JPH08337975A - Leathery sheet-like product and its production - Google Patents

Abstract

PURPOSE: To obtain a leathery sheet-like product imparted with both air permeability and moisture permeability as well as having both appearance and touch feeling in close resemblance to those of natural leather. CONSTITUTION: This leathery sheet-like product is composed of a fibrous base material, a polyurethane resin layer thereon and surface finishing layer thereon. The polyurethane resin layer is obtained by impregnating and/or coating the fibrous base material with a polyurethane resin solution containing synthetic resin fine particles 5-100μm in average diameter soluble in polar solvents such as dimethylformamide but insoluble in nonpolar solvents followed by conducting a wet solidification.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a leather-like sheet material having excellent breathability and moisture permeability, which is preferably used as a material for shoe laces, insole soles, 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 wetted by impregnating and / or coating a polyurethane resin solution containing synthetic resin fine particles having an average particle diameter of 5 to 100 μm soluble in a polar solvent and insoluble in a nonpolar solvent on a fiber base material. It is characterized in that it is a polyurethane resin layer having a large number of air holes on the surface obtained by solidification.

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 having an average particle size of 5 to 100 μm, soluble in a polar solvent and a non-polar solvent. Of impregnating and / or applying a polyurethane resin solution containing fine particles of a synthetic resin insoluble in water, a fibrous base material impregnated and / or applied with a polyurethane resin solution is dipped in a non-solvent to wet-coagulate and desolvate the polyurethane resin A step of forming a polyurethane resin porous layer having a large number of fine ventilation holes on the surface by drying after washing with water,
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 polar solvent such as dimethylacetamide, N-methylpyrrolidone or dimethylsulfoxide, particularly preferably dimethylformamide, to obtain a polyurethane resin solution having an appropriate concentration.

In the leather-like sheet of the present invention, synthetic resin fine particles soluble in a polar solvent and insoluble in a non-polar solvent are added to the above polyurethane resin solution in order to impart air permeability and moisture permeability. . As the synthetic resin forming the synthetic resin fine particles, polyacrylonitrile resin, polymethacrylate resin, and polymethylmethacrylate resin are particularly preferable. The polar solvent here is a solvent generally used as a solvent for polyurethane resin solutions such as dimethylformamide, dimethylacetamide, and dimethylsulfoxide, and the nonpolar solvent is methanol, acetone, toluene, methyl ethyl ketone, or the like. A general solvent.

The fine particles of synthetic resin are dissolved in a solvent of polyurethane resin which is a polar solvent, and in addition, they are phase-separated without being mixed uniformly with the solution of polyurethane resin in a solution state. As a result, when the polyurethane resin is wet-solidified, the synthetic resin fine particles act as a solidifying nucleating agent to form fine vent holes on the surface of the polyurethane resin layer, which communicate with the fine pores inside the polyurethane resin layer. Therefore, after applying and / or impregnating the polyurethane resin solution containing the synthetic resin fine particles, the polyurethane resin is wet-coagulated to form an appropriate size of vent hole, specifically, a diameter on the surface of the polyurethane resin layer. Ventilation holes of about 1 to 60 μm are formed to give the leather-like sheet breathability and moisture permeability.

According to the findings of the present inventors, the above-mentioned synthetic resin fine particles are dissolved in a polyurethane resin solution, but the size of the pores developed on the surface of the polyurethane resin layer of the obtained leather-like sheet is polyurethane. It is approximately proportional to the size of the synthetic resin fine particles added to the resin solution. Therefore, the synthetic resin fine particles used in the leather-like sheet of the present invention have a size for forming ventilation holes of an appropriate size on the surface of the polyurethane resin layer of the leather-like sheet, specifically, an average particle size of 5 It is important to be in the range of -100 μm, preferably 10-70 μm. When synthetic resin fine particles having an average particle size of less than 5 μm are used, the problem that the synthetic resin fine particles are aggregated and the air holes appearing on the surface of the polyurethane resin layer become too small, so that sufficient air permeability and moisture permeability are imparted. The average particle size is 1
When the synthetic resin fine particles having a diameter of more than 00 μm are used, there is a problem that the pores formed on the surface of the polyurethane resin layer become too large and the water resistance deteriorates.

The amount of the synthetic resin fine particles added is 1 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the polyurethane resin. If the addition amount of the synthetic resin fine particles is too small, there is a problem that air permeability and moisture permeability are not sufficiently imparted, and conversely, if the addition amount of the synthetic resin fine particles is too large, the mechanical strength of the polyurethane resin layer deteriorates.

Further, in order to prevent water from penetrating through the ventilation holes and adhesion of dirt, the above-mentioned polyurethane resin layer contains
The content of fluorine in all the polymers forming the polyurethane resin layer is 0.02 to 1.6% by weight, preferably 0.07 to
The fluorine-containing polyurethane resin may be added within the range of 1.0% by weight. If the fluorine content is too high, the water / oil repellency effect becomes too large, the surface finishing in the subsequent step becomes difficult, and the mechanical strength of the obtained leather-like sheet may deteriorate.

The surface finish layer formed on the surface of the polyurethane resin layer is a polyurethane resin solution containing a colorant and various additives in a conventional gravure roll coater, a polyamide resin solution, as in a conventional leather-like sheet. , An acrylic resin solution, a polyamino acid resin solution, a mixed solution thereof, or the like is applied. It is desirable that the surface treatment agent is applied in a small amount so that the vent holes formed on the surface of the polyurethane resin layer are not blocked. Specifically, the coating amount per one time, solids and 5 g / m ² or less, which is to the total adhesion amount several times 5 to 20 g / m ² or less desirable. 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 block the ventilation holes formed on the surface is selected and used.

The surface finish layer is not limited to the one formed by applying a surface treatment agent such as a polyurethane resin solution containing a colorant and various additives with a gravure roll coater as described above. , A transfer foil mainly composed of a polyurethane resin, an acrylic resin, or a copolymer resin thereof or a mixture of the above resins through a binder layer which is formed as needed before applying the surface treatment agent. The transfer foil may be formed by transferring the transfer foil, and further applying the above-mentioned surface treatment agent thereon. In this way, by providing the surface finishing layer formed via the transfer foil between the polyurethane surface treatment layer and the polyurethane resin layer, the surface can be smoothed, and pattern printing, embossing, etc. are facilitated. Therefore, it is possible to obtain a leather-like sheet having a good design. Further, natural leather-like creases are generated, and a leather-like sheet-like material that is very similar in appearance to natural leather can be obtained.

The transfer foil is a film having a thickness of 1 to 20 μm, which is mainly composed of a polyurethane resin, an acrylic resin or a copolymer resin thereof, or a mixture of the above resins, and has a shape. The film may be a film alone or a film held on a support having releasability such as a PET film or a release paper. As the transfer foil, a transfer foil formed by covering the ventilation holes formed in the polyurethane resin surface layer is applied to the polyurethane resin surface treatment agent to reproduce the ventilation item. It is necessary to select one that is soluble in the solvent used.

Before the transfer foil is transferred onto the surface of the polyurethane resin layer, a binder layer provided as necessary is a water-based polyurethane resin or acrylic resin so that the shape of the vent holes on the surface of the polyurethane resin layer can be maintained as much as possible. It is desirable to use a system resin. By providing the above binder layer, the adhesion between the polyurethane resin layer and the transfer foil can be improved.

In the surface finishing layer consisting of the binder layer, the transfer foil and the polyurethane surface treatment layer, which are provided as necessary, at least the leather-like sheet finally obtained has a diameter of 1 to 50 μm on the surface. The ventilation holes of are exposed to ensure air permeability and moisture permeability.

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. In particular, the rubbing process promotes the separation of the synthetic resin fine particles remaining inside the polyurethane resin layer, and thus the obtained leather-like sheet-like product is more effectively breathable. This rubbing process is usually done for finishing natural leather, artificial leather, etc. Staking machine, Yamasa rubbing machine (Yamasa Momi Planning Co., Ltd.)
Manufactured] etc. can be used. The rubbing process may be performed before the surface finishing layer is formed or after the surface finishing layer is formed.

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 synthetic resin fine particles is applied and / or impregnated on a fiber substrate on which polyvinyl alcohol or the like has been fixed or whose surface has been smoothed. Means for applying and / or impregnating the polyurethane resin solution is similar to the conventional means, for example, dipping,
Examples thereof include coating with a knife coater or the like.

Then, the fiber substrate coated and / or impregnated with the polyurethane resin solution is immersed in water or an aqueous solution of a 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 ventilation holes 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 treating 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.

When the surface finish layer is formed from the transfer foil and the polyurethane resin surface treatment layer, first,
The transfer foil is heated and pressed onto the surface of the polyurethane resin layer to transfer it, and then a polyurethane resin surface treatment agent is applied to obtain a leather-like sheet. At this time, before the transfer of the transfer foil, a binder such as an aqueous polyurethane resin or an acrylic resin may be applied to the surface of the polyurethane resin layer with a gravure roll coater or the like.

Further, like the conventional leather-like sheet material,
The obtained leather-like sheet material may be subjected to embossing with an embossing roll or the like to give unevenness to the surface of the leather-like sheet, or to be subjected to secondary processing such as rubbing. In particular, in the method for producing a leather-like sheet material of the present invention, rubbing is effective in improving air permeability.
This kneading process can be performed under the same conditions as in the conventional case and the leather-like sheet material. Further, the rubbing process can be performed before forming the surface finishing layer and / or after forming the surface finishing layer.

[0029]

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,
Immerse in treatment liquid consisting of 95 parts by weight of water, squeeze rate 120%
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 1 by the DIP-NIP method (unit weight: 700 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: 800 g / m ² ).

[0032]

[Table 1] Polyester polyurethane resin ^{* 1} 100 parts by weight Polyacrylonitrile resin fine particles ^{* 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, Inc. (100% modulus 35 kg / cm ² , solid content 30%) * 2 Tough Tick AM: Toyobo Co., Ltd. Made (average particle size 7-10 μm)

[0033]

[Table 2] Polyester polyurethane resin ^{* 1} 100 parts by weight Polyacrylonitrile resin fine particles ^{* 2} 5 parts by weight Anionic surfactant 1 part by weight Nonionic surfactant 1 part by weight Silicone foam stabilizer 0.5 parts by weight Coloring Agent 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. A large number of air holes having a diameter of 5 to 50 μm were formed on the surface of the obtained polyurethane resin layer.

Further, a polyurethane resin surface treatment agent to which a colorant has been added is applied to the polyurethane resin layer four times with a 100 mesh gravure roll, and then the surface is 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 by the following methods. The results are shown in Table 9.

[Test Method] (1) Air Permeability According to the method specified in "JIS P 8117", measurement is performed using a Gurley densometer, and the amount of air passing per hour (L / cm ² · hr) ). (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,
Immerse in treatment liquid consisting of 95 parts by weight of water, squeeze rate 120%
After squeezing with a hot air circulation type dryer for 7 minutes at 100 to 130 ° C., a roll heated to 180 ° C. was pressed and pressed for 2 minutes for surface smoothing to obtain a fiber base material. .

The resulting fibrous base material was impregnated with a polyurethane resin solution having the composition shown in Table 3 by the DIP-NIP method (basis weight of 600 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: 680 g / m ² ).

[0039]

[Table 3] Polyester polyurethane resin ^{* 3} 100 parts by weight Polymethylmethacrylate resin fine particles ^{* 4} 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) 125 parts by weight * 3 Resamine CU4310: manufactured by Dainichiseika (100% modulus 40 kg / cm ² , solid content 26%) * 4 Techpolymer MB-20: Sekisui Made by Kasei Co., Ltd. (average particle size 5-100 μm)

[0040]

[Table 4] Polyester polyurethane resin ^{* 3} 100 parts by weight Polymethylmethacrylate resin fine particles ^{* 4} 3 parts by weight Fluorine-containing polyurethane resin ^{* 5} 1 part by weight Anionic surfactant 0.5 parts by weight Nonionic surfactant 2 parts by weight Part Silicone-based foam stabilizer 1 part by weight Colorant 10 parts by weight Dimethylformamide (solvent) 50 parts by weight * 5 Crisbon Assister FX3D: manufactured by Dainippon Ink and Chemicals, Inc.

