as embossing or kneading with an embossing roll, if necessary.

Next, the method for producing the leather-like sheet of the present invention will be described.

First, if necessary, raised or napped treatment,
A polyurethane resin solution containing the above-mentioned vinyl chloride-ethylene copolymer resin is applied and / or impregnated on a fiber base material such as polyvinyl alcohol or the like, which has been subjected to a surface smoothing treatment. Means for applying and / or impregnating the polyurethane resin solution includes, for example, dipping, application with a knife coater, etc., as in the conventional means.

Then, the fiber substrate coated and / or impregnated with the polyurethane resin solution is immersed in water or an aqueous solution of the solvent used in the polyurethane resin solution, preferably a non-solvent such as a 0 to 20% aqueous solution of dimethylformamide. The polyurethane resin is solidified and desolvated, washed with water and dried.
The solidification temperature of the polyurethane resin at this time is 15 to 40.
It is preferably selected in the range of ° C. By this step, appropriate pores are formed on the surface of the polyurethane resin layer.

Further, a polyurethane resin solution containing a colorant and various additives, a polyamide resin solution, an acrylic resin solution, a polyamino acid resin, etc., is formed on the polyurethane resin layer by a conventional gravure roll coater or the like. A surface treatment agent such as a solution or a mixed solution of these resins is applied and surface finishing is performed to obtain a leather-like sheet. Further, similarly to the conventional leather-like sheet material, the obtained leather-like sheet material is subjected to embossing with an embossing roll or the like to give unevenness to the leather-like sheet surface,
It is also possible to perform secondary processing such as rubbing processing.

[0021]

The leather-like sheet material of the present invention forms a polyurethane resin layer by adding a vinyl chloride-ethylene copolymer resin to the polyurethane resin forming the polyurethane resin layer and wet coagulating the polyurethane resin solution. Therefore, appropriate pores are formed on the surface of the polyurethane resin layer, and the polyurethane resin layer has air permeability and moisture permeability.

[0022]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples shown below.

Example 1 Nylon / Polyester (5
0/50), the entanglement obtained by needle punching a fiber web of split type fibers having a single yarn fineness of 1.0 denier after splitting and a fiber length of 30 to 40 mm, followed by high speed fluid flow processing. A non-woven fabric (weight: 250 g / m ² , apparent density: 0.25 g / cm ³ ) and silicone (Geranex S
H: Matsumoto Yushi Co., Ltd.) 2 parts by weight, polyvinyl alcohol (Gosereul GL-05: Nippon Gosei Co., Ltd.) 3 parts by weight,
Immersion in a treatment liquid consisting of 95 parts by weight of water, 110% squeezing
After squeezing with a hot air circulation type dryer for 10 minutes at 100 to 130 ° C, rolls heated to 180 ° C
The surface was smoothed by pressure and pressure for a minute to obtain a fiber base material.

The resulting fiber base material was impregnated with a polyurethane resin solution having the composition shown in Table 1 by the DIP-NIP method (a basis weight of 730 g / m ² ), and then the polyurethane resin solution shown in Table 2 was added. It was evenly coated using a knife coater (Basis weight: 820 g / m ² ).

[0025]

[Table 1] Polyester polyurethane resin ^{* 1} 100 parts by weight Vinyl chloride-ethylene copolymer resin ^{* 2} 3 parts by weight Anionic surfactant 0.5 parts by weight Nonionic surfactant 0.5 parts by weight Silicone foam stabilizer 0.5 parts by weight Colorant 10 parts by weight Dimethylformamide (solvent) 130 parts by weight * 1 Crisbon 8006HV: Dainippon Ink and Chemicals Incorporated (100% modulus 35 kg / cm ² , solid content 30%) * 2 Luron E1300: Tosoh Manufactured (polymerization degree 1300, ethylene content 2% by weight)

[0026]

[Table 2] Polyester polyurethane resin ^{* 1} 100 parts by weight Vinyl chloride-ethylene copolymer resin ^{* 2} 3 parts by weight Anionic surfactant 1 part by weight Nonionic surfactant 1 part by weight Silicone foam stabilizer 0.5 parts by weight Parts colorant 10 parts by weight dimethylformamide (solvent) 55 parts by weight

