JPS6075680A - Manufacture of leathery sheet having silver layer - Google Patents

Abstract

PURPOSE:To provide the titled sheet having excellent durability and deep luster colored in high fastness, by three-dimensionally entangling composite fibers capable of forming ultrafine fibers, and blasting a high-speed fluid jet toward the entangled fibers, thereby carrying out the application of the resin containing colorant, the ultrafibrillation of the fiber, and the dyeing with a reactive dye at the same time. CONSTITUTION:(A) Multi-component fibers capable of forming ultrafine fibers finer than 0.05 denier are subjected to the three-dimensional entanglement to obtain a fiber sheet. (B) A high-speed fluid jet is blasted toward at least one surface of the sheet to effect the splitting of the multi-component fibers and the mutual entanglement of the fibers. (C) The surface blasted with the high-speed fluid jet is coated with a resin containing 3-300%, preferably 10-100% colorant (based on the solid content of the resin) (the amount of the resin is <=10g/m<2> when flexibility is required, and 5-50g/m<2> when abrasion resistance is required.). (D) The fibers are fibrillated to form ultrafine fibers. (E) The product is dyed with a reactive dye. The above process may be carried out in the order A B D C or A D B C interposing the step E at an arbitrary position.

Description

Detailed Description of the Invention The present invention provides a leather-like sheet autumn material having a colored grain layer, which has a supple texture and touch, a deep luster, excellent durability, and high robustness. The present invention relates to a method for producing a leather-like notebook having a colored silver layer.

Conventionally, many proposals have been made regarding leather-like sheet materials having a grain layer. These are made of a porous or non-porous layer of a high molecular weight polymer such as polyurethane, or a non-porous layer of a high molecular weight polymer such as polyurethane, on a substrate containing a resin mainly composed of an elastic polymer in a fiber aggregate such as a non-woven fabric or a knitted or woven fabric. The basic method was to form a grain layer by laminating and integrating porous layers. In such sheet-like materials, in order to prevent the appearance of irregularities on the substrate surface and obtain a smooth silver surface, the coating layer is thickened, and a thick undercoat layer is applied in advance, so that the gloss of the surface is reduced. It had the disadvantages of being uniform, lacking depth in luster, lacking a sense of unity, and having a strong rubbery, repulsive texture. In order to improve these drawbacks, as a means for smoothing the surface of the base material, we have developed a system in which a relatively thin surface coating layer is formed by pressing the surface of the base material using ultrafine fibers as the constituent fibers of the base material. Alternatively, methods have been attempted in which fine fiber fluff is grown on the surface and the fluff fibers are integrated with a high molecular weight polymer to form a grain layer. However, even in these methods, if the surface coating layer is made as thin as possible, blood-like defects occur in the fiber bundles, resulting in an ugly appearance.Also, in order to obtain sufficient coloring properties, pigments, etc. If the colorant content is increased, the polymer becomes brittle and sufficient strength cannot be obtained, so the surface coating layer has to have a certain thickness. However, even in such cases, if the fibers are rubbed strongly or subjected to repeated shearing forces, there are problems in that the surface becomes fluffy and peeling occurs along the arrangement of the fiber bundles.

On the other hand, ultrafine fibers are preferably used as constituent fibers of the base material in order to obtain the surface smoothness, texture, and flexibility of the notebook. If the fiber fineness is made thinner, there will be disadvantages such as a decrease in color development due to an increase in serum on the fiber surface, and poor fastness. This tendency becomes particularly noticeable when the thickness becomes ultra-fine with a thickness of 0.05 denier or less. Therefore, in the conventional artificial leather having a grain layer using an ultrafine fiber structure in the base part, only the grain layer has a sufficient hue, and the ultrafine fiber part of the base material is colored only in a single color. I hadn't. Moreover, although the conventional method produces an extremely light color, its fastness is not at a level that is sufficiently satisfactory for washing and dry cleaning. There were serious problems such as washing and contaminating other items to be washed.

The present inventors have fully considered the problems of the conventional leather-like sheet material having a grain layer, and have developed a leather-like sheet material that has a supple texture and touch that does not cause any problems even when washed or dry cleaned, and has a deep texture. After extensive research into colored leather-like sheet materials that are glossy and have excellent durability, they finally arrived at the present invention.

That is, the present invention has the following configuration.

In the method for producing a leather-like sheet material having a grain layer, at least the following A-+B-+C→D, A→B-+D-+C
and A-+ ])-+ B-+ C. A method for producing a leather-like article having a grain layer, characterized by carrying out a combination of steps selected from A-+])-+ B-+ C and an optional step of the step E below.

Step A: A step of obtaining a fiber sheet having a three-dimensional entangled structure of multicomponent fibers capable of forming ultrafine fibers of 0.05 denier or less, Step B: Spraying a high-speed fluid stream on at least one side of the fiber sheet. , a step of splitting and entangling the fibers, Step C: a step of applying a resin containing 6 to 600% of a coloring agent based on the resin solid content to the surface onto which the high-speed fluid stream has been sprayed, Step D: a step of A step of forming ultrafine fibers from multicomponent fibers. Step E: Coloring with a reactive dye.

The leather-like sheet autumn material having a grain layer obtained by the production method of the present invention has a grain layer made of a fiber structure of densely intertwined microfibers and/or bundles thereof and a resin containing a colorant. The ultrafine fibers that make up the notebook are colored by dye i-1 molecules bound by chemical covalent bonds rather than physical ionic bonds, so they have a unique texture. It is supple to the touch, fully cures to a deep luster, has excellent durability, and is colored with high sturdiness.

The fineness of the ultrafine fibers formed from the multicomponent fibers used in the present invention must be 0.05 denier or less. If the fineness is thicker than this, the rigidity of the fiber is too high, which not only impairs the flexibility of the grain layer and the form of wrinkles on the surface, but also tends to cause cracks due to rubbing, etc., and the grain surface has a smooth and deep luster. You don't get layers. By using multi-component fibers that can form ultra-fine fibers of 0.05 denier or less, the fibers can be tightly intertwined for the first time, forming a silver layer as a composite with a resin containing a colorant. During this process, a leather-like sheet material with a smooth touch and a deep luster can be obtained without any cracks or the like.

Next, Step A of the present invention will be explained.

Multicomponent fibers that can form ultrafine fibers of 0.05 denier or less include, for example, chrysanthemum-shaped cross-section fibers in which one component is interposed radially between other components, multilayer bimetal fibers, and multilayer bimetal fibers with donut-shaped cross sections. Type fiber, mixed spun fiber made by melt-mixing and spinning two or more components,
There are polymer mutual array fibers in which a large number of ultrafine fibers continuous in the 1+lQi direction are arranged and aggregated and bonded and/or partially bonded with other components to form a single fiber.

0.05 when at least one component is dissolved and removed
Multi-component fibers that yield bundles of fibers mainly consisting of ultrafine fibers of tenier or less are particularly preferable because they yield leather-like/human-like materials with particularly supple texture and a smooth grain layer.

The components that make up the ultrafine fibers of the multicomponent fibers are as follows:
In order to color the ultrafine fibers with good fastness, nylon 6, nylon 66. -J-i0712,
Polyamides such as J-polymerized nylon are suitable, and in history, polyesters such as polyethylene terephthalate, copolymerized polyethylene terephthalate, polybutylene terephthalate, copolymerized polybutylene terephthalate, etc., which have introduced or added the proton-containing group, polyethylene, polypropylene, etc. Examples include polyolefins, polyurethanes, polyacrylonitrile, and vinyl 111 combinations.

However, the polymer into which the proton 1 group is introduced is not particularly preferable because it tends to have poor crystal orientation, low strength, and unstable spinning. In addition, it is also possible to introduce the proton group using a graft nail platform after forming into 4*#lll fibers, but this also tends to cause a decrease in crystal orientation and a hard texture. Therefore, you need to be careful.

On the other hand, binding components or dissolved components constituting multicomponent fibers include polystyrene, polyethylene, polypropylene, polyurethane, copolymerized polyethylene terephthalate that is easily soluble in alkaline solutions, polyvinyl alcohol, copolymerized polyvinyl alcohol, and styrene-acrylonitrile copolymer. A copolymer of styrene and a higher alcohol ester of acrylic acid and/or a higher alcohol ester of methacrylic acid is used. Polystyrene, styrene-acrylonitrile copolymers, and copolymers of styrene and higher alcohol esters of acrylic acid and/or higher alcohol esters of methacrylic acid are preferably used in terms of ease of spinning and ease of dissolution and removal. Further, a copolymer of styrene and a higher alcohol ester of acrylic acid and/or a higher alcohol ester of methacrylic acid is more preferably used since the stretching ratio can be reduced by 1% and a fiber with high strength can be obtained.

Although the fineness of such multicomponent fibers is not particularly limited, it is preferably 1 to 1 o denier from the viewpoint of stability during spinning and ease of sheet formation. After the multi-component fibers are made into staples, they are passed through a card and a cross wire to form a web, and then the multi-component fibers are intertwined using means such as needle punching to form a fiber sort having a three-dimensional entangled structure. Form.

Alternatively, following the spinning of the multicomponent fibers, the multicomponent fibers may be drawn, placed randomly on a wire mesh, and the obtained web may be needle punched in the same manner as described above to form bifibers/t. Alternatively, fibers may be placed on a nonwoven fabric, woven fabric, or knitted fabric made of ordinary fibers or other multicomponent fibers, and the fibers may be entangled and inseparably integrated to form a fiber sheet.

In such a method, a non-woven entangled single-layer structure is particularly preferred because it does not peel off at the interface with the laminated or knitted/woven fabric.

Next, Step B of the present invention will be explained.

In the present invention, the high-speed fluid flow that is sprayed onto the fiber sheet is a liquid or a gas, and in special cases, it may contain extremely fine solids; Water is most preferably used in view of the amount of collision energy. 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 from a nozzle with a small hole diameter or slits with narrow intervals to form a high-speed columnar flow or curtain-like flow, and are sprayed against the fiber sheet to split and entangle the fibers. The pressure applied to the liquid varies depending on the ease of splitting the multicomponent fiber or the ultrafine fiber bundle.For easily splittable fibers, a relatively low pressure of 5 to 100 IXy/art may be sufficient; For fibers that are difficult to bend, the range is 100 to 3001
a! A high pressure of . It is also possible to increase the degree of splitting and entanglement by increasing the number of times the spray is applied, and the pressure may be changed each time the spray is applied.

Next, Step C of the present invention will be explained.

In this way, a resin containing 3 to 300% of pigment and/or dye based on the solid content of the resin is applied to the surface of the fiber sheet on which the ultrafine fibers and/or bundles thereof are densely intertwined, and which has been sprayed with a high-speed fluid stream. The resin and the densely entangled fiber structure are integrally composited to form a grain layer.

The grain layer formed by the method of the present invention has a conventional structure, for example, a fiber structure with little entanglement in which the fibers are entangled only by needle punching, or a structure in which ultrafine fibers or bundles thereof are simply arranged in a plane. Alternatively, ultrafine fibers or bundles thereof are densely grown on the surface of the base material in a fluff-like manner, and the resin layer is integrated with a structure in which the fibers or their bundles are curled and end-faced. The surface does not easily fluff or crack even when subjected to repeated shearing forces, is supple to the touch, and has a deep luster.

There are no particular limitations on the resin used for the grain layer VC of the present invention, such as polyamide, polyester, polyvinyl chloride, polyacrylate copolymer, polyurethane,
Synthetic resins or natural polymer resins such as neoprene, styrene-butadiene copolymers, acronitrile-butadiene copolymers, polyamino acids, polyamino acid-polyurethane copolymers, silicone resins, or mixtures of these resins can be used.

In addition, commonly used pigments or dyes can be used as the coloring agent added to the resin, but dyes generally have poor affinity with the resin and are inferior in fastness, so pigments are preferable. . Of course, pigments and dyes may be used in combination within the range that fastness allows. The amount of the colorant added is preferably in the range of 3 to 300% based on the solid content of the resin. Furthermore, a range of 10 to 100% is particularly preferred. If it is outside this range, the coloring property may be insufficient and the fastness, especially the fastness to dry rub, may be poor.

Furthermore, if necessary, plasticizers, fillers, stabilizers, crosslinking agents, etc. may be added. Polyurethane resins or polyurethane resins to which other resins and additives are added are preferably used because they have a particularly soft feel and feel and provide a grain layer with good bending resistance.

Regarding the method of applying resin, a solution or dispersion of the resin is applied by commonly used methods such as reverse roll coating, gravure coating, knife coating, slit coating, and spraying, and then solidified by wet or dry methods. Just let it happen. Thereafter, it is preferable to stack the fibers on a roll surface or a sheet surface, pressurize them, and heat as necessary to further integrate the fibers and resin and at the same time smooth the surface. At this time, it is more 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.

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.

Also, apply (☆1 The amount of fat is not particularly limited, but if flexibility and soft feel are particularly required, such as for clothing, the solid content is 30 f/m2 or less, especially 10) /
-The following are preferred. In addition, when particularly high scratch resistance is required, 5 to 50! ? / m” range is suitable.

The leather-like sheet material obtained by the production method of the present invention is
Even if it does not contain a resin as a binder, it rarely stretches abnormally and the shape retention of sheet-like products is good, and conventional leather-like sheet-like products that use nonwoven fabric as the base material have made resin gold indispensable. They also differ greatly in points. Of course, the resin as a binder may be applied on stilts, but for clothing, it is preferable that the resin material be added in an amount of 0 to 60 parts.

Next, the process of the present invention will be explained.

In the present invention, to form ultrafine fibers from multicomponent fibers,
This may be carried out by commonly used chemical or physical means such as dissolving some components, decomposing them, and peeling off the components. At this time, there is no particular limitation on the means of ultra-thinness, but
The ultra-fine method by dissolving and removing some components creates a soft texture.

This is a particularly preferred method because a smooth silver surface can be obtained.

1) The process steps of the present invention may be performed after the high-speed fluid flow treatment as described above, or may be performed before the high-speed fluid flow treatment. In this case, the multicomponent fibers of the fiber sheet are transformed into bundles of ultrafine fibers by dissolving and removing some of the components and peeling off the components, so they can be easily split and intertwined to a high degree with low fluid pressure. This is a preferred method because it allows High-velocity fluid flow treatment may be performed before and after the shriveling process. Furthermore, a process may be performed after forming the grain layer.

In this case, it is particularly preferable that the process is carried out by means of dissolution and removal, since a softer texture can be obtained.

Further, if necessary, it may be impregnated with a solution or dispersion of a resin as a binder, such as a polyurethane elastomer, and coagulated by a wet or dry method. In this case, the step of applying the resin as a binder can be carried out after the fiber is made ultra-fine, or it can be carried out between the high-speed fluid flow treatment step B and the fiber ultra-fine process. be.

Furthermore, when dissolving and removing some components in the process, it is necessary that the resin applied as a binder does not dissolve in the solvent used to dissolve and remove the some components. ! ) A space is created between the ultrafine fiber bundle of the fiber sheet and the resin, where the component was present, and the degree of freedom in mutual movement is increased, so this is a preferable method for making the texture soft.

Next, Step E of the present invention will be explained.

0,0 constituting the leather-like sheet material of the present invention.
For coloring ultrafine fibers of 5 deniers or less, conventionally used acidic dyes, basic dyes, etc., which have a bonding mode of dye molecules mainly based on ionic bonds, cannot be washed or washed.
Even with fixation treatment, sufficient robustness cannot be obtained. Regarding the binding mode between fiber and dye, van der Walls force,
Hydrogen bonds, ionic bonds, and covalent bonds can be considered, and the bond strength increases in this order, but when coloring ultrafine fibers of 0.05 denier or less, it is necessary to color them by covalent bonds that have the largest bond strength. . If the bonding mode is less than ionic bonding, the dye molecules stained by the surfactant contained in the washing or dry cleaning solution are easily drawn out of the fiber.

The reason for this is that the more the fibers become ultra-fine, the more their surface area increases.
It is thought that it becomes more susceptible to the action of surfactants.

In the present invention, we aim to color with the covalent bond that has the maximum bonding strength, but it is generally said that reactive dyes exhibiting this covalent bonding mode are slightly inferior in light fastness compared to other dyes. However, in the present invention, the coloring agent in the grain layer compensates for these weaknesses, and the leather-like sheet material having the grain layer has sufficient light fastness of 6 to 10. It becomes possible to obtain. In addition, in general, the finer the fiber, the lower the color development, but in the present invention, the color development is strangely not affected by the fineness.
Even if it becomes ultra-fine, the color development does not deteriorate.

The reactive dye used in the present invention may be any commonly used reactive dye having a reactive group, such as dichlorotriazine, dichloroquinolaline, vinyl sulfone, monochlorotriazine, or trichloropyrimidine. Good too.

Regarding the method of coloring ultrafine fibers with such reactive dyes, the uniqueness of the reactive dye used, the heat resistance of the rolled grain layer or the resin as a binder contained if necessary,
Coloring conditions vary depending on the alkali resistance, but the conditions for coloring cannot be generalized, but basically they may be the same as when coloring cellulose fibers with reactive dyes.

In fact, such coloring of the ultrafine fibers of the present invention with reactive dyes is achieved by applying a resin containing a coloring agent, as described above.
Even if it is performed after step C of integrating to form a grain layer,
Further, even if it is carried out before forming the grain layer, the effects of the present invention will not be hindered. Further, the darkening coloring step E may be applied to any stage of the main manufacturing process in the present invention, and may be appropriately selected depending on the multicomponent fiber used and various other requirements. For example, when using split-peelable multicomponent fibers, the coloring step E may be performed after the step A of forming a three-dimensional entangled fiber sheet or after the step B of spraying the sheet with a high-speed fluid stream. No problem.

When a multi-component fiber of which some components are dissolved and removed is used, it is preferable to color the obtained ultrafine fibers after a step of extracting and removing some of the components with a solvent. In the method of overcasting, as described above, it may be applied either before or after the formation of the grain layer.

Furthermore, if step 8E is carried out after the process, the ultrafine fibers are colored with a reactive dye after the formation of the ultrafine fibers, so the ultrafine fibers are easily colored and the color can be easily adjusted, which is preferable.

In addition, when this step 1 filler is carried out at the final stage of each step of steps A, B, C, and D, since the silver σσ layer has already been formed, it is easy to match the color of the silver surface layer and the ultrafine fibers. It is preferable because there is. In addition, in this case, if the method of coloring with the reactive dye in step E is a method of simultaneously imparting kneading, which is usually done in artificial leather, it is possible to impart an elegant kneaded pattern to the grain layer at the same time as coloring. Particularly preferred. Furthermore, if necessary, treatments such as applying a finishing agent and rubbing may be performed.

The leather-like material of the present invention thus obtained has a supple texture, a smooth touch and a deep luster,
It has good bending resistance, shear fatigue resistance, scratch resistance, and washability.
There is no problem with dry cleaning, and the color is highly durable, so it is especially suitable for silver-finished artificial leather for clothing, shoe uppers, handbags, bags, belts, bags, gloves, ball leather, etc. It is preferably used for various purposes.

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

In the examples, parts and parts refer to weights not otherwise specified.

Example 1 A copolymer of acrylic acid and styrene (hereinafter referred to as As resin) was composed of 65 parts as a binding component, and nylon 6 was 65 parts as an ultrafine fiber component, with 12 island components in one filament, Furthermore, in the island component, 0.001 to 0
．． Forming a web through a card cloth wrapper using a 4.0 denier, 51 mx staple of polymeric interlayer fibers as shown in Japanese Patent Publication No. 47-37648, which contains a large number of 0001 denier ultrafine fiber components. After that, needle punching was performed using a needle with one hook to entangle the polymeric mutually arranged fibers to produce a nonwoven fabric. The basis weight of the non-woven fabric is 385 in/in
”, the apparent density was 0.17 f/cnl.

Next, the nonwoven fabric was heated to 85°C with polyvinyl alcohol (
The nonwoven fabric was immersed in a 7 aqueous solution of 1) VA (hereinafter referred to as VA), and the nonwoven fabric was shrunk at the same time as the PVA0 impregnation, dried to remove moisture, and then dipped in trichlorethylene, immersion and squeezing were repeated to extract and remove the AS resin, and then dried. . The obtained nonwoven fabric is a nonwoven fabric in which ultrafine fibers are substantially intertwined into bundles, and a pressure of 50 Ey/ct & The applied water was sprayed at high speed and the treatment was performed on each surface three times in total under the same conditions to dissolve the PVA and simultaneously branch and intertwine it. The final treatment was carried out while vibrating the nozzle. 1) After VA was removed, the sample was passed through a water-containing T-sized mangle and nipped, and then dried. The resulting nonwoven fabric had a fiber structure in which the ultrafine fiber bundles in the surface layer were highly branched and densely intertwined. After that, one side was lightly huffed with sandpaper.

Next, on the other side, a prepolymer of p1p'-diphenylmethane diisocyanate kp'', p' was prepared using polyethylene butylene adip-1 as the diol component.
- A solution containing a red insoluble azo pigment at a ratio of 50 parts to the solid content of the polyurethane was applied to polyurethane obtained by chain extension with diaminodiphenylmethane in an amount of 7 y/m.
The polyurethane-applied side of the hindlimb was passed through a heated embossing roll and pressed to create a leather-like grain pattern.

This sheet material was dyed using a jet dyeing machine with a vinyl sulfone type reactive dye DiamiraBrill at a bath ratio of 1:50.
Iced 2, dye concentration of r/A, 6 at liquid temperature 50℃
It was dyed for 0 minutes, washed and finished in the usual way.

The obtained leather-like sheet material having a grain layer has a pliable texture with a sense of unity and low repulsion.
The color tone of the silver surface was deep and glossy, and it had excellent scratch resistance and bending resistance. Also JIS-L0844, -■ノ0860
According to (k), the fastness to washing and dry cleaning was evaluated to be very good, and it also met JIS-LO842.
No photobleaching was observed regarding the light fastness of the color surface.

Comparative Example 1.2 Dyeing with disperse dye I (ayalon F'ast Red)
R2f/stone dyeing 7i4a degree, bath ratio 1:50.120℃
A leather-like sheet material having a grain layer was obtained in the same manner as in Example 1, except that after high-pressure dyeing, normal reduction washing was performed (Comparative Example 1).

In addition, dyeing can be done using acid dye Kayanol Mill Re.
d R8125% A leather-like sheet with a grain layer was prepared in the same manner as in Example 1, except that after dyeing at 95° C. for 60 minutes, fixation treatment was performed with tannic acid and tartar stone, and second processing was performed. (0) f: Obtained (Comparative Example 2).

Table 1 shows their fastness, and the leather-like sheet materials (U) and (0) of ratio 1 bite examples 1 and 2 were poor in fastness.
The problem was that it could not be washed or dry cleaned.

Table 1 The numbers in the table represent the respective grades.

Example 2 A pore size of 0.2+11 was formed on both sides of the nonwoven fabric made in Example 1.
J! Pitch Q: 1 from nozzles lined up in a row at 6m1n
00 Immediate/cf! The high-speed fluid stream was applied four times each while vibrating the nozzle at a pressure of . The obtained nonwoven fabric had a fiber structure in which the surface layer of mutually arranged polymer fibers branched into ultrafine fibers or bundles thereof, and were densely intertwined with each other. After drying, the surface was smoothed by pressing with a heating roll.

After that, the same resin used in Example 1 was applied at a coating amount of 4y.
/ml' and then pressed through a heated embossing roll to emboss a leather-like grain pattern. After that, the AS
The resin was almost completely extracted and removed. Next, dyeing and finishing were performed in the same manner as in Example 1.

The obtained leather-like sheet material has a smooth surface that follows the grain pattern and has a deep luster, and has a flexible texture, and even when washed in a washing machine with a lot of scrubbing, the surface does not become fuzzed or cracked. There was no occurrence of color fading, there was no color fading into the washing liquid, and the product had excellent durability and high fastness.

Comparative Example 6 A leather-like sheet material was obtained by carrying out the same treatment as in Example 2, except that the step of spraying a high-speed fluid stream onto both surfaces of the nonwoven fabric was omitted. In addition to the grain pattern, this leather-like sheet material had irregularities along the vein-like microfiber bundles, and when washed in a washing machine while scrubbing, no color fading was observed in the washing liquid. Cracks were observed to occur here and there along the ultrafine fiber bundles.

Example 6. Comparative Example 4 6. Polymer mutually arranged fibers containing 36 ultrafine fibers in one filament at a ratio of 55 parts of styrene copolymer as a binding component and 6.45 parts of nylon as an ultrafine fiber component. A nonwoven fabric was made in the same manner as in Example 1 using a 5 denier, 51 mm. This nonwoven fabric had a basis weight of 545y/'' and a thickness of 2.8 mm.

Using the same nozzle as in Example 2, one side of this nonwoven fabric was
A columnar flow of water injected at a pressure of 0.00 IrP/ct& was brought into contact, and the treatment was carried out three times under the same conditions and twice by lowering the pressure to 60 IrP/Ca. Furthermore, it was placed in hot water at 80°C and subjected to a shrinkage treatment and a nip using a mangle. The thickness of the obtained interlaced nonwoven fabric was reduced to about 2.0 mm, and the layer having a thickness of about I from the water-flow treated surface was composed of ultrafine fibers with an average fineness of about 0.04 denier branched from the polymer interlayer fibers. and their bundles are intertwined with each other in a dense and dense manner,
Its surface had very few irregularities. Thereafter, the same polyurethane as in Example 1 was impregnated with carbon black using an impregnating solution with a concentration of 6 ml at a ratio of 0.03 to the solid content of the polyurethane, followed by coagulation, hot water washing, and drying. Next, polystyrene and polyethylene glycol were dissolved and removed using trichlorethylene, and the mixture was cut in half with a slicer into 0.8 pieces to obtain sheets (C) and (D).

After that, using sheet (C), on the surface layer of the water-treated side, use a gravure coater to coat the polyurethane solution with carbon blank and complex salt dye added at 15% and 5%, respectively, to the polyurethane solid content. 5y/m
”, dried, pressed and integrated to form a composite and textured.The other side was puffed to fluff the ultra-fine fibers, and then reactive dye was used in accordance with the printing method. The resulting leather-like sheet material was dyed and subjected to the usual finishing process.The obtained leather-like sheet material had a texture with a sense of unity with little repellency, and one side had fluff of ultra-fine fibers with relatively long piles. The other side had a silver surface with an elegant appearance, and had a structure very similar to natural bank leather.

On the other hand, Sort (D) was subjected to the same treatment as in Example 3 without adding carbon black and dye to the polyurethane solution (Comparative Example 4). The resulting leather-like sheet material has poor commercial value because the polyurethane used for the grain layer has poor affinity for dissolving reactive dyes, and the resin layer is not colored at all, and the surface is irritated because only the ultrafine fibers are colored. Met. Also, J.I.
When light resistance was evaluated using S-LO842, the color of the sheet obtained from sheet (D) had completely faded, whereas the product of the present invention (0) had no pigment or complex salt contained in the resin layer. The dye compensated for this and almost no fading was observed.

When the leather-like sheet material obtained from the sheet (0) of the present invention was made into a coat, it did not feel stiff and maintained an elegant silhouette, and no fuzzing or cracking was observed even when the surface was strongly rubbed by hand. I couldn't. Further, even when dry-cleaned, there were no problems and no contamination of other items to be washed.

Example 4 The nonwoven fabric obtained in Example 1 was partially dissolved and removed using trichlorethylene in the same manner as in Example 1.
Furthermore, a high-speed fluid stream was sprayed on both sides of the sheet to branch and entangle the fibers, remove PVA, and puff one side, and the process was completed immediately before applying the resin for the grain layer of Example 1. Formed.

Thereafter, the sheet (entangled body consisting only of ultrafine fibers) was dyed black with a reactive dye using a Wins type dyeing machine. Next, the same resin for the grain layer as used in Example 3 was applied to the unpuffed side, and pressed with a heated roll to form a composite with the densely entangled fiber entanglement. At the same time, grain shaping was performed. Next, it was finished by kneading it with moist heat.

The obtained leather-like sheet material is flexible, has a firm surface feel, has a deep luster, and has an elegant texture due to the combination of the textured pattern and the textured pattern produced during the kneading process. It had an appearance. In addition, even if you rub the surface strongly with your fingertips, the silver layer will not peel off or become fluffy, and of course, even if you scrub it in the washing machine, the color will not fade into the washing liquid, making it durable. In addition to having excellent properties, it also had high fastness.

Patent applicant: Toshi Co., Ltd.

Claims (5)

[Claims] (1) In the method for producing a leather-like sheet material having a grain layer, at least the following A −+ B −) C−+ DA
−+B −+ D −+ C and A −+ D −+
A method for manufacturing a leather-like product having a grain layer, characterized by carrying out a combination of steps selected from B − + C and the optional step E below Step A: o, o Ultrafine fibers of denier or less are A step of obtaining a fiber sheet having a three-dimensional entangled structure of formable multicomponent fibers, Step B: Spraying a high-speed fluid stream onto at least one side of the woven fiber-1 to split and entangle the fibers. , Step C: A step of applying a resin containing 3 to 300% of a coloring agent based on the solid content of the resin to the surface onto which the high-speed fluid stream has been sprayed. Step D: A step of forming ultrafine fibers from the multicomponent fiber. Step E: A step of coloring with a reactive dye. (2) A method for producing a leather-like sheet material having a grain layer according to claim 11, characterized in that step E is carried out after the step. (3) Production of a leather-like sheet-like article having a grain layer according to claim (1), characterized in that step E is performed after any of steps A, B, C, and D. Law. (4) A method for producing a leather-like notebook having a grain layer according to any one of claims (1) to (3), wherein the ultrafine fibers are made of polyamide. (5) The silver according to any one of claims (1) to (4), wherein the ultrafine fiber is formed by dissolving and removing at least one component of the multicomponent fiber. A method for producing a leather-like sheet material having a surface layer.