JPH02242979A - Production of leathery sheet-like product - Google Patents

Abstract

PURPOSE:To obtain the subject flexible sheet excellent in surface characteristics by applying a specific aqueous resin composition liquid on the surface where the finely porous portion in the porous layer of a leathery sheet-like product has been exposed followed by further coating an organic solvent-contg. resin composition liquid to form a coating film layer. CONSTITUTION:The surface of a base material sheet made up of (A) base layer comprising (1) a fibrous polymer such as fiber-interlaced nonwoven fabric made from ultrafine fiber and (2) an elastomer such as of polyurethane and (B) a porous layer of said polymer is buffed to expose the finely porous portion. The resultant surface is coated with an aqueous resin composition liquid comprising (a) an aqueous dispersion of polyurethane and/or acrylic resin, (b) a lubricant, (c) an emulsifying agent and (d) a casein aqueous dispersion and, if needed, further coated with a resin composition liquid comprising (3) an acrylic resin- or polyurethane emulsion and (4) a pyroxylin lacquer solution and another resin composition liquid containing organic solvent comprising (5) a lubricant and (6) an emulsifying agent, followed by drying to form a coating film layer, thus obtaining the objective flexible leathery sheet-like product similar to natural leather, high in air- and moisture-permeability with its surface free from tack and giving slimy feel.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention has a surface that has low repulsion, is flexible, feels slimy to the touch, and has excellent air permeability, moisture permeability, and surface strength. , relates to a method for producing a leather-like sheet material having good resistance to destruction of the porous structure.

<Prior Art> Conventionally, there have been many proposals for improving the physical properties of the surface of a leather-like sheet material having a porous surface layer made of a polymer mainly composed of polyurethane. In particular, we have been studying the structure and composition of leather-like sheets, the raw materials used, manufacturing conditions, etc., in order to improve the surface folds, air permeability, moisture permeability, resilience, etc. For example, from the point of view of the structure and composition of a leather-like sheet, the average diameter is 20 to 200.
By grinding the porous surface of the honeycomb-like porous structure with a diameter of 10 μm and removing the epidermis (skin layer), the bubble diameter of most of the exposed surface is reduced to 10 μm.
A leather-like sheet material with a so-called silver surface finish by forming a polymer coating layer on the exposed surface of the bubbles is disclosed in Japanese Patent Publication No. 40-20273 and Japanese Patent Publication No. 47-38.
This method has been proposed in Japanese Patent Publication No. 623 and Japanese Patent Publication No. 54-963. Furthermore, the applicant has determined that the pore size on the surface is between 3 and 100.
A polyurethane solution is applied to the surface layer of a porous structure having many μm microholes, and the microholes are shaped into fine pores to produce a leather-like sheet material having microholes on the surface. This method is proposed in Japanese Patent Publication No. 56-10346.

<Problems to be Solved by the Invention> Conventional leather-like sheet materials can be improved in appearance performance, such as by making the folded form similar to natural leather, or by improving drapability to obtain a solid appearance, or In terms of performance, the focus was on improving air permeability and moisture permeability. However, conventional leather-like sheet materials are flexible but have a dry and dry feel. Therefore, in order to produce a leather-like sheet material with a slimy, flexible texture and feel, treatments are carried out with softeners, plasticizers, or oils to improve the texture. It is not preferable to improve the feel by using only a processing agent, as the stickiness characteristic of the processing agent may occur, and over a long period of time, the processing agent may bleed or have an unfavorable effect on the polyurethane.

On the other hand, on the surface of a conventional leather-like sheet material having a porous layer or a non-porous layer, for example, a composition of a flexible polymer or a treatment agent such as a flexible polymer and an oil or fat can be applied without removing the skin layer. If a substance is applied, the frictional resistance on the surface increases, resulting in poor wear resistance or decreased heat resistance, which is undesirable. Furthermore, problems such as poor moldability due to surface embossing occur.

The present invention has a surface that has a low repulsive feeling, is flexible, and has a slimy feel to the touch; To provide a leather-like sheet material that has excellent moisture permeability, has a surface and fold shape similar to natural leather, and has visual performance that gives a sense of solidity and flexibility. be.

Means for Solving the Problems The present invention provides a leather-like fiber assembly comprising a base layer containing a polymer mainly composed of an elastic polymer and a porous layer composed of a polymer mainly composed of an elastic polymer. In the sheet-like product, after the fine porous portion inside the porous layer of the leather-like sheet-like product is made into an exposed surface, an aqueous dispersion of polyurethane and/or acrylic resin, an oil or fat, an emulsifier, and an aqueous casein dispersion are added. Alternatively, it is a method for producing a leather-like sheet material, which is characterized by applying an aqueous resin composition liquid [I] consisting of an aqueous solution and drying it.

