JP4291192B2 - Method for producing leather-like sheet - Google Patents

Description

  The present invention relates to a method for producing a leather-like sheet, and more particularly, a leather-like material suitable for artificial leather with a silver-tone tone that is excellent in wear resistance and is formed by bonding a fibrous base material and a film layer with an adhesive. The present invention relates to a method for manufacturing a sheet-like material.

  Silver-like leather-like sheet-like material having a polymer elastic body on the surface is used for a wide range of applications such as shoes, balls, bags, furniture / vehicle skins, clothing as artificial leather or synthetic leather, In recent years, there has been a demand for excellent wear resistance while maintaining flexibility in each application. And among the methods for producing leather-like sheets, it is said that leather-like sheets obtained by laminating a film layer on a fibrous base material have a relatively thick film layer and are excellent in wear resistance. Yes.

  As a technique for further improving the abrasion resistance of the leather-like sheet material by the laminating method, for example, Patent Document 1 discloses a synthetic leather in which a film layer is formed of silicone-modified polyurethane, and Patent Document 2 discloses a film. A leather-like sheet has been proposed in which the layer is a silicone-modified polyurethane resin crosslinked with a polyisocyanate curing agent and the adhesive layer is composed of a non-crosslinked polyurethane resin.

  However, although these films lower the friction coefficient of the film layer and lower the wear resistance at a glance, there is a problem that the adhesive force between the film layer and the adhesive layer tends to decrease, and peeling easily occurs. In addition, since the adhesive is solvent-based, there is also a problem that the polymer elastic body constituting the adhesive and the solvent easily enter the fibrous base material, and the leather-like sheet is hardened.

  Also, when the thickness of the polymer elastic body existing on the surface is increased in order to improve the wear resistance, the flexibility and texture of the fibrous base material disappears, and the surface becomes artificial leather with a hard surface. There was a problem that. In particular, when there are many fibers on the surface of the substrate, the fibers are fixed by the adhesive between the substrate and the film layer, and the decrease in the texture is remarkable.

Japanese Patent Laid-Open No. 9-31862 JP 2000-248472 A

  The present invention has been made against the background of the above-described prior art, and its purpose is to improve the abrasion resistance of the sheet-like material while being excellent in peel strength, and at the same time excellent in texture such as flexibility and flexibility. It is in providing the manufacturing method of a thing.

  In the method for producing a leather-like sheet of the present invention, a treatment liquid mainly composed of a water-based polymer elastic body having a solid content concentration of 20 to 60% by weight is applied in advance to any one surface of a fibrous base material. The water-based polymer elastic body is infiltrated so as to have a sinking amount in the range of 15 to 50 μm from the surface, dried, and then the elastic film is bonded to the coated surface via a water-based adhesive. And

Furthermore, the solid content adhesion amount after drying of the water-based polymer elastic body to the fibrous base material is 15 to 60 g / m ² , or the treatment liquid contains the silicone compound in the solid content weight of the water-based polymer elastic body. It is preferable to contain 0.5-8 weight% with respect to.

  According to the production method of the present invention, a leather-like sheet-like material having excellent peel strength while improving the abrasion resistance of the sheet-like material, and at the same time, excellent texture such as flexibility and flexibility is provided.

Hereinafter, the present invention will be described in detail.
In the production method of the present invention, a treatment liquid mainly composed of a water-based polymer elastic body is previously applied to any one surface on a fibrous base material, infiltrated, dried, and then water-based on the coated surface. This is a method for producing a sheet-like material by a so-called laminating method, in which an elastic film is bonded through an adhesive. Furthermore, it is essential that the solid concentration of the treatment liquid to be applied in advance is 20 to 60% by weight, and the sinking range into which the water-based polymer elastic body penetrates after the treatment liquid is applied is 15 to 50 μm from the surface. This is a manufacturing method.

  The fibrous base material used in the present invention is not particularly limited as long as it is conventionally used as artificial leather or synthetic leather, but preferably the fibrous base material is not composed of only a fiber assembly. A composite made of a fiber assembly and a polymer elastic body is preferable.