Then, the fibrous base material coated and impregnated with the polyurethane resin is dipped in a 13% aqueous solution of dimethylformamide (liquid temperature 25 ° C.) to solidify the polyurethane resin, and then 60 ° C. in warm water at 60 ° C. Desolvation for 1 minute, washing with water, 1
A polyurethane resin layer was formed by drying for 10 minutes with a hot air circulation dryer at 00 to 130 ° C. Many pores having a diameter of 10 to 70 μm were formed on the surface of the obtained polyurethane resin layer.

Further, a polyurethane resin surface agent to which a colorant was added was applied onto the polyurethane resin layer 5 times with a 100 mesh gravure roll, and then the surface was embossed by heating and pressing with an embossing roll having a pore-drawing pattern. The leather-like sheet was obtained by processing and then rubbing. The obtained leather-like sheet material had a feeling of unity, had a suitable waist and a soft texture, and was excellent in breathability, moisture permeability and water resistance. Further, the obtained leather-like sheet was tested for air permeability, moisture permeability and water resistance by the following methods. The results are shown in Table 5.

[Test Method] (1) Air Permeability According to the method defined in “JIS P 8117”, the amount of air passing per hour (l / cm ² · hr) was measured using a Gurley densometer. ). (2) Water vapor transmission rate The water vapor transmission rate (g / m ² · 24 hr) was measured according to the method of condition B defined in “JIS Z 0208”. (3) Water resistance The water pressure resistant water column (mmH ₂ O) was measured according to the method A specified in “JIS L 1092”.

Example 2 Nylon / Polyester (5
0/50), the entanglement obtained by needle punching a fiber web of split type fibers having a single yarn fineness of 0.2 denier after splitting and a fiber length of 30 to 40 mm, followed by high speed fluid flow processing. A non-woven fabric (weight: 200 g / m ² , apparent density: 0.23 g / cm ³ ) and silicone (Geranex S
H: Matsumoto Yushi Co., Ltd.) 2 parts by weight, polyvinyl alcohol (Gosereul GL-05: Nippon Gosei Co., Ltd.) 3 parts by weight,
Immersion in a treatment liquid consisting of 95 parts by weight of water, 110% squeezing
After squeezing with a hot air circulation type dryer for 10 minutes at 100 to 130 ° C, rolls heated to 180 ° C
The surface was smoothed by pressure and pressure for a minute to obtain a fiber base material.

The obtained fiber base material was impregnated with the polyurethane resin solution having the composition shown in Table 3 by the DIP-NIP method (Basis weight 630 g / m ² ), and then the polyurethane resin solution shown in Table 4 was used. It was evenly coated using a knife coater (Basis weight: 650 g / m ² ).

[0032]

[Table 3] Polyester polyurethane resin ^{* 3} 100 parts by weight Vinyl chloride-ethylene copolymer resin ^{* 4} 4 parts by weight Anionic surfactant 0.5 parts by weight Nonionic surfactant 0.5 parts by weight Silicone foam stabilizer 0.5 parts by weight Colorant 10 parts by weight Dimethylformamide (solvent) 125 parts by weight * 3 Resamine CU4310: manufactured by Dainichi Seika (100% modulus 40 kg / cm ² , solid content 26%) * 4 Sekisui PVC VE-K : Sekisui Chemical Co., Ltd. (Polymerization degree 1050, ethylene content 4% by weight)

[0033]

[Table 4] Polyester polyurethane resin ^{* 3} 100 parts by weight Vinyl chloride-ethylene copolymer resin ^{* 4} 5 parts by weight Anionic surfactant 0.5 parts by weight Nonionic surfactant 2 parts by weight Silicone foam stabilizer 1 part by weight Parts colorant 10 parts by weight dimethylformamide (solvent) 50 parts by weight

Then, the fibrous base material coated and impregnated with the polyurethane resin is dipped in a 13% aqueous solution of dimethylformamide (liquid temperature 25 ° C.) to solidify the polyurethane resin, and then 60 ° C. in warm water at 60 ° C. Desolvation for 1 minute, washing with water, 1
A polyurethane resin layer was formed by drying for 10 minutes with a hot air circulation dryer at 00 to 130 ° C. A large number of pores having a diameter of 5 to 60 μm were formed on the surface of the obtained polyurethane resin layer.