The present invention also provides a leather-like sheet-like article comprising a base layer containing a polymer mainly composed of an elastic polymer in a fiber aggregate and a porous layer composed of a polymer mainly composed of an elastic polymer. After exposing the fine porous portion inside the porous layer of the sheet-like sheet, an aqueous resin composition consisting of an aqueous dispersion of polyurethane and/or acrylic resin, an oil or fat, an emulsifier, and an aqueous casein dispersion or aqueous solution is prepared. liquid [1]
After coating, a resin composition solution C11) containing an organic solvent consisting of a resin composition solution of an acrylic resin emulsion or a polyurethane emulsion and a solution of nitrified cotton lacquer, oil and fat, and an emulsifier is applied and dried to form a coating layer. This is a method for producing a leather-like sheet-like material, which is characterized by forming a leather-like sheet-like material.

That is, the present invention applies polyurethane to fiber aggregates such as woven fabrics, knitted fabrics, or fiber-entangled nonwoven fabrics made of any fibers such as ordinary fibers, ultrafine fibers and/or bundled fibers thereof, and special porous fibers. , acrylic polymers, acrylonitrile-butadiene copolymers, styrene-butadiene copolymers, and other synthetic rubbers. The obtained base layer consists of a polymer mainly composed of an elastic polymer and a fiber aggregate. On one side of the base layer, a sheet-like material with a surface layer of a porous layer of a polymer mainly composed of an elastic polymer such as polyurethane or plasticized polyvinyl chloride is formed, and this is used as a base material for a leather-like sheet-like material. The skin layer on the surface of the porous layer of the base sheet is ground with sandpaper or the like to expose the fine porous portion inside the porous layer. Thereafter, an aqueous dispersion of polyurethane and/or acrylic resin is applied to the exposed microporous surface.
A resin composition liquid [I] consisting of an oil, an emulsifier, and an aqueous casein dispersion or aqueous solution is applied, dried, and a resin composition treatment agent is applied mainly to the pore walls of the porous portion to produce a leather-like sheet-like product. It is something to do.

Furthermore, a resin composition of an acrylic resin emulsion or a polyurethane emulsion and a solution of a nitrified cotton lacquer is applied to the surface to which the resin composition treatment agent is applied, mainly the pore wall surface of the porous portion of the surface of the porous layer of the sheet-like material. A leather-like sheet material is produced by applying a resin composition solution (n) containing an organic solvent consisting of a liquid, an oil, fat, and an emulsifier, and drying it to form a coating layer.

In the present invention, the polyurethane used for finishing treatment is a polymer diol having an average molecular weight of 500 to 2500, for example,
At least one polymer diol selected from the group of polyester diol, polyether diol, polyester ether diol, polycaprolactone diol, polycarbonate diol, etc., and an organic polyisocyanate such as aromatic diisocyanate, aromatic triisocyanate, alicyclic Diisocyanate, aliphatic diisocyanate having a cyclic group, triphenylmethane4.
A polyurethane obtained by reacting at least one type of organic polyisocyanate selected from the group such as 4', 4'-triisocyanate with a low molecular weight compound having at least two active hydrogen atoms as a chain extender. Polyurethane is ultimately used as an aqueous dispersion. Also,
The acrylic resin is, for example, an acrylic resin obtained by polymerizing at least one type of acrylic seventh polymer such as methyl acrylate, ethyl acrylate, butyl acrylate, or methyl methacrylate, or an acrylic seventh polymer. It is an acrylic resin that is a copolymer of - and other vinyl heptamers. This acrylic resin is finally used as an aqueous dispersion.

In addition, examples of oils and fats to be blended as a compounding agent for the polymer include natural oils and fats such as hydrogenated oils such as castor oil, linseed oil, cottonseed oil, poppy oil, tung oil, and castor oil, and unsaturated higher fatty acids such as ricinoleic acid and cruic acid. The emulsifier includes a resin selected from nonionic surfactants, anionic surfactants, resin compositions, and active agents capable of emulsifying oils and fats. It is an emulsifier. An aqueous solution or aqueous dispersion of casein is blended thereto to obtain aqueous resin compositions CI and II.

Furthermore, it is also preferable to add a coloring agent, for example, a coloring agent selected from inorganic pigments, organic pigments, metal complex dyes, acid dyes, etc. to the aqueous resin composition liquid [I]. The preferred resin composition of the aqueous resin composition liquid (1) is Resin 100.
10 to 40 parts by weight of oil and fat, 1 to 1 part by weight of emulsifier
0 parts by weight, 10-50 parts by weight of casein, 1-20 parts by weight of colorant
It is a resin composition blended in a range of parts by weight. Further, if necessary, additives selected from additives such as light stabilizers, antioxidants, water fillers, and oil repellents may be added. This resin composition is apparently used as an aqueous dispersion, but a small amount of an organic solvent such as ethers, alcohols, ketones, ethyl acetate, butyl acetate, etc. is added to the dispersion as long as the stability of the liquid is not impaired. It is also good to add an organic solvent selected from the group of esters, aromatic hydrocarbons such as toluene, benzene, and xylene.

The concentration of the resin composition in the aqueous dispersion is in the range of 5 to 30% by weight, and if the concentration of the resin composition is low, the desired effect cannot be obtained unless the number of applications is increased.

Moreover, if the concentration of the resin composition is high, it will not penetrate into the fine pores sufficiently, so that the desired effect will not be sufficiently obtained. The method for applying this aqueous resin composition [I] to a porous surface is as follows:
For example, the coating is carried out by a roll coating method using a roll such as a split roll or a smooth surface roll, a spray coating method, a surface contact method, or the like. A preferred coating method is roll coating because of its uniformity of coating and ease of penetration into fine pores. The coating amount is 2 as the resin composition.
The range is from 0 to 100 g/m''. If the amount applied is too small, the purpose cannot be fully achieved, but if the amount applied is too large, the porous pores will be clogged, reducing air permeability, moisture permeability, etc. It will spoil the appearance.

Further, a coating layer may be further provided on the surface of the porous layer of the sheet-like material to which the resin composition is applied mainly to the pore wall surfaces of the porous portion of the present invention. The resin composition for forming the coating layer is a resin composition liquid consisting of an emulsion of acrylic resin or polyurethane and a solution of nitrified cotton lacquer.

The resin mixing ratio of acrylic resin or polylanthanum (R) and nitrified cotton lacquer (N) is (R)/(N)- in weight ratio.
40/a.

-20/80, and if the amount of nitrified cotton lacquer is small beyond this range, the surface frictional resistance becomes large. On the other hand, if the amount of nitrified cotton lacquer is too large, the surface will feel dry to the touch, and the adhesive strength of the coating layer will become weak, which is undesirable.

The blending ratio of the oil, fat, and emulsifier to be blended into this resin composition may be the same as that of the aqueous resin composition liquid [I] applied to the pores of the porous portion. In addition, this resin composition may be used apparently as an aqueous resin composition liquid (It), or an organic solvent that does not impair the stability of the resin composition liquid or impair the porous structure, such as thinner, Resin composition liquid (II) to which at least one organic solvent selected from the group of ethers, alcohols, esters such as ethyl acetate and butyl acetate, toluene, benzene, xylene, cyclohexane, cyclohexanone, and ketones is added. It is also good to leave it as The concentration of the resin composition in the resin composition liquid [II] is 5 to 30% by weight, and outside this concentration range it is difficult to form a sufficiently good coating layer, and the air permeability, moisture permeability, etc. is damaged and becomes undesirable. The method of applying this resin composition liquid (n) to form a coating layer includes, for example, a roll coating method using a roll having a split or a smooth surface roll, a spray coating method, a surface contact method, etc. Apply by method such as method. A preferred coating method is roll coating from the viewpoint of uniformity of coating and high air permeability and moisture permeability of the coating film. The coating amount of resin composition liquid CI is 20 to 20% as a resin composition.
There is a range of 50g/n''.

When the amount of the resin composition applied is small, it is difficult to finish the surface with a glossy smooth surface without impairing flexibility. On the other hand, if the coating amount is increased, air permeability and moisture permeability will be impaired, and the appearance performance will be poor. In addition, when a surface coating layer is formed by applying this resin composition, the internal pores are not exposed on the surface of the porous layer, or the resin composition [I] is not sufficiently applied to the internal pores of the porous layer. If a coating layer of the resin composition [11] is formed on the surface, there are undesirable problems such as the coating layer peeling off during the finishing treatment performed later, insufficient embossing, or wrinkles from being rubbed. Become something.

Resin composition (1) or resin composition [I] and (I
The sheet-like material obtained by applying I) is dried and subjected to finishing treatments such as embossing, softening treatment by rubbing, and surface color or gloss adjustment to form a leather-like sheet-like material. Get the product.

The leather-like sheet material obtained in the present invention has a smooth texture with no tackiness on the surface, similar to natural leather in fold form and drapability, and has a solid appearance and deep color. Moreover, the color tone appears to be dark, and the leather-like sheet-like material has air permeability, moisture permeability, and excellent surface properties such as compression resistance, abrasion strength, and scratch resistance of the surface layer.

The leather-like sheet material of the present invention is suitable for use in shoe uppers such as sports shoes and men's shoes, bags, bags, clothing, gloves, and the like.

<Examples> Next, embodiments of the present invention will be described using specific examples, but the present invention is not limited to these examples. Note that parts and percentages in the examples are by weight unless otherwise specified.

Example 1 One surface of a base layer consisting of an entangled nonwoven fabric of polyethylene terephthalate ultrafine fiber bundles containing polyester polyurethane containing a blue colorant in a porous state was wet-processed from a polyester/polyether polyurethane composition solution. A base sheet having a porous surface layer formed thereon with an average thickness of 0.35 mm was obtained by solidification. The cell structure of the porous surface layer of this base sheet has an average diameter in the range of 120 to 210 μm, and has an apparent density of 0.28 g/cm, in which bubbles extending almost perpendicular to the surface are predominant. ” surface layer.

The surface of the porous layer of this base sheet was puffed with sandpaper to remove a skin layer with a thickness of about 0-08 mm, leaving a surface where air bubbles inside the porous layer were exposed. As water-based resin composition liquid (I) to be applied to the exposed surface of the bubbles, 160 parts of acrylic resin emulsion (resin concentration 45%),
Casein aqueous dispersion containing black pigment (casein concentration 30%)
'), 30 parts of a vegetable oil emulsion mainly composed of castor oil (vegetable oil concentration: 50%), and 200 parts of water. This aqueous resin composition liquid [
'I] is applied to the exposed surface of the internal bubbles of the porous layer by a roll coating method using an opening roll in an amount of the aqueous resin composition that is 80 g/m2 as the resin composition amount (residual component amount after drying). Then, a sheet-like material A to which a resin was applied was obtained by drying. In this sheet-like material A, most of the resin composition was applied to the surface of the cells inside the porous layer. Next, a resin composition was applied, and the surface of the porous layer was heat-embossed at a temperature of 150° C. using a satin-patterned embossing roll to finish it into a leather-like sheet-like material.

The obtained leather-like sheet material has a moist texture on the surface, a deep blackness, and an air permeability of 65 seconds/100.
cc, moisture permeability 1495 g/m"24 hr.

Comparative Example 1 Without removing the skin layer of the porous layer of the base sheet of Example 1, the aqueous resin composition liquid [I] used in Example 1 was applied in the same manner and dried, so that the surface did not become acrylic. A sheet-like material B on which a coating layer of the resin composition was formed was heated and 1-embossed under the same conditions, but under the conditions of Example 1, the surface coating layer peeled off due to the high temperature, and the embossing cannot be multiplied. For that, embossing temperature! The temperature was lowered to 10°C and heat embossing was performed to produce a leather-like sheet-like product. Since the obtained leather-like sheet material cannot be sufficiently embossed,
Appearance is poor, air permeability is 10 minutes or more, moisture permeability is 375g101
The performance was not good at 2.24 hours.

A soccer pole was made from this leather-like sheet material, and the kicking condition of the soccer pole was examined. As a result, the shoes made from the leather-like sheet-like material of Example 1 had good kickability (flying the ball in the target direction) from the pole, and had good wear resistance, and could be used for a long period of time. . On the other hand, the shoes made of the leather-like sheet-like material of the comparative example had good ball kicking performance up to about 10 times, but after that, the porous layer on the surface was damaged.

Example 2 Sheet-like material A provided with the aqueous resin composition (I) of Example 1
Resin composition liquid (n) for forming a coating layer on the surface of a porous layer of
As an acrylic resin emulsion (resin concentration 45%)
) 40 parts, nitrified cotton lacquer solution (resin concentration 30%) 10
A resin composition solution (II) was prepared, which consisted of 0 parts, 30 parts of a vegetable oil emulsion (vegetable oil concentration: 50%) mainly consisting of castor oil, and 150 parts of an organic solvent. This resin composition liquid [II] is applied to the surface of the porous layer with a resin composition liquid CI having a resin composition amount (residual composition amount after drying) of 50 g/m2 by a roll coating method using an opening roll, and then dried. A coating layer was formed. Next, the surface of the porous layer and the coating layer were heated and embossed with a calf-like pattern using an embossing roll to obtain a calf-like leather-like sheet material. This leather-like sheet material was further rubbed and finished.

The obtained leather-like sheet material had a soft texture, a folded surface shape and texture similar to natural leather, and had a deep hue and a solid appearance.

Also, air permeability 335 seconds/100cc, moisture permeability 975g/
'm2・24h Otsu is in good condition.

Example 3 Polycaprolactone/polyoxytetramethylene is coated on one side of a base layer containing polyurethane in a porous state made of a polyethylene adipate/polyoxytetramethylene mixed soft segment colored with a black pigment on a nylon-6 fiber interwoven nonwoven fabric. A base sheet provided with a microporous surface layer of polyurethane made of mixed soft segments was used, and the surface skin layer of the microporous layer was puffed with sand vapor to expose the internal air bubbles. Polycarbonate-based polyurethane emulsion (tilt fat concentration 4
0%), 100 parts of a casein aqueous dispersion containing black pigment (30% casein concentration), 30 parts of a vegetable oil emulsion (50% vegetable oil concentration), 1 part of a hindered amine light stabilizer, and 200 parts of water. Adjust the solution [I]. This aqueous resin dispersion [I] was applied to the surface of the surface layer where the air bubbles were exposed as a resin composition amount (residual component amount after drying) of 6.
A water-based resin composition liquid amount of 5 g/m2 was applied by a roll coating method and dried to obtain a sheet material C. This sheet-like material C
Using an embossing roll with a calf-like pattern on the surface of the
Heat embossing was performed at 50°C to produce a leather-like sheet.

The obtained leather-like sheet material has a moist and slimy surface, deep illuminance, and an air permeability of 80 seconds/100.
cc, moisture permeability of 1675 g/m"24hr, and had good performance.

Example 4 As the resin composition liquid (II) for forming a coating layer on the surface of the sheet material C obtained in Example 3, 85 parts of polycarbonate polyurethane and 1 part of polyoxyethylene polyurethane were used.
5 parts polyurethane mixed emulsion (resin concentration 40%)
) 50 parts, nitrified cotton lacquer solution (resin concentration 30%) 10
0 parts, black thread pigment 2.5 parts, vegetable oil emulsion (vegetable oil concentration 5
Prepare a resin composition solution (n) consisting of 30 parts (0%), 1.5 parts of a hindered amine stabilizer, and 150 parts of an organic solvent, and apply this resin composition solution (n) on the surface of the sheet-like material C as a resin composition amount. (Residual component amount after drying) 40g/
The resin composition liquid (II) having a value of a+2 was applied by a roll coating method and dried to form a coating layer. Next, heat embossing was performed on the surface coating layer using an embossing roll with a satin pattern to obtain a leather-like sheet-like material. This leather-like sheet material was further rubbed and finished.

The obtained leather-like sheet material has a blackness and a moisture permeability of 129
0g/n+"・24hr, and the wear test result of 1000 times at a load of 500 gs using a Gakushin type flat abrasion tester is grade 1 (no abnormality).

This leather-like sheet material was a suitable material for sports shoes.

<Effects of the Invention> The leather-like sheet of the present invention has a porous layer surface that has a slimy feel without tackiness, has a fold shape and drapability similar to natural leather, and has a solid appearance and color. It looks deep and dark in color, has high air permeability and moisture permeability, and has excellent surface properties such as surface compression resistance, abrasion strength, and scratch resistance.

Claims (2)

[Claims] (1) In a leather sheet-like article comprising a base layer containing a polymer mainly composed of an elastic polymer in a fiber aggregate and a porous layer of a polymer mainly composed of an elastic polymer, the leather-like sheet-like article After exposing the fine porous portion inside the porous layer of the object, an aqueous resin composition liquid [I ] A method for producing a leather-like sheet material, which comprises applying and drying. (2) In a leather-like sheet-like material comprising a base layer containing a polymer mainly composed of an elastic polymer in a fiber aggregate and a porous layer of a polymer mainly composed of an elastic polymer, the leather-like sheet-like material After exposing the fine porous portion inside the porous layer of the object, an aqueous resin composition liquid [I ], then apply a resin composition solution [II] containing an organic solvent consisting of a resin composition solution of an acrylic resin emulsion or a polyurethane emulsion and a solution of nitrified cotton lacquer, oil and fat, and an emulsifier, and dry to form a coating film. A method for producing a leather-like sheet material, characterized by forming a layer.