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 10 to 30 μm were formed on the surface of the obtained polyurethane resin layer.

Further, a polyurethane resin surface treating agent to which a colorant has been added is applied onto the polyurethane resin layer four times with a 100-mesh gravure roll, and then the surface is 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 had a feeling of unity, had an appropriate waist and a soft texture, and was excellent in breathability, moisture permeability, water resistance and stain resistance. Further, regarding the air permeability, moisture permeability, and water resistance of the obtained leather-like sheet material,
The test was performed in the same manner as in Example 1. The results are shown in Table 9.

Example 3 Polyester fiber (1.2 denier) and rayon fiber (1 denier) were mixed-spun (weight ratio 65/35), and a double-sided brushed cloth woven into a twill weave was coated with silicone (Geranex SH: Matsumoto). 2 parts by weight,
It is immersed in a treatment liquid consisting of 3 parts by weight of polyvinyl alcohol (Goseruru GL-05: manufactured by Nippon Gosei Co., Ltd.) and 95 parts by weight of water, squeezed at a squeezing ratio of 110%, and dried at a hot-air circulation dryer at 100 to 130 ° C. After being dried for 10 minutes at 80 ° C., pressure-bonding was performed for 2 minutes by a roll heated to 180 ° C. to perform surface smoothing to obtain a fiber base material.

The obtained fibrous base material was impregnated with a polyurethane resin solution having the composition shown in Table 5 by the DIP-NIP method (basis weight: 600 g / m ² ), and then the polyurethane resin solution shown in Table 6 was used. It was evenly applied using a knife coater (area weight: 750 g / m ² ).

[0045]

[Table 5] Polyester / ether polyurethane resin ^{* 6} 100 parts by weight Polymethacrylate resin fine particles ^{* 7} 2 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) 130 parts by weight * 6 Crisbon MP-145: manufactured by Dainippon Ink and Chemicals, Inc. (100% modulus 40 kg / cm ² , solid content 30%) * 7 Matsumoto Microsphere M: Matsumoto Yushi-Seiyaku Co., Ltd. (average particle size 5-20 μm)

[0046]

[Table 6] Polyester / ether polyurethane resin ^{* 6} 100 parts by weight Polymethacrylate resin fine particles ^{* 7} 4 parts by weight Anionic surfactant 1 part by weight Nonionic surfactant 2 parts by weight Silicone foam stabilizer 1 part by weight Coloring Agent 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 12% 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 30 μm were formed on the surface of the obtained polyurethane resin layer.

Further, a polyurethane resin surface treatment agent to which a colorant was added was applied onto the polyurethane resin layer four times with a 100 mesh gravure roll, and then the surface was heated and pressed with an embossing roll having a leather pattern. The leather-like sheet was obtained by embossing. 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 9.

Example 4 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, and then performing high speed fluid flow processing. Nonwoven fabric (weight: 350 g / m ² , apparent density: 0.23 g / cm ³ ), polyvinyl alcohol (Gosenol GL-05: manufactured by Nippon Gosei Co., Ltd.) 4 parts by weight, water 96
It is dipped in a treatment liquid consisting of parts by weight, squeezed at a squeezing ratio of 120%, dried at 100 to 130 ° C. for 10 minutes by a hot air circulation dryer, and then pressed for 2 minutes by a roll heated to 180 ° C. The cloth was put on and subjected to surface smoothing to obtain a fiber base material.

The resulting fibrous base material was impregnated with the polyurethane resin solution having the formulation shown in Table 7 by the DIP-NIP method (Basis weight 850 g / m ² ), and then the polyurethane resin solution shown in Table 8 was used. It was evenly applied using a knife coater (area weight: 750 g / m ² ).

[0051]

[Table 7] Polyester polyurethane resin ^{* 8} 100 parts by weight Anionic surfactant 1 part by weight Nonionic surfactant 1 part by weight Silicone foam stabilizer 0.5 parts by weight Colorant 10 parts by weight Dimethylformamide (solvent) 200 Parts by weight * 8 Crisbon 8006HV: manufactured by Dainippon Ink and Chemicals, Inc. (100% modulus 35 kg / cm ² , solid content 30%)

[0052]

[Table 8] Polyester polyurethane resin ^{* 8} 100 parts by weight Polyacrylonitrile resin fine particles ^{* 9} 5 parts by weight Anionic surfactant 1 part by weight Nonionic surfactant 1 part by weight Silicone foam stabilizer 0.5 parts by weight Coloring Agent 10 parts by weight Dimethylformamide (solvent) 58 parts by weight * 9 Toughtic A20: manufactured by Toyobo Co., Ltd. (average particle size 25 μm)

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.

A polyurethane resin solution (Dispercoll U-5) was used as an aqueous binder on the surface of the polyurethane resin layer.
3: Bayer) was applied once with a 100-mesh gravure roll and dried.

Next, a polyester film having a thickness of 3.5 is used.
Transfer foil coated with μm acrylic ester resin (SUPER LUCIDO: manufactured by MENPHIS)
Was bonded to the surface of the polyurethane resin layer coated with the binder by heating while heating at 140 ° C. with a heating roll. After that, the polyester film was peeled off to obtain a sheet-like material having a transfer foil formed on the surface of the polyurethane resin layer.

Further, a polyurethane resin surface treating agent containing a coloring agent was applied onto a transfer foil formed on the surface of the polyurethane resin layer of this sheet-like material three times with a 100-mesh gravure roll, and then the surface was coated. Embossing was performed by heating and pressing with an embossing roll having a squeeze pattern to obtain a leather-like sheet.

The obtained leather-like sheet material has a feeling of unity, an appropriate waist and a soft texture and a natural leather-like crease, and is excellent in breathability, moisture permeability and water resistance. Met. 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 9.

Example 5 A leather-like sheet was formed in the same manner as in Example 1 except that a rubbing process was performed twice using a vibration staking machine (manufactured by CARTIGLIANO) before applying the polyurethane resin surface treatment agent. I got a thing. The leather-like sheet thus obtained had a feeling of unity, had an appropriate waist and soft texture, and had a crease like natural leather, and was excellent in breathability, moisture permeability and water resistance. . Further, the air permeability of the obtained leather-like sheet material,
The moisture permeability and water resistance were tested by the following methods. The results are shown in Table 9.

Example 6 Before applying the polyurethane resin surface treatment agent, a Yamasa kneading machine (manufactured by Yamasa Momi Planning Co., Ltd.)
A leather-like sheet was obtained in the same manner as in Example 2, except that the surfaces of the leather-like sheet were combined and subjected to rubbing once. The leather-like sheet thus obtained had a feeling of unity, had an appropriate waist and soft texture, and had a crease like natural leather, 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 9.

[Example 7] A leather-like sheet material was prepared in the same manner as in Example 3 except that the composition was rubbed twice using a vibration staking machine (manufactured by CARTIGLIANO) before applying the polyurethane resin surface treatment agent. Got The leather-like sheet thus obtained had a feeling of unity, had an appropriate waist and soft texture, and had a crease like natural leather, 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 9.

[Example 8] Before applying the polyurethane resin solution to the surface of the polyurethane resin layer, rubbing was performed twice using a vibration staking machine (manufactured by CARTIGLIANO), and the transfer foil was transferred to the surface of the polyurethane resin layer. After that, a leather-like sheet material was obtained in the same manner as in Example 4 except that the same rubbing process as described above was performed.
The leather-like sheet thus obtained had a feeling of unity, had an appropriate waist and soft texture, and had a crease like natural leather, 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 9.

Comparative Example 1 A leather-like sheet material was obtained in the same manner as in Example 1 except that the polyacrylonitrile-based resin fine particles were not added to the polyurethane resin solutions shown in Tables 1 and 2. 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 9.

[Comparative Example 2] A leather-like sheet was obtained in the same manner as in Example 1 except that the addition amount of the polyacrylonitrile resin fine particles added to the polyurethane resin solution shown in Tables 1 and 2 was changed to 0.1 part by weight. A substance 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 9.

[Comparative Example 3] Polyacrylonitrile-based resin fine particles to be added to the polyurethane resin solutions shown in Tables 1 and 2 were crosslinked synthetic resins (Toughtic AR: manufactured by Toyobo Co., Ltd.) having an average particle diameter of 20 μm and insoluble in polar solvents Except instead of
A leather-like sheet material was obtained in the same manner as in Example 1. 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 9.

[Comparative Example 4] Polymethylmethacrylate resin fine particles to be added to the polyurethane resin solutions shown in Tables 3 and 4 having an average particle diameter of 1 to 2 μm (MP-140
0: manufactured by Soken Kagaku Co., Ltd.), and a leather-like sheet material was obtained in the same manner as in Example 2. 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 9.

[Comparative Example 5] Except that the polyacrylonitrile-based resin fine particles added to the polyurethane resin solutions shown in Tables 1 and 2 were replaced with those having an average particle size of 1000 to 2000 μm (Toughtic N-23: manufactured by Toyobo Co., Ltd.). Was obtained in the same manner as in Example 1 to obtain a leather-like sheet. The obtained leather-like sheet had a feeling of unity, had an appropriate waist and soft texture, and was excellent in breathability and moisture permeability, but was inferior in 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 9.

[0067]

[Table 9]

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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 (10)

[Claims] 1. A leather-like sheet having a fiber base material, a polyurethane resin layer, and a surface finishing layer, wherein the polyurethane resin layer has an average particle size of 5 to 100 μm on the fiber base material.
and a polyurethane resin solution containing synthetic resin fine particles soluble in a polar solvent and insoluble in a non-polar solvent of m.
Alternatively, a leather-like sheet material which is a polyurethane resin layer having a large number of ventilation holes on the surface obtained by applying and wet coagulating. 2. The leather-like sheet material according to claim 1, wherein the synthetic resin fine particles are one or more resins selected from polyacrylonitrile-based resins, polymethacrylate-based resins, and polymethylmethacrylate-based resins. 3. A surface-finishing layer is formed on a transfer foil having a thickness of 1 to 20 μm, which is mainly composed of one or more resins selected from polyurethane resins, acrylic resins, or copolymer resins thereof, and transfer foils. The leather-like sheet material according to claim 1, comprising a polyurethane resin surface-treated layer. 4. The leather-like sheet material according to claim 3, wherein the transfer foil is soluble in an organic solvent contained in the polyurethane resin surface treatment agent forming the polyurethane resin surface treatment layer. 5. The leather-like sheet material according to claim 3, which has a binder layer between the polyurethane resin layer and the transfer foil. 6. The content of fluorine in all the polymers forming the polyurethane resin layer is 0.02 in the polyurethane resin layer.
The leather-like sheet material according to any one of claims 1 to 5, to which a fluorine-containing polyretane resin is added in an amount of about 1.6% by weight. 7. A step of impregnating and / or applying a polyurethane resin solution containing synthetic resin fine particles having an average particle diameter of 5 to 100 μm, which is soluble in a polar solvent and insoluble in a nonpolar solvent, to a fiber base material. Polyurethane having a large number of fine ventilation holes on the surface by immersing a fibrous base material impregnated and / or coated with a resin solution in a non-solvent to wet-coagulate the polyurethane resin, desolvating and washing with water, and then drying. A method for producing a leather-like sheet material, which comprises a step of forming a resin porous layer and a step of surface finishing. 8. The surface finishing step comprises 1 to 20 made of one or more resins selected from polyurethane resins, acrylic resins, or copolymer resins thereof.
The leather-like sheet according to claim 7, comprising a step of transferring a transfer foil having a thickness of μm to the surface of the polyurethane resin layer, and a step of applying a polyurethane resin surface treatment agent on the transfer foil to form a polyurethane resin surface treatment layer. Method for manufacturing a shaped article. 9. The method for producing a leather-like sheet material according to claim 8, further comprising a step of applying a binder to the surface of the polyurethane resin layer before transferring the transfer foil. 10. A rubbing process is performed before the surface finishing step and / or during the surface finishing step and / or after the surface finishing step.
The method for producing a leather-like sheet material according to the item.