Further, a polyurethane resin surface agent to which a colorant was added was applied onto the polyurethane resin layer five times with a 100 mesh gravure roll, and then the surface was embossed by heating and pressing with an embossing roll having a leather pattern. A leather-like sheet was obtained by processing. The obtained leather-like sheet material had a feeling of unity, had a suitable waist and a soft texture, and was excellent in breathability, moisture permeability and water resistance. Further, the obtained leather-like sheet was tested for air permeability, moisture permeability and water resistance in the same manner as in Example 1. The results are shown in Table 5.

Comparative Example 1 A leather-like sheet material was obtained in the same manner as in Example 1 except that the vinyl chloride-ethylene copolymer resin was not added to the polyurethane resin solutions shown in Tables 1 and 2. The leather-like sheet obtained has a sense of unity,
Although it had an appropriate waist and a soft texture, it was inferior in breathability and moisture permeability. In addition, regarding the air permeability, moisture permeability, and water resistance of the obtained leather-like sheet material, Example 1
It tested by the method similar to. The results are shown in Table 5.

Comparative Example 2 Leather was prepared in the same manner as in Example 1 except that the amount of the vinyl chloride-ethylene copolymer resin added to the polyurethane resin solutions shown in Tables 1 and 2 was changed to 0.5 part by weight. A sheet-like product was obtained. The obtained leather-like sheet had a feeling of unity and had a proper waist and a soft texture, but was inferior in breathability and moisture permeability. Further, the obtained leather-like sheet was tested for air permeability, moisture permeability and water resistance in the same manner as in Example 1. The results are shown in Table 5.

[Comparative Example 3] A leather-like sheet was obtained in the same manner as in Example 1 except that the addition amount of the vinyl chloride-ethylene copolymer resin added to the polyurethane resin solution shown in Tables 1 and 2 was changed to 35 parts by weight. A substance was obtained. The obtained leather-like sheet was excellent in breathability and moisture permeability, but inferior in flexibility. Further, the obtained leather-like sheet was tested for air permeability, moisture permeability and water resistance in the same manner as in Example 1. The results are shown in Table 5.

[0039]

[Table 5]

[0040]

As described above in detail, the leather-like sheet material of the present invention and the leather-like sheet material obtained by the method for producing the leather-like sheet material of the present invention have excellent breathability and moisture permeability. , And also excellent in water resistance, applications where the occurrence of stuffiness is a problem, such as shoe lining materials, insole sole materials,
It is preferably used as a material for clothing and the like.

Claims (3)

[Claims] 1. A leather-like sheet material having a fiber base material, a polyurethane resin layer, and a surface finish layer, wherein the polyurethane resin layer comprises 100 parts by weight of a vinyl chloride-ethylene copolymer resin on the fiber base material. To 1
A leather-like sheet material which is a polyurethane resin layer obtained by impregnating and / or applying a polyurethane resin solution containing 30 parts by weight and wet coagulating. 2. A vinyl chloride-ethylene copolymer resin having a degree of polymerization of 800 to 2200 and an ethylene content of 1 to 1.
The leather-like sheet material according to claim 1, which is 0% by weight. 3. A fiber base material containing 1 to 30 parts of vinyl chloride-ethylene copolymer resin per 100 parts by weight of polyurethane resin.
A step of impregnating and / or applying a polyurethane resin solution contained by weight, a fiber base material impregnated and / or applied with a polyurethane resin solution is dipped in a non-solvent to wet-coagulate the polyurethane resin, and then desolventized and washed with water. And then drying to form a polyurethane resin porous layer having fine pores on the surface, and finishing the surface, a method for producing a leather-like sheet.