WO2005106108A1

WO2005106108A1 - Artificial leather with silvered tone

Info

Publication number: WO2005106108A1
Application number: PCT/JP2005/007863
Authority: WO
Inventors: Masaru Makimura; Hisao Yoneda
Original assignee: Kuraray Co., Ltd.
Priority date: 2004-04-28
Filing date: 2005-04-26
Publication date: 2005-11-10
Also published as: CN1957136B; KR20070006870A; KR101166273B1; CN1957136A; JP4560511B2; EP1749920A1; JPWO2005106108A1; TWI372806B; TW200609411A; EP1749920A4

Abstract

An artificial leather with a silvered tone which comprises a base layer and a coating layer (Y) formed on one side of the base layer. The base layer comprises an interlacing nonwoven fabric (X) made of bundles of microfine fibers having an average single-fiber fineness of 0.07 dtex or smaller and a polymeric elastomer (A) and a polymeric elastomer (B) each infiltrated in inner parts of the fabric (X). The interlacing nonwoven fabric (X) comprises a lower layer (XA) and an upper layer (XB). Mainly the polymeric elastomer (A) has been infiltrated in the lower layer (XA) substantially in the state of being not bonded to the microfine-fiber bundles. Mainly the polymeric elastomer (B) has been infiltrated in the upper layer (XB) substantially in the state of being not bonded to the microfine-fiber bundles. The coating layer (Y) is composed of a 1-10 μm-thick coating layer (YB) of the polymeric elastomer (B) formed on the upper layer (XB), a coating layer (YC) of a polymeric elastomer (C) formed on the coating layer (YB), and a finish layer (YE) formed on the coating layer (YC). The artificial leather with a silvered tone, which has such structure, combines an excellent appearance similar to those of natural leathers with excellent softness, flexibility, and high peel strength.

Description

Artificial leather with silver

Technical field

[0001] The present invention also relates to a silver-tone artificial leather having a natural leather-like elegant appearance, excellent softness, flexibility, and high peel strength. The artificial leather with a silver tone can be widely used for applications such as shoes, balls, and so on.

Background art

[0002] In recent years, synthetic leather and artificial leather have been widely used as alternatives to natural leather in all fields such as shoes, clothing, gloves, gloves, balls, and interiors. These products are required to have higher quality, aesthetics, and comfortable feeling of use, and it is strongly desired that they have an elegant natural leather-like appearance, flexibility, and peel strength, especially for shoes. .

[0003] Conventionally, many natural leather-like sheets having flexibility have been proposed. For example, a leather-like sheet manufactured by adhering a resin film that reproduces natural leather-like grain to a substrate obtained by impregnating and coagulating polyurethane resin into an entangled nonwoven fabric having an ultrafine fiber strength of 0.1 deciters or less is proposed. Have been. Although the peel strength of such a leather-like sheet is high and suitable for sports shoes, the finish layer on the surface does not provide a natural leather-like property that does not allow a sense of unity with a thick substrate. Also, it was difficult to form a deep grain pattern.

Further, there has been proposed a leather-like sheet produced by coating a polyurethane solution on the surface of the substrate and wet-solidifying to form a foamed layer, and then coloring and embossing the foamed layer. Such a leather-like sheet has the appearance of a natural leather. However, when emphasis is placed on softness and flexibility, a relatively small amount of a soft elastic body is filled in the substrate, so that sufficient peel strength cannot be obtained.ゝIn addition, in order to obtain sufficient peel strength, a relatively hard elastic body needs to be filled in a large amount, and as a result, softness and flexibility are lost. As described above, it has been extremely difficult to produce a leather-like sheet having all of peeling strength, flexibility, softness and natural leather appearance.

[0004] An entangled nonwoven fabric made of ultrafine fiber-generating fibers is impregnated with polyurethane resin and wet-coagulated, and one component is removed from the ultrafine fiber-generating fibers to produce an ultrafine fiber bundle of 0.1 dtex or less. There has been proposed a leather-like sheet obtained by obtaining a substrate consisting of and then subjecting the substrate to a surface finishing process (for example, see Patent Document 1). Has a natural leather appearance, but has insufficient flexibility and peel strength. There has been proposed a leather-like sheet made of the same elastic resin as that impregnated in the surface layer of the base and having a surface porous layer provided continuously with the surface layer of the base (see, for example, Patent Document 2). However, when a surface porous layer was formed using a soft resin in order to obtain a natural leather-like appearance, sufficient peeling strength was obtained and it was difficult. In order to obtain sufficient peel strength, the surface porous layer is formed directly on the substrate using a relatively hard elastic body, or the surface porous layer is formed on the substrate surface via a high-density resin layer. It is also known to form a porous film layer on the surface porous layer. In such a leather-like sheet, when a natural leather-like appearance is obtained by embossing, sufficient peel strength is obtained, but softness is reduced. Conversely, if priority is given to softness, it becomes difficult to obtain the appearance of natural leather by embossing. If a resin with good embossability is used for the surface porous layer and a resin that is not easily deformed by embossing is used for the high-density resin layer, the same is used for the surface porous layer and the high-density resin layer. Sufficient embossability was difficult to obtain compared to the case where the resin was used.

[0005] In order to solve the above problem, the present inventors impregnated a polyurethane resin, which is less likely to be thermally deformed than the polyurethane resin constituting the surface porous layer, into the upper layer of the fibrous base layer which is in close contact with the surface porous layer. A leather-like sheet was proposed (see Patent Document 3). However, in order to have a natural leather-like appearance, it was necessary to form a surface porous layer made of a soft polyurethane resin and then embossed. For this reason, when the surface layer is thickened, a unified feeling may not be obtained as a whole.

As described above, silver-finished artificial leather that combines excellent peel strength, soft surface, flexibility, and a clear and elegant appearance comparable to that of natural leather is still available.

Patent Document 1: Japanese Patent Publication No. 63-5518

Patent Document 2: JP-A-11-140779

Patent Document 3: JP 2003-105679 A

Disclosure of the invention [0007] An object of the present invention is to provide artificial leather with silver that combines an elegant appearance of natural leather with excellent softness, flexibility, and high peeling strength. More specifically, it has a soft surface and high peeling strength. And silver-like artificial leather excellent in flexibility and a method for producing the same.

[0008] That is, the present invention provides a entangled nonwoven fabric X comprising a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, and a base comprising a polymer elastic body A and a polymer elastic body B impregnated therein. And a covering layer Y formed on one surface of the base layer. The entangled nonwoven fabric X comprises a lower layer X and an upper layer X.

A B A

Is mainly impregnated with the polymer elastic body A substantially not bonded to the ultrafine fiber bundle, and the upper layer X is mainly impregnated with the polymer elastic body B substantially in contact with the microfine fiber bundle.

B

The coating layer Y is formed on the upper layer X with a thickness of 1 to

B

A coating layer Y made of a 10 / z m polymer elastic body B, and a polymer bullet formed on the coating layer Y

B B

A coating layer Y composed of the active substance C and a finishing layer Y formed on the coating layer Y

C C E

The present invention provides an artificial leather with silver, characterized in that:

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

The artificial leather with silver of the present invention is provided on a base layer comprising an entangled nonwoven fabric X and a polymer elastic body A and a polymer elastic body B impregnated therein, and on one surface of the base layer. Made of the coating layer Y. The base layer is mainly composed of the lower layer X containing the elastic polymer A and the main layer.

A

Thus, the upper layer X including the elastic polymer B is formed. The coating layer Y provided on the upper layer X

B B

In order, the coating layer Y made of the polymer elastic body B, the coating layer Y made of the polymer elastic body C

B C

And finishing layer Y.

E

The substrate layer used in the present invention comprises a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, preferably 0.0001 to 0.07 dtex, more preferably 0.0001 to 0.05 dtex. This is a smooth surface layer composed of the three-dimensional entangled nonwoven fabric X and the polymer elastic bodies A and B contained therein. If the average single fiber fineness exceeds 0.07 deciters, the texture and the smoothness of the substrate layer will be poor, and it will be difficult to form a uniform grain pattern by embossing. The bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less is produced by a conventionally known method. For example, at least two It can be obtained by dissolving or decomposing and removing at least one component from a polymer ultrafine fiber-generating fiber, or by peeling off at the interface between two components by mechanical or chemical treatment. In order to keep the single fiber fineness of the ultrafine fibers constituting the ultrafine fiber bundle at 0.07 dtex or less, it is more advantageous to use sea-island type ultrafine fiber generating fibers than to use laminated type ultrafine fiber generating fibers. It is. It should be noted that the ultrafine fiber bundle and the elastic polymer constituting the artificial leather with silver of the present invention need not be substantially bonded to each other in terms of the soft feeling of natural leather. It is necessary to form an ultrafine fiber bundle from the ultrafine fiber-generating fibers in order to make the state substantially not adhered, and it is preferable to form them from sea-island type ultrafine fiber-generating fibers.

[0010] Examples of the polymer constituting the ultrafine fibers in the ultrafine fiber-generating fibers include melt-spinnable polyamides such as 6 nylon and 66 nylon, polyethylene terephthalate, polyethylene terephthalate, and cationic dyeable modified polyethylene terephthalate. Examples include at least one polymer selected from the group consisting of spinnable polyesters. In addition, the polymer to be dissolved or decomposed and removed is different from the polymer constituting the ultrafine fiber in solubility in a solvent or decomposability by a decomposer, and has low compatibility with the polymer constituting the ultrafine fiber and spinning conditions. It is a polymer that has a lower melt viscosity or a lower surface tension than the polymer that makes up the microfiber below. For example, at least one kind of polymer, such as polyethylene, polystyrene, polyethylene propylene copolymer, and modified polyester, which is also selected for its polymer power is used.

[0011] The ultrafine fiber generating fibers are defibrated with a card and formed on a web through a webber.

The obtained web is laminated so as to have a desired weight and thickness, and then entangled by a known method such as needle punching or high-speed water flow to obtain an entangled nonwoven fabric X. If necessary, a woven or knitted fabric having a bundle strength of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less can be laminated on the web. The surface of the entangled nonwoven fabric X can be uniformly smoothed by a press treatment or the like before impregnation with the elastic polymer to improve the surface smoothness of the resulting silver-finished artificial leather and form a grain pattern uniformly. It is preferred in that respect. The thickness of the obtained entangled nonwoven fabric X or the pressed entangled nonwoven fabric X is selected according to the use of the artificial leather with silver, and is not particularly limited. When using entangled nonwoven fabric X in a single layer Has a thickness of 0.2 ~: preferably about LOmm, preferably about 0.4 ~ 5mm. Density ί or 0. 15~0. 60g / cm ³ power preferably, 0. 20~0. 40g / cm ³ force ^ good more preferable. When the density is within the above range, an appropriate amount of the polymer elastic body can be impregnated, a rubber-like texture can be avoided, a decrease in peel strength can be prevented, and a soft texture can be obtained. Preferable because artificial leather with silver tone can be obtained.

Next, the entangled nonwoven fabric X is impregnated with a solution or a dispersion of the polymer elastic bodies A and B, and then a coating layer Y is formed. As the polymer elastic bodies A, B and C used in the present invention, known polymer elastic bodies can be used as long as they are conventionally used in the production of artificial leather. Above all, polyurethane is preferably used from the viewpoint of obtaining natural leather-like feeling and physical properties.

Preferred examples of the polymer elastic bodies A to C that impregnate the entangled nonwoven fabric X and form the multilayer Y are one type of a polymer diol such as a polyester diol, a polyether diol, and a polyester ether diol. At least one of organic polyisocyanates, preferably aliphatic, aromatic or alicyclic organic diisocyanates; and having two active hydrogen atoms such as low molecular weight diols, low molecular weight diamines, and hydrazines And polyurethanes made from chain extenders.

[0013] Above all, a polyurethane having a mass percentage of nitrogen atoms of isocyanate in an organic polyisocyanate unit present in the polyurethane (hereinafter referred to as N%) of 2.5 to 5% with respect to the total mass of the polyurethane, or the polyurethane or the polyurethane. A mixture mainly composed of When the N% is within the above range, the properties of the coating layer Y and the base layer such as abrasion resistance and pulling resistance are good, the bending shear becomes coarse and the texture becomes hard, and artificial leather is produced. It is preferable because it can be prevented from becoming cheap and the physical properties of the artificial leather such as flex fatigue resistance are good.

The elastic polymer C used for the coating layer Y of the present invention has a natural leather tone by embossing.

C

It is preferable to use polyurethane capable of forming a grain pattern. Examples include hard segments mainly composed of polymer glycols having hydroxyl groups at both terminals and having a molecular weight of 500 to 5000, 4,4'-diphenylmethane diisocyanate, and lower alkylene glycols having 2 to 6 carbon atoms. Polyurethanes or have hydroxyl groups at both ends And polymer polyurethanes having a molecular weight of 500 to 5,000, aliphatic or alicyclic diisocyanates, and polyurethanes having a hard segment mainly composed of organic diamine or organic acid dihydrazide. However, a copolymer or a mixture of these may be used as long as the softness, flexibility, durability, workability, porous film forming property, and the like are sufficient.

[0015] Examples of the polymer glycol having a hydroxyl group at both terminals and having a molecular weight of 500 to 5,000 include polyester glycols such as polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, and polycaprolactone glycol; Polycarbonate glycols such as hexamethylene carbonate glycol; polyetherene glycols such as polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol and polyhexamethylene ether glycol; and mixtures thereof are used. Particularly preferred are polyester glycols, polycarbonate glycols, mixed glycols of polyester glycols and polycarbonate glycols, and mixed dalicols of polyester glycols, polycarbonate glycols and polyether glycols.

[0016] Aliphatic diisocyanates include tetramethylene diisocyanate and hexamethylene diisocyanate, and alicyclic diisocyanates include cyclohexanediisocyanate and 4,4'-dicyclohexylmethane diisocyanate. can give. Examples of organic diamines include p-phenylenediamine, metaphenylenediamine, 4,4'-diaminediphenylmethane, ethylenediamine, propylenediamine, diethanolamine, 4,4'-diaminodicyclohexynolemethane, and isophoronediamine. Examples of the organic acid dihydrazide include adipