JPS6075688A - Leathery sheet - Google Patents

Abstract

PURPOSE:A leathery sheet colorable clearly and deeply, capable of having luster with depth, having a silver face layer obtained by integrating a fibrous structure extremely thin fiber of specific copolymer polyester entangled densely with a resin. CONSTITUTION:A leathery sheet having a silver face layer consisting of a fibrous structure wherein extremely thin fiber having <= 0.05 denier fineness and/or its bundle made of fiber comprising copolymer polyethylene terephthalate containing 2.0-5.5mol%, preferably 4.0-5.5mol% ethylene isophthalic acid sulfonate in the wole structure unit and/or core-skin type conjugated fiber constituting the polyethylene terephthalate as a skin component is densely entangled so as to make <=200mu, preferably <=100mu distance between points of fiber entanglement and a resin, formed at least one side. A polyurethane containing a group selected from -SO3X (X is H, or alkali metal) or -COOX is preferable as the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a leather-like sheet material with excellent colorability, especially a flexible texture and touch, a vivid and deep coloring, a deep luster, and a strong resistance to rolling. The present invention relates to a leather-like sheet material having a grain layer with excellent shear fatigue resistance and scratch resistance.

Many leather-like sheet products have been proposed in the past, which are made of fiber aggregates such as non-woven fabrics, knitted fabrics, etc. containing resins such as elastic polymers. Preferably, ultrafine fibers are used.

Ultrafine fibers can provide a soft texture similar to natural leather, and if the leather-like sheet material has a suede feel, a supple touch and an elegant appearance as seen in lighting effects can be obtained. In addition, in the case of having a grain layer, a smooth grain layer can be obtained by integrating resin with fine fluff from ultrafine fibers, which is essential for forming high-grade leather-like sheets. It is impossible. In addition, microfibers have many excellent chemical and physical properties such as high strength, durability, and abrasion resistance, low water absorption, quick drying, excellent wrinkle recovery, and good heat setting properties. Polyesters, particularly polyethylene terephthalate, are preferably used because they have excellent properties.

However, although such polyethylene terephthalate has the above-mentioned excellent properties, it has the drawbacks of being highly oriented, highly crystalline, and having a high refractive index, making it difficult to dye and having poor color development. In the case of ultrafine fibers, the thinner the fibers, the more the above-mentioned features are utilized, but the surface area of the fibers also increases, and the amount of light reflected on the surface increases, further reducing color development. This tendency is particularly strong when the fineness of the ultrafine fibers is 0.2 denier or less, and it becomes very difficult to dye them in deep colors.

Many techniques have been proposed to improve the disadvantages of polyester fibers, such as examining dyes to be applied, roughening the fiber surface, or forming a film with a low refractive resin, and these techniques have been applied to general thick denier fibers. Although some of these techniques have been put into practical use, it is difficult to apply such techniques to ultrafine fibers, and there has been no example of application to ultrafine fibers of 0.05 denier or less.

Although it has been proposed to improve the dyeability by simply roughening the fiber structure by chemical or physical means, such a method deteriorates the wet fastness and is therefore not a preferred method.

On the other hand, attempts have been made to introduce polar groups into the polymer main chain to improve dyeability and color development, but when polar groups are introduced into the polymer main chain, the strength decreases significantly, and the polymer fiber alone Because it was difficult to use, it was necessary to mix it with other fibers. In addition, in recent years, studies have been conducted to satisfy both the properties of color development and strength by forming a core-sheath structure in which the above polymer is used as a sheath and another polymer with high strength is used as the core. It is becoming possible to create ultrafine fibers that have properties. However, even in this method, the finer the fiber, the more it is necessary to increase the proportion of the sheath component that exhibits high color development, and as a result, sufficient strength cannot be maintained. The power of the system had to be low.

On the other hand, in conventional leather-like sheet materials having a grain layer, if the grain layer is simply applied with a resin such as a urethane polymer and laminated on the substrate, a smooth grain layer cannot be obtained.
In addition, there has always been a problem with strong rubber-like repulsive sensations, so as mentioned above, we have developed products that are formed by integrating the fluffy fibers on the surface of the substrate and resin, or are made of a planar arrangement of fine fiber bundles and a porous material. Some proposals have been made, such as one in which a grain layer is formed by combining surface fibers, or one in which a grain layer is formed by melting or melting surface fibers and partially bonding them together to form a surface. If the surface is bent or subjected to shear stress, the surface may become fluffy or
However, the problem still remains that cracks and fissures occur relatively easily on the surface, resulting in extremely poor appearance.

The inventors of the present invention have taken these problems into consideration, and have developed a system that can be colored vividly and darkly, with a deep luster, and that also has good resistance to rubbing, shear fatigue, scratch resistance, etc. We have conducted extensive research on leather-like sheets with excellent grain layers,
Finally, we have arrived at the present invention.

That is, the present invention has the following configuration.

It has a grain layer mainly formed from a resin and a fiber structure in which the distance between the fiber entanglement points of ultrafine fibers of 0.05 denier or less and/of bundles of crushed bamboo shoots is 200 microns or less, and The ultrafine fibers consist of fibers made of copolymerized polyethylene terephthalate containing 2.0 to 5.5 mol% of ethylene isophthalic acid sulfonate in its total constituent units and/or a core made of polyethylene terephthalate as a sheath component. A leather-like sheet material characterized by:

The leather-like sheet material of the present invention contains ethylene isophthalic acid sulfonate in which a polar group (-SO3X: where X represents hydrogen or an alkali metal) has been introduced into the main chain and has high coloring properties in the ultrafine fiber component. Using a copolymerized polyester, the ultrafine fibers and/or bundles thereof are closely intertwined with each other, and the densely entangled ultrafine fibers and/or bundles are composited and integrated with a resin to form a grain layer. This combination is the basis for creating a silver surface that can be vividly and deeply colored, yet has a supple texture and touch, and has excellent durability such as resistance to rubbing, resistance to shear fatigue, and resistance to scratches. It has now become possible to provide a leather-like sheet material having layers.

The fineness of the ultrafine fibers constituting the leather-like sheet material of the present invention is as follows:
It needs to be 0.05 denier or less. If the fineness is too thick, the rigidity of the fibers will be too high, which will impair the flexibility of the grain layer and the form of wrinkles on the surface, and cracks will easily occur due to rubbing, and the smooth and durable grain layer will not work properly. Not only is this not possible, but the intertwining density of the fibers cannot be sufficiently increased. By using ultrafine fibers of 0.05 denier or less, the intertwining of the fibers becomes extremely dense, and when a grain layer is formed as a composite with resin, cracks do not occur, resulting in a smooth A leather-like sheet material with a touch is obtained.

However, as mentioned above, as the fiber becomes ultra-fine, its coloring property decreases significantly. Therefore, in the present invention, 2.0 to 5.5 moles of ethylene isophthalic acid sulfonate is added to the polyester constituting the ultra-fine fiber, based on the total constituent units. % copolymerized polyester is used. The copolyester can be obtained by a known method, for example, the method described in Japanese Patent Publication No. 3-4-10497.

If the content of ethylene isophthalic acid sulfonate is less than 2 mol%, sufficient color development cannot be obtained.
In addition, if the amount exceeds 5.5 mol%, the melt viscosity becomes too high during spinning, making spinning very difficult.
．． A preferred range is 0 to 5.5 mol%. In particular, in order to obtain sufficient color development in the ultrafine fibers and to obtain a clear deep hue when forming a grain layer using the fibers, 4.0~
A range of 5.5 mol% is preferred. By using the above-mentioned copolymerized polyester as an ultrafine fiber component, the leather-like sheet material of the present invention can be colored deep and vividly despite the ultrafine fibers having a diameter of 0.05 denier or less, and in particular, the grain layer thereof can be colored deeply and vividly. can be clear, dark, and have a deep luster.

In addition, as mentioned above, introducing polar groups into the polymer main chain in this way reduces the strength, so in the conventional technology,
Fibers made of this polymer cannot be used alone,
In the present invention, it was necessary to use the fiber as a so-called core-sheath structural fiber using another polymer in the core for reinforcement.

By having the fiber structure described below, sufficient durability can be obtained even when the polyester is used alone or as a core-sheath structure. Of course, the component ratio of the core and sheath may be arbitrarily selected from the viewpoint of colorability.

The fiber structure of the leather-like sheet material of the present invention, the fiber structure of the grain layer, requires that the ultrafine fibers of 0.05 denier or less and/or bundles thereof are closely intertwined with each other. That is, the fiber entanglement density is high. One way to measure the fiber entanglement density is to measure the distance between fiber entanglement points, which will be described later, but the fibers in the grain layer have an entanglement density of 200μ or less as measured by this method. It is necessary.

This value is different from that of conventional leather-like sheet materials (those with a structure larger than 200 μm, for example, those with a fiber structure with less tangles in which the fibers are entangled only by needle punching, as mentioned above, low-strength fibers are used. Not only will sufficient strength (durability) not be obtained if the substrate is used, but even if a silver-plated type is made using the substrate, it will not be possible to obtain a fiber structure with less entanglement, or ultrafine fibers or bundles thereof 75; Those with an arrayed structure, or those with a structure in which bundles of ultra-fine single fibers are densely grown like fluff on the surface of the base material and left to age to form hematopoiesis, have little or no entanglement of fibers, so they are ultra-fine single filaments. Regardless of the strength of the fibers, when subjected to abrasion, kneading, repeated shearing forces, etc., the surface tends to become fluffy or crack, which is undesirable.To eliminate these defects, the distance between fiber entanglement points must be must be 200μ or less.If it is 100μ or less, a more favorable result can be obtained.

By adopting the above fiber structure, the characteristics of the copolymerized polyester can be fully exhibited and its weaknesses can be compensated for.In the grain layer, the coloring of the resin and the high coloring of the ultrafine fibers are combined. It has now become possible to form a leather-like sheet material that has a dark and clear hue and has a grain layer with excellent durability, which was unprecedented.

Further, at this time, other fibers may be included in the ultrafine fibers forming the grain layer, for example, in an amount of about 5% or less, to the extent that the effect of high color development of the copolyester is not substantially inhibited.

Here, the distance between fiber entanglement points is a value determined by the following method, and is a measure of the denseness of intertwining of fibers, and the smaller the value, the more dense the entanglement is. . The figure is an enlarged schematic view of the constituent fibers in the grain layer when observed from the surface side. The constituent fibers are fl,
f2, f3..., and the point where any two fibers f1, f2 are intertwined is 81, and the fiber f2 on the top at al is forced under the other fibers. Trace the intersection to the point where it intersects a, b('fz
and f3). Similarly a? , a4, a5...
...and so on. Next, the straight horizontal distance between the intersecting points thus obtained is a1 a2, ”2 a3. a3 a4, a4
a5, a5a6. a6a7, a7a3. a3aB,a
8a7,878g, a9 a6... limited,
The average value of these many measured values is expressed as the distance between fiber entanglement points.

Examples of the resin used in the grain layer of the present invention include polyamide, polyester, polyvinyl chloride, polyacrylic acid ester copolymer, polyurethane, neoprene, styrene-butadiene copolymer, acrylonitrile butadiene copolymer, and bo-1 amino acid. , a polyamino acid polyurethane copolymer, a synthetic resin such as a silicone resin, a natural polymer resin, or a mixture of these resins. Furthermore, -803X, -COOX
(Here, X represents hydrogen or an alkali metal) polyurethane is particularly suitable for use with dark colors, clear and deep luster, a supple texture and touch, and a silver surface with good bending resistance. This is particularly preferred since a layer can be obtained. Furthermore, if necessary, plasticizers, fillers, stabilizers, pigments, dyes, crosslinking agents, etc. may be added.

The amount of resin attached to the silver layer is not particularly limited and may vary depending on the purpose, but if flexibility and soft feel are particularly required, such as for clothing, the amount of resin attached to the silver layer may be 30% in solids.
No/m2 or less, especially 10! f/m2 or less is preferable. Further, when particularly high scratch resistance is required, it is preferable to fill the voids in the grain layer with the resin almost without any gaps, and in this case, the amount applied is preferably in the range of 5 to 50 f/ni''.

The leather-like sheet material of the present invention can be specifically obtained, for example, by the following novel method.

(f) It is possible to form ultrafine fibers with a core-sheath structure consisting of copolymerized polyethylene terephthalate containing 2.0 to 5.5 mol% of ethylene isophthalic acid sulfonate in its total constituent units, or having the polyethylene terephthalate in the sheath part. obtain a multicomponent fiber.

For example, a copolymerized polyester obtained by the method disclosed in Japanese Patent Publication No. 34-10497 is used as an ultrafine fiber component or as a sheath component of an ultrafine fiber having a core-sheath structure, and the copolyester and the above copolyester are used in the core. For example, polyethylene prephthalate with a high degree of polymerization is used, which has good compatibility and high strength. In addition, as binding components or dissolving and removing components, examples include polystyrene, polyethylene, polypropylene, polyamide, polyurethane, copolymerized polyethylene terephthalate easily soluble in alkaline solutions, polyvinyl alcohol, copolymerized polyvinyl alcohol, styrene-acrylonitrile copolymer, styrene and acrylic. Using a copolymer of a higher alcohol ester of an acid and/or a higher alcohol ester of methacrylic acid, for example, Japanese Patent Publication No. 18369/1982, Japanese Patent Application Laid-Open No. 116417/1982
A multi-component fiber made of two or more components capable of forming ultrafine fibers is produced using a spinning apparatus shown in, et al.

The forms of the multicomponent fibers include, for example, fibers with a chrysanthemum-shaped cross section in which one component is interposed radially between other components, multilayer bimetallic fibers, and a large number of ultrafine fibers with a donut-shaped cross section arranged and aggregated to form a cross-section with one component interposed radially between the other components. combined and/or partially combined with 1
Polymer interlayer array fibers formed into book fibers, and furthermore,
It is a multi-component fiber that has a plurality of core-sheath structural units, and these are either twisted together by a sea component and bound as a fiber, or are interposed and bonded by an intervening component and bound as a fiber.

Next, after making this multicomponent fiber into a stable card,
A web is formed through the cross wrapper, and then needle punched to intertwine the multicomponent fibers to form a fiber sheet.

Alternatively, following the spinning of the multicomponent system, the web is stretched and placed randomly on a wire mesh, and the resulting web is needle punched in the same manner as described above to form a fiber sheet. Alternatively, the multicomponent fibers are placed on a nonwoven fabric, woven fabric, or knitted fabric made of ordinary fibers or other multicomponent fibers, and the multicomponent fibers are spun out and three-dimensionally entangled to form an inseparable unit to form a fiber sheet. You may.

However, when inserting or integrating knitted or woven fabrics into a non-woven structure, peeling may occur at the interface of such knitted or woven fabrics, or the knitted or woven fabrics may peel on the surface.
A non-woven single-layer structure is preferable since the stitches of the fabric may be exposed.

Next, the fiber sheet thus obtained is brought into contact with a high-speed fluid stream to branch at least a portion corresponding to the grain layer into ultrafine fibers and/or bundles thereof, and at the same time to entangle them densely. The fluid here refers to liquid or gas, and in special cases it may contain extremely fine solids, but from the viewpoint of ease of handling, cost, and amount of collision energy as a fluid, is most preferably used. Furthermore, depending on the purpose, various organic solvents capable of dissolving some components of the multicomponent fibers, or aqueous solutions of alkali or acids such as sodium hydroxide can be used. These fluids are pressurized and injected through small-diameter nozzles or narrowly spaced slits to form a high-speed columnar or curtain-like flow, which is brought into contact with the fiber sheet to branch and entangle the fibers.

The pressure applied to the liquid varies depending on the ease of branching of the multicomponent fiber or ultrafine fiber bundle; for fibers that are easy to branch, a relatively low pressure of 5 to 100 cr/crl is sufficient, but for fibers that are difficult to branch, So, 100-300
High pressure of murmur/crtt is preferred. It is also possible to increase the degree of branching and entanglement by increasing the number of contacts, and the pressure may be changed each time the contacts are made.

Before or after this high-speed fluid flow treatment, the multicomponent fibers constituting the fiber sheet are made extremely fine. In this case, it is necessary to treat the obtained fiber sheet with a solvent that dissolves some of the components of the multicomponent fiber to dissolve and remove some of the components.

In the present invention, it is necessary to dissolve and remove some components as a means for making the multicomponent fiber ultrafine.

The reason for this is that if the binding components of the multi-component fiber remain, these components will inhibit the color development of the present invention, making it impossible to obtain a deep hue.

Here, some of the components may be dissolved and removed before being treated with the high-speed fluid flow, and in this case, the multicomponent fibers of the fiber sheet are transformed into bundles of ultrafine fibers by dissolving and removing the some of the components. This is a preferred method because it allows easy and highly branched and entangled results at low fluid pressures. Furthermore, high-speed fluid flow treatment may be performed before and after the step of dissolving and removing the partial components.

In addition to the above, the step of applying a resin as a binder can be carried out between the high-speed fluid flow treatment step and the step of dissolving and removing some components of the fibers. It is necessary that the applied resin does not dissolve with the solvent used to dissolve and remove the partial components, but the space where the partial components existed between the ultrafine fiber bundles of the obtained fiber sheet and the resin must be This is the preferred method for making the texture more flexible as it increases the degree of freedom in mutual movement. If necessary, it may be impregnated with a solution or dispersion of a resin such as a polyurethane disstomer as a binder and coagulated by a wet or dry method. Further, the amount of resin applied as the binder varies depending on the purpose of use of the sheet material.

When used for clothing, the amount applied is preferably 0 to 80 parts based on the weight of the fiber. Thereafter, a solution or dispersion of the resin for the grain layer described below is applied to the layer of the obtained fiber sheet in which the ultrafine fibers and/or their bundles are intertwined by reverse roll coating, gravure coating, or knife coating.

Apply by methods such as slit coating or spraying,
It is coagulated by a wet or dry method, and is placed on a roll surface or a sheet surface, pressurized, and heated as necessary to integrate the fibers and resin and at the same time smooth the surface.

Here, it is also a preferable method to subject the fiber sheet to a treatment such as pressing to smooth the surface before applying the resin. At this time, it is preferable to use an emboss roll or a textured sheet with a textured pattern on the surface because integration, smoothing, and texture formation can be performed at the same time.

In addition, in the present invention, after forming the grain layer as described above, it is possible to dissolve and remove some components of the multicomponent fiber, and in this case, a softer texture can be obtained. Particularly preferred. Furthermore, if necessary, treatments such as applying a finishing agent and rubbing may be performed.

The leather-like sheet material of the present invention can be colored in a deep color using commonly used basic dyes, particularly cationic dyes.

Generally, it is said that non-acrylic fibers have somewhat poor light resistance when colored with the cationic dye, but this is thought to be due to the so-called ring dyeing of the fibers. However, with ultrafine fibers, it is possible to dye not only the surface but also the interior, so there is no particular problem with respect to light resistance.

Furthermore, since the ultrafine fibers of the present invention are composed of a specific copolymerized polyester, there is no need to use a polyester dyeing method using high temperature and high pressure. Can be dyed at temperatures below 100℃.

When dyed, the leather-like sheet material of the present invention is vividly and deeply colored, has a deep luster, has a supple texture, a smooth surface feel, and is resistant to bending and shear fatigue. Because of its good hardness and scratch resistance, it is preferably used in a variety of applications, including silver-beaten artificial leather for clothing, uppers for shoes, handbags, bags, belts, bags, gloves, and the outer leather for balls.

Examples shown below are intended to clarify the present invention, but the present invention is not limited thereto.

In the examples, parts and percentages refer to weights unless otherwise specified. Moreover, the value of the average distance between interlacing points was taken as the average value of 100 measured values.

Example 1 By copolymerizing dimethyl 5-sodium sulfoisophthalate as an acid component, 45 parts of polyethylene terephthalate containing 5.0 mol% of ethylene isophthalic acid sulfonate in its total constituent units was obtained as an ultrafine fiber component.
A copolymer of acrylic acid and styrene (hereinafter referred to as As resin) is used as a bonding component and has 12 island components in one filament at a ratio of 55 parts, and 0.
．． Using a stable between 3.8 denier and 76 denier polymer mutual array fibers as shown in Japanese Patent Publication No. 47-37.648 in which a large number of ultrafine fibers of 0.01 to 0.0001 denier are mounted. A web was formed through a cross wrapper, and then needle punched using a needle with one hook to entangle the fibers of the polymeric interlayer arrangement to form a nonwoven fabric. The basis weight of the non-woven fabric is 435 f.
/nt2, and the apparent density jd was 0.18 p/cni.

Next, the nonwoven fabric was immersed in a 5% aqueous solution of polyvinyl alcohol (hereinafter referred to as PVA) heated to 95°C, and the nonwoven fabric was shrunk at the same time as the VA impregnation and dried to remove moisture, and then dipped in trichlorethylene and immersed. The AS resin was extracted and removed by repeating the squeezing solution and dried. The obtained nonwoven fabric is a nonwoven fabric in which ultrafine fibers are substantially intertwined in bundles, and pores with a pore diameter of 0.1 mytb are formed on both sides with a distance between the centers of the pores of 0.1 mytb.
50Ky/ using nozzles lined up in a row with a pitch of 6u
Water under a pressure of c4 was jetted at high speed, and each surface was treated a total of three times under the same conditions to dissolve the PVA and simultaneously branch and entangle it. the last one of each
The treatment was carried out while vibrating the nozzle, and after removing the PVA, the sample was passed through a mangle and nipped while still containing water, and then dried. The surface layer of the obtained nonwoven fabric had a fiber structure in which the original ultrafine fiber bundles were highly branched and densely intertwined.

Thereafter, a prepolymer of polyethylene, butylene adipate, and hydrogenated diphenylmethane-4,4'-diisocyanate was reacted with sodium aniline sulfonate, and the chain was extended with 4,4'-diaminodicyclohexylmethane to obtain a polyurethane. A 12% solution was applied using a gravure coater to give a solid content of 5 y/m2, and then pressed through a heated embossing roll to emboss a leather-like grain pattern. Then I lightly puffed the other side with sandpaper.

After that, it was dyed using a jet dyeing machine under the following conditions and finished.

Dyeing conditions Temperature
tf2t/) Temperature x Time = 70°C x 20 minutes The obtained leather-like sheet material is dark and vividly colored, has a deep luster, and has a shape substantially only due to the entanglement of fibers. Despite being fixed, it had good shape retention properties, the fiber structure was extremely similar to natural leather, and it had excellent flexibility and a full texture. Furthermore, when the folded end was pinched with fingers, it exhibited a rounded feel and shape similar to that of natural leather, and no cracks or fuzz were observed even when strongly rubbed or pulled by hand.

The polyurethane and finishing agent on the grain layer of this leather-like sheet were removed with a solvent, and the average distance between fiber entanglement points of the constituent fibers was measured and found to be 15 tt.

Comparative Example 1 For comparison, the nonwoven fabric obtained in Example 1 was immersed in a 95° C. PVA aqueous solution, and shrunk simultaneously with the PVA impregnation, and then the AS resin was extracted and removed with tri-4lene. Next, a glue that is sprayed with a high-speed fluid stream is impregnated with a 15% solution of polyether polyurethane in dimethylformamide (hereinafter referred to as DMF), and after wet coagulation, PVA and DMF are removed by hot water washing, and the solid content is 65%. A sheet containing % polyurethane was obtained. Thereafter, in the same manner as in Example 1, the subsequent operations of applying polyurethane to the surface were carried out to complete the work.

In addition to the grain pattern, the obtained leather-like sheet material had irregularities along the ultrafine fiber bundles, such as protruding blood vessels, and cracks that occurred during dyeing were observed here and there along the ultrafine fiber bundles. The microfibers were exposed.

Further, although the resin content was 65%, the tensile strength of the sheet was low.

As in Example 1, the polyurethane and finishing agent were extracted and removed with a solvent, and the distance between fiber entanglement points of the constituent fibers on the surface of the grain layer was measured, and the distance in the comparative example was 665μ.

Example 2.3, Comparative Examples 2 to 4 Nonwoven fabrics with a basis weight of about 500 y/'Fn'' were obtained in the same manner as in Example 1, except that the content of ethylene isophthalic acid sulfonate was changed as shown in the table. Ta.

Next, water was applied to these nonwoven fabrics at a pressure of 10 D''!/cnt using the same nozzle as used in Example 1, and was sprayed onto the surface at high speed while the nonwoven fabric was moving, under the same conditions. 10 times, then increase the pressure to 50
The same process was carried out once while the nozzle was vibrated. The obtained nonwoven fabrics had a fiber structure in which the surface layer of mutually arranged polymer fibers were branched into ultrafine fibers or bundles thereof, and were densely intertwined with each other. The distance between fiber entanglement points in each of these sheets was about 60μ.

Thereafter, these nonwoven fabrics were introduced into a PVA aqueous solution at 95° C., and PVA application and shrinkage operations were performed. Thereafter, it was impregnated with a polyester-based polyurethane solution, the liquid adhering to the surface was removed with a souffle flavor, and the material was introduced into water to solidify. After that, wash thoroughly in hot water at 80℃])
P was removed.

Next, the same silver surface-forming polyurethane as in Example 1 was applied to the surfaces of these sheets onto which the high-speed fluid stream had been sprayed, at a solid content of about 6 f/m2. Next, after performing graining and integration using a heating roll, the As resin was almost completely extracted and removed with trichlorethylene. After that, the other mf was lightly puffed with sandpaper.

I did it.

All of the obtained leather-like sheets had a soft and unified texture, but as shown in the table,
Those that do not contain ethylene isophthalic acid sulfonate at all or have a content as low as 2.0 mol% are:
These silver surface layers, in which the ultrafine fibers are sufficiently colored, are unevenly colored, as if the surface resin had been applied unevenly. In addition, the parts other than the silver surface layer were not colored at all or were only slightly colored, and were inferior in terms of commercial value.

Example 2.6 of the present invention In particular, the silver surface layer of the notebook obtained from Example 6 has excellent coloring properties due to the combination of the ultrafine fibers and the coloring of the resin, and has a clear and deep luster. A certain hue was obtained, and areas other than the grain layer were also deeply dyed, giving an appearance extremely similar to natural silver-beaten leather.

Furthermore, the bending resistance, shear fatigue resistance, and scratch resistance of these leather-like sheets were measured and found to be very good.

Example 4 By the same method as in Example 1, the fabric weight was 560 mm/〃' and the thickness was 2.
．． 8 pieces of nonwoven fabric were obtained. Both sides of this nonwoven fabric were brought into contact with a columnar stream of water injected at a pressure of l0DKy/'aA using the same nozzle as in Example 1, five times under the same conditions, and then lowered to 30Ky/cnf for two times. Processed twice. Furthermore, it was placed in hot water at 95°C and subjected to a shrinkage treatment and a nip using a mangle. The obtained year-round woven fabric is
The thickness is about 2. The layer with a thickness of approximately - from the water-treated surface is mainly composed of ultrafine fibers with an average fineness of about 0,002 denier branched from the polymer interlayer fibers and their bundles, which are closely and densely intertwined. The surface was extremely rough and uneven. Thereafter, impregnation, coagulation, hot water washing, and drying were performed using an impregnating solution of polyester polyurethane having a concentration of 6%. Next, polystyrene and polyethylene glycol were dissolved and removed using trichlorethylene, and after slicing into 91 μm slices, a paint made by adding carbon black and dye to a polyurethane solution was applied to the surface layer of the water-treated side using a gravure coater.
The composite was dried and pressed to form a composite, and then textured.

The other side was puffed to fluff the ultrafine fibers, then dyed using a basic dye in the same manner as in Example 1, and processed for a normal finish. The obtained leather-like sheet material is darkly colored and has a texture with a sense of unity with little repellency.One side has fluff of relatively long ultrafine fibers, and the other side has a fluff of relatively long microfibers. It had a silver surface with a deep luster and an elegant appearance due to the combination of the coloring of the resin and the high color development of the ultrafine fibers, and had a structure extremely similar to natural silver beaten leather.

Also, if you use this item as a reversible item, the surface 70
%, I made a blouson using 60% of the back side. It has excellent drapability and is comfortable to wear, and even if you scrub your elbow against the armrest of a chair or the surface of a desk, the surface film will not peel off or become fluffy like traditional leather-like sheets. There was nothing to do.

The polyurethane and finishing agent on the grain layer of this leather-like sheet were removed, and the average distance between fiber entanglement points of the constituent fibers was measured and found to be 85μ.

[Brief explanation of the drawing]

The figure is an enlarged schematic view of the constituent fibers in the grain layer when observed from the surface side force. In the figure, fl, f2, f3, fl, f5 and f6 are constituent fibers, 21% a2s a3s ”4s a5, a
6, a7, a8 and a9 indicate the entwining points of the constituent fibers, respectively. Patent applicant Toshi Co., Ltd.

Claims (3)

[Claims] (1) having a grain layer mainly formed on at least one side of a resin and a fiber structure in which ultrafine fibers of o, o s deniers or less and/or a fiber structure in which the distance between fiber entanglement points of the bundle thereof is 200 microns or less; Moreover, the ultrafine fibers contain 2.0% of ethylene isophthalic acid sulfonate among their total constituent units. [)
A leather-like material comprising a fiber made of copolymerized polyethylene terephthalate containing ~5.5 mol% and/or a core crystal made of the polyethylene terephthalate as a sheath component. (2) The lower layer of the grain layer consists of ultrafine fiber bundles and /''!, or ultrafine fibers branched from the ultrafine fiber bundles, intertwined with each other, and the fibers are substantially continuous in the grain layer and the lower layer. A leather-like sheet material according to claim (1), characterized in that: (3) The resin forming the grain layer is -503X and -co
Claims (1) and (2) are characterized in that the polyurethane contains at least one group selected from ox (where X represents H or an alkali metal). leather-like sheet material.