  Here, the fiber aggregate constituting the fibrous base material may be a woven fabric, a knitted fabric, a non-woven fabric, or the like, but is preferably a non-woven fabric from the viewpoint of texture. Examples of fibers constituting these fiber aggregates include polyamide fibers such as nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, polyethylene terephthalate, polytriethylene terephthalate, polybutylene terephthalate, and the like. Examples thereof include polyester fibers such as copolyesters containing these as main components, and several types of mixed fibers thereof. Among them, polyethylene terephthalate or nylon-6 is preferable from the viewpoints of production stability, cost, etc., and it is particularly preferable to be a peelable split type composite fiber made of polyester and nylon.

  The fineness of the fiber is preferably 2 dtex or less, and more preferably in the range of 2 to 0.001 dtex industrially. In the case of fibers having a fineness exceeding 2 dtex, the texture of the fibrous base material tends to be hard, and finally the leather-like sheet-like material tends to be hard. These fibers can be obtained by a conventionally known spinning method, and in order to further improve the texture, for example, a production method capable of obtaining a fineness such as a mixed spinning fiber, a sea-island spinning fiber, or a peeled split fiber may be used. preferable.

Furthermore, the apparent density of the fiber assembly is preferably in the range of 0.25 to 0.35 g / cm ³ . When the density is low, it is preferable to shrink the fiber after it is entangled with a needle punch or the like. It is appropriate that the shrinkage rate at this time is 20 to 50% smaller than the original area. In order to smooth the surface, it is also preferable to nip the surface of the nonwoven fabric with a mirror metal roll.

  In addition, the fibrous base material of the present invention is preferably a composite of the fiber assembly and a polymer elastic body. Such a fibrous base material is, for example, an impregnated composite obtained by impregnating a fiber aggregate with a solution or dispersion of a polymer elastic body and drying. Examples of the polymer elastic body used for the impregnation include SBR, NBR, polyurethane, polyester elastomer, acrylate ester, and the like, and polyurethane is preferable from the viewpoint of texture and strength. As a method of combining the polymer elastic body with the fiber assembly, the fiber assembly is impregnated with a solution in which the polymer elastic body is dissolved in a solvent, or a dispersion in which the polymer elastic body is dispersed in a dispersion medium. A general method is to extract or evaporate the solvent or dispersion medium. Among them, a method using an aqueous dispersion of a polymer elastic body is preferable in terms of working environment. Other methods include a method of impregnating a fiber structure with a hot melt of a polymer elastic body, a method of forming a polymer elastic body after impregnating a raw material of the polymer elastic body or an unreacted intermediate, etc. can give. The surface of the fibrous base material used in the present invention is preferably such that the film of the polymer elastic body is not formed and the fibers are exposed on the surface from the viewpoint of securing the texture. For example, such a surface can be obtained by impregnating a fiber assembly with a solution, dispersion, or liquid of a polymer elastic body, and then scraping the polymer elastic body liquid present on the surface before drying or solidifying. Obtainable.

  From the balance of texture and physical properties as a leather-like sheet, the thickness of the fibrous base material is preferably in the range of 0.5 to 2.0 mm. When the fibrous base material is a composite of a fiber assembly and a polymer elastic body, the fiber / elastic body ratio R / F is preferably 10 to 40%.

  In the present invention, the surface of such a fibrous base material is preliminarily coated with a treatment liquid mainly composed of a water-based polymeric elastic body and allowed to permeate. It is characterized by increasing the abundance ratio of the body. The aqueous polymer elastic body exists as an aqueous dispersion or an aqueous solution, and examples thereof include SBR, NBR, polyurethane, polyester elastomer, and acrylate. Since this treatment liquid is aqueous, even if the fibrous base material is a composite composed of a fiber assembly and a polymer elastic body, the impregnated polymer elastic body does not re-dissolve and the texture is improved. The existence ratio of the polymer elastic body to the fiber can be improved without deteriorating. In addition, since the polymer elastic body is not an organic solvent solution type dissolved in an organic solvent but an aqueous system, it is easy to control the penetration thickness of the treatment liquid into the fibrous base material and keep the texture uniform. be able to.

  The concentration of the polymer elastic body dispersion or aqueous solution used as the treatment liquid needs to be 20 to 65% by weight, and more preferably 40 to 60% by weight. When the concentration is less than 20% by weight, the abundance ratio of the polymer elastic body on the surface of the fibrous base material cannot be sufficiently increased, and the wear resistance is not improved. On the other hand, when the concentration exceeds 60%, the texture of the artificial leather to be obtained, particularly the texture of the surface becomes hard, which is not preferable. The viscosity is preferably in the range of 1000 to 20,000 mPa · s.

There is no particular limitation on the method for applying the polymer elastic body to any one of the surfaces on the fibrous base material. For example, a knife coating method is used in which the treatment liquid existing on the base material is scraped with a knife having a clearance. Adopt it. At this time, the adhesion amount of the polymer elastic body is preferably 15 to 60 g / m ² in terms of the solid content weight after drying. When the amount of the polymer elastic body applied and penetrated exceeds 60 g / m ² , it is necessary to deepen the penetration because the texture becomes hard or the amount of the polymer elastic body is large. The presence density of the polymer elastic body in the surface portion of the base material becomes small, and the finally obtained sheet-like product tends to have a reduced wear resistance. Further, even when the amount of the polymer elastic body that has penetrated is less than 15 g / m ² , the absolute amount of the polymer elastic body on the surface of the fiber aggregate or the composite structure is small, and the wear resistance tends to decrease. is there.

  The polymer elastic body coated in this way is allowed to penetrate into the fibrous base material by adjusting the viscosity of the treatment liquid, adjusting the surface tension by adjusting the amount of surfactant added, and the gap between the support roll and the knife during coating. . The gap between the support roll and the knife is preferably in the range of minus 20 μm to plus 200 μm of the fibrous base material thickness. When the gap is reduced too much, not only the surface coating amount of the resin decreases, but conversely, the penetration of the resin tends to become too deep. In that case, the resin on the surface disappears, and the surface smoothness of the leather-like sheet obtained by the fluff of fibers coming out on the surface tends to decrease. On the other hand, when the gap is too large, a coating layer made of a polymer elastic body is formed on the entire surface, and the adhesiveness to the elastic film layer tends to be lowered. The surface of the fibrous base material after infiltrating the polymer elastic body is preferably in a state where fibers and the polymer elastic body are mixed.

  The penetration depth of the polymer elastic body of the treatment liquid needs to be in the range of 15 μm to 50 μm from the surface of the fibrous base material. When the permeation depth of the permeated polymer elastic body exceeds 50 μm, the density of the polymer elastic body on the surface of the fiber assembly or the composite structure is reduced, and the wear resistance of the present invention is obtained. I can't. Further, even when the depth of the penetrated polymer elastic body does not reach 15 μm, the absolute amount of the fiber aggregate or the polymer elastic body on the surface of the composite structure is small, and the wear resistance of the present invention can be obtained. I can't.

  Furthermore, it is preferable to add and mix a silicone compound in the treatment liquid of the water-based polymer elastic body, so that further improvement in flexibility and wear resistance can be achieved. Examples of the silicone compound include dimethyl silicone oil, polymer dimethyl silicone, amino-modified silicone oil, polymer amino-modified silicone, reactive H-silicone, and modified compounds thereof. Among them, reactive H-silicone is preferable because it has the effect of improving the flexibility and wear resistance of the present invention. The reason for this is that an H-silicone that is in an oily state when an aqueous dispersion of an elastic polymer or an aqueous solution is coated on the surface of a fiber assembly or a composite structure and water as a dispersion medium is dried. It is considered that the elastic body is ejected on the surface together with the solidification of the elastic body and then reacted and solidified to prevent adhesion of the fibers in the fibrous base material by the polymer elastic body. That is, since a solidified silicone film is formed on the surface of the polymer elastic body between the fibers present in the surface layer of the fibrous base material, the friction coefficient between the water-based adhesive and the fibers at the time of lamination described later is It is considered that the degree of freedom decreases, the flexibility of the fibers increases and flexibility is obtained, and the wear resistance is improved.

  These silicone compounds are used as an aqueous dispersion or an aqueous solution mixed with the treatment liquid using an emulsifier. In general, the silicone compound does not dissolve in the polar organic solvent but dissolves in the non-polar organic solvent. Therefore, the silicone compound dissolves in the water-dispersed or water-based aqueous processing solution of the present invention without any problem.

  At this time, the mixing ratio of the polymer elastic body and the silicone compound is preferably a polymer elastic body: the silicone compound = 99.5: 0.5 to 93: 7 by weight ratio. When the mixing ratio of the silicone compound exceeds 7, the adhesive strength is lowered due to the strength reduction of the adhesive layer, and the flex resistance tends to be lowered. A more preferable mixing ratio is in the range of polymer elastic body: the silicone compound = 99: 1 to 96: 4.

  The treatment liquid of the water-based polymer elastic body is infiltrated into the surface of the fibrous base material and then dried. At this time, when the treatment liquid contains a silicone compound, the polymer elastic body penetrates between the fibers, so that the silicone compound of the present invention works effectively and exhibits a softening effect and an abrasion resistance improving effect. . When the polymer elastic body penetrates between the fibers, the silicone compound discharged to the surface of the polymer elastic body prevents the polymer elastic body from adhering to the fiber due to the releasing effect, and maintains the degree of freedom of the fiber. It is considered that the softening effect appears because it solidifies. In addition, when the surface of the obtained artificial leather is worn, the silicone compound present on the surface of the polymer elastic body has a sliding effect, so that the wear resistance is greatly improved.

  In the production method of the present invention, it is important that the treatment liquid of the polymer elastic body is permeated into the surface of the fibrous base material in advance. By the permeation of the polymer elastic body, a smooth surface composed of the fiber and the polymer elastic body is formed on the surface of the fibrous base material. By adopting such a configuration in the present invention, the surface of the fibrous base material is a layer composed of the three components of the fiber and the polymer elastic body of the treatment liquid and the adhesive when the film layer is laminated, or the fiber. When the base material is composed of a fiber assembly and an impregnated polymer elastic body, a four-component layer is formed with the impregnated polymer elastic body added, and minute voids are generated between the components. By doing so, it is considered that a sheet-like material excellent in texture, abrasion resistance and adhesiveness can be obtained.

  The polymer elastic film for laminating used in the present invention is formed, for example, by applying a polymer elastic body on a release paper. Examples of the polymer elastic body used in the film include SBR, NBR, polyurethane, polyester elastomer, acrylate, and the like. From the viewpoint of performance, polyurethane is preferable, and non-yellowing type polyurethane is more preferable.

  As a method for forming a polymer elastic body film on a release paper, for example, a solution obtained by dissolving a polymer elastic body in a solvent or a dispersion liquid in which a polymer elastic body is dispersed in a dispersion medium is coated on the mold release. A method of evaporating the solvent or the dispersion medium is employed. Among these, a method using an aqueous dispersion of a polymer elastic body is preferable in terms of working environment and the like.

  The thickness of the film of the polymer elastic body should be determined to be a thickness suitable for the texture in balance with the thickness of the artificial leather base of the fibrous base material, but is preferably 10 μm to 70 μm. If the thickness is too thin, the performance of the leather-like sheet such as yellow discoloration resistance, hydrolysis resistance, and adhesion tends to decrease. If it is too thick, the surface becomes hard and the texture of the sheet tends to be lowered.

  In the production method of the present invention, an elastic film is bonded to the surface of the fibrous base material coated with the treatment liquid via an aqueous adhesive. For example, it can be bonded by applying and bonding an adhesive on a polymer elastic film formed on a release paper. At this time, the adhesive used in the present invention is a water-dispersed or water-soluble adhesive. In the conventional artificial leather manufacturing method, it is common to use an organic solvent solution type dissolved in an organic solvent, but this method contains an organic solvent when adhering to a fiber assembly. Since it is also a good solvent for the molecular elastic body, the polymeric elastic body may swell or dissolve and re-adhere, which may impair the texture of the original sheet. In the present invention, it is essential that the adhesive is water-dispersed or water-soluble in order to reduce the adverse effect on the texture caused by the organic solvent during bonding.

Since the adhesive of the present invention is water-dispersed or water-soluble, the resulting adhesive layer also tends to swell or dissolve in water. To solve this problem, the adhesive is a cross-linking reaction type. A so-called two-component adhesive is preferable. Adhesives include urethanes and olefins, but urethanes are preferred in terms of wear resistance and flexibility. Examples of the crosslinking agent include melamine-based, polyisocyanate-based, epoxy-based, etc. Among them, polyisocyanate-based is preferable in terms of work environment and flexibility. The application amount of such an adhesive is preferably 50 to 250 g / m ² in terms of solution weight.

  In addition, by adding and mixing thermally expanded microcapsule particles in the adhesive liquid, the adhesive layer becomes porous and the surface becomes soft when it becomes artificial leather. Can do. The thermally expandable microcapsule contained in the adhesive is preferably one that undergoes thermal expansion at a temperature of 80 ° C. or higher. More specifically, for example, capsules such as those microencapsulated with a shell wall of a copolymer such as vinylidene chloride and acrylonitrile are preferable, and the diameter is preferably 10 to 30 μm. Moreover, it is preferable that thermal expansion start temperature is 80 to 120 degreeC. The content of the microcapsule that thermally expands is preferably 0.5 to 10 wt%, more preferably 1 to 5 wt%, based on the solid content weight of the adhesive.

  More specifically, for example, the method for producing a leather-like sheet-like material of the present invention forms a polymer elastic film on a release paper, and an aqueous water-dispersed or water-soluble adhesive is applied thereon, Next, after arbitrary drying, a fibrous base material in which a treatment liquid of a polymer elastic body has been permeated in advance is overlapped and bonded under an arbitrary pressure. Furthermore, it is preferable to perform thermal bonding with a metal heating cylinder having a temperature of 100 to 130 ° C. Thereafter, after sufficiently reacting the adhesive, the fibrous base material is peeled off from the release paper to obtain a leather-like sheet.

Hereinafter, the present invention will be described more specifically with reference to examples.
In addition, each item in an Example was measured with the following method.

(1) Abrasion resistance In accordance with the ASTM D-3886 method, HANDY ROLL P320J (manufactured by NORTON) was used as sandpaper, and the size at which the abrasion-exposed fiber layer reached a diameter of 10 mm was determined.

(2) Peel strength According to JIS K6301 method, the average value of five minimum values for every 20 mm when peeled 100 mm at a pulling speed of 50 mm / min was expressed as N / cm and was taken as peel strength.

(3) Flexibility A flexibility test piece 25 mm × 90 mm is prepared, and the lower 20 mm in the longitudinal direction is held in the vertical direction by a holder, and tested on a U gauge measuring unit located at a height of 20 mm from the holder. Slide the holder while bending the test piece so that it hits the center at 20 mm from the tip of the other end of the piece, and read the stress 5 minutes after fixing from the recorder. The degree of flexibility was calculated by converting the stress per cm. The unit is expressed in g / cm.

(4) Bending resistance A test according to the JIS K6545 method and the JIS K6505 method was performed, and the bending resistance was expressed by the number of cracks on the surface.

[Example 1]
(Create fiber base material)
Nylon-6 (intrinsic viscosity 1.1 in m-cresol) dried at 120 ° C. was fed to an extruder and melted. Separately dried polyethylene terephthalate (at an intrinsic viscosity of 0.64 in o-chlorophenol) at 160 ° C. was melted with an extruder separate from the foregoing.

  Subsequently, the nylon-6 mixture melt flow was introduced into a spin block maintained at 275 ° C. at a conduit polymer temperature of 250 ° C., the polyethylene terephthalate melt flow at 300 ° C., and a rectangular shape having hollow forming discharge holes in a lattice arrangement. The two polymer melt flows are combined using a spinneret, combined and discharged at a rate of 2 g / min. / Hole, and an air pressure of 0.35 MPa (spinning speed converted from the discharge rate and composite fiber fineness is about 4860 m / min). Towed at high speed.

  The pulled composite fiber is subjected to a high voltage application treatment at −30 kV, collided with a dispersion plate together with an air flow, opened, and a net conveyor as a web composed of a split split composite fiber having a 16-split multi-layer laminated cross section. Collected 1m wide above.

The obtained web was passed through a pair of upper and lower embossed calender rolls heated to 100 ° C., entangled with a needle punch, dipped in water, lightly squeezed with a mangle, and then applied to a sheet-like material strike-type squeezing machine. Then, an exfoliation division process was performed to obtain an ultrafine fiber nonwoven fabric having a basis weight of 210 g / m ² . Next, this nonwoven fabric was contracted in warm water at 70 ° C. to obtain an area of 60% of the area before contraction.

The obtained fiber assembly had a basis weight of 350 g / m ² , a thickness of 1.0 mm, and a flexibility of 0.25 g / cm. In addition, the single fineness of each fiber after splitting was 0.15 dtex.

  After impregnating the above fiber assembly with a 10% by weight polyurethane (Dainippon Ink Chemical Co., Ltd .; Crisbon TF50P) -dimethylformamide (hereinafter referred to as DMF) solution, excess fiber assembly surface The solution was scraped off and immersed in water to solidify the polyurethane and sufficiently wash and remove DMF, followed by drying at 120 ° C. to obtain a fibrous base material 1 composed of fibers and a polymer elastic body.

The surface of the obtained fibrous base material 1 was a mixture of fibers and polyurethane. The basis weight was 455 g / m ² , the thickness was 1.0 mm, and the flexibility was 0.82 g / cm.

(Creation of leather-like sheet 1)
On the surface of the obtained fibrous base material, 100 parts of water-dispersed polyurethane adhesive (Hydran A441 manufactured by Dainippon Ink & Chemicals, Inc., 45% concentration) as a polymer elastic body C was added to an H silicone aqueous dispersion ( 2 parts Dick Silicone Conch V, manufactured by Dainippon Ink & Chemicals, Ltd. 2 parts of catalyst (Dick Silicone, manufactured by Dainippon Ink & Chemicals, Inc., Catalyst SC30), Colorant (Dainippon Ink Chemical Co., Ltd.) 5 parts of Dirac Black HS9530), 6 parts of cross-linking agent (Hydran Assister C-50 manufactured by Dainippon Ink & Chemicals, Inc.) and thickener (Hydran Assister T1 manufactured by Dainippon Ink & Chemicals, Inc.) The mixed liquid whose viscosity was adjusted to 5000 mPa · s by mixing was coated with a coating bar having a diameter of 15 mm with a gap of 1.0 mm which is the same as the substrate thickness. Subsequently, it was dried at a temperature of 90 ° C. for 2 minutes and at a temperature of 110 ° C. for 1 minute. The amount of solid content after drying of the treatment liquid mainly composed of a water-based polymer elastic body (polyurethane) to the obtained fibrous base material is 42 g / m ² , and the polyurethane which is a polymer elastic body by a microscope is used. The penetration depth from the surface was 32 μm.

Next, on a release paper (R53 manufactured by Lintec Corporation), 100 parts of 33% aqueous polyurethane dispersion (Hydran WLS201 manufactured by Dainippon Ink & Chemicals, Inc.) was added to a thickener (Hydran Assister T1), and a colorant ( Dirac Black HS9530) 5 parts added with stirring and a viscosity adjusted to 8000 mPa · s was coated at a weight of 90 g / m ² and dried at a temperature of 70 ° C. for 2 minutes and at 110 ° C. for 2 minutes to form a polymer. An elastic film was formed. Furthermore, on the surface, 100 parts of a water-dispersible polyurethane adhesive (Dai Nippon Ink Chemical Co., Ltd. Hydran A441, 45% concentration), 5 parts of a colorant (Dilack Black HS9530), thermal expansion microcapsules (Matsumoto Yushi) Pharmaceutical preparation Matsumoto Microsphere F-50 (1.5 parts) and a thickener (Hydran Assister T1) mixed to adjust the viscosity to 5000 mPa · s and coat with a basis weight of 150 g / m ² did. Next, after drying for 2 minutes at a temperature of 90 ° C., the fibrous base material 1 composed of a fiber assembly and a polymer elastic body is superposed and passed through a roll with a gap of 0.6 mm on a heating cylinder surface at a temperature of 110 ° C. did. Then, after leaving for 2 days in an atmosphere at a temperature of 60 ° C., the release paper was peeled off to obtain a leather-like sheet 1. The obtained leather-like sheet 1 has a softness of 0.55 g / cm, a soft surface, wear resistance of 1600 times, flex resistance of 200,000 times or more, and peel strength of 41 N / cm. there were.

[Example 2]
Example 1 except that the solid adhesion amount after drying of the treatment liquid mainly comprising an aqueous polymer elastic body to be treated on the surface of the fibrous base material 1 obtained in Example 1 is 34 g / m ^2. A leather-like sheet-like material 2 was prepared by the same operation. In this case, the penetration depth from the surface of the polyurethane, which is a polymer elastic body, was 25 μm.

  The obtained leather-like sheet-like material 2 has a softness of 0.90 g / cm, a soft surface, abrasion resistance of 2100 times, bending resistance of 200,000 times or more, and peel strength of 44 N / cm. there were.

[Comparative Example 1]
The sheet-like material 3 is operated in the same manner as in Example 1 except that the surface of the fibrous base material 1 obtained in Example 1 is not subjected to surface treatment with a treatment liquid mainly composed of an aqueous polymer elastic body. It was created.

  The obtained sheet-like material 3 has a flexibility of 1.50 g / cm, abrasion resistance of 390 times, bending resistance of 70,000 times, and peel strength of 7 N / cm. However, the physical properties of the present invention could not be obtained, and it was unsuitable for artificial leather. Moreover, in the observation of the cross section with a microscope, the adhesive used for the lamination penetrated deeply from the surface of the fiber assembly to the inside.

[Comparative Example 2]
On the surface of the fibrous base material 1 obtained in Example 1, the treatment liquid mainly composed of the water-based polymer elastic body used in Example 1 is used to measure the fiber aggregate thickness with a doctor knife having a thickness of 0.3 mm. Coated with an 80% gap of 0.8 mm. Subsequently, it was dried at a temperature of 90 ° C. for 2 minutes and at a temperature of 110 ° C. for 1 minute. The amount of polyurethane adhering to the obtained fibrous base material was 18 g / m ² , and the penetration depth of the polymer elastic body from the base material surface by a microscope was 86 μm. Next, a sheet-like material 4 was prepared by the same operation as in Example 1.

The obtained sheet-like material 4 has a flexibility of 1.70 g / cm, abrasion resistance of 460 times, bending resistance of 60,000 times, peel strength of 11 N / cm, and it can be folded like paper and has a texture. However, the physical properties of the present invention could not be obtained, and it was not suitable as artificial leather. When the cross section was observed with a microscope, the adhesive penetrated deeply from the surface of the fiber assembly.

  The leather-like sheet-like material of the present invention is excellent in peeling strength while improving wear resistance, and at the same time excellent in flexibility and flexibility, so that it can be used for sports shoes, women's / men's shoes, etc. It can be preferably used for various ball applications, industrial material applications such as furniture / vehicles, interior materials and interior materials, bookbinding applications such as notebooks and notebooks, and clothing applications.

Claims (6)

  A treatment liquid mainly composed of a water-based polymer elastic body having a solid content concentration of 20 to 60% by weight is previously applied to any one surface on the fibrous base material, and the water-based polymer elastic body is 15 to 50 μm from the surface. A method for producing a leather-like sheet-like material, comprising impregnating so as to have a sinking amount in the range of, and drying, and then adhering an elastic film to the applied surface via a water-based adhesive. The process according to claim 1 leather-like sheet according solids deposition amount after drying of the aqueous elastic polymer to the fibrous base material is 15 to 60 g / m ^2.   The method for producing a leather-like sheet according to claim 1 or 2, wherein the treatment liquid contains a silicone compound in an amount of 0.5 to 8% by weight based on the solid content weight of the water-based polymer elastic body.   The method for producing a leather-like sheet material according to any one of claims 1 to 3, wherein the aqueous adhesive contains 1 to 20% by weight of thermally expanded microcapsule particles with respect to the adhesive solid content.   The method for producing a leather-like sheet according to any one of claims 1 to 4, wherein the fibrous base material is a composite comprising a fiber assembly and a polymer elastic body.   The method for producing a leather-like sheet-like material according to any one of claims 1 to 5, wherein the polymer elastic body in the treatment liquid is a polyurethane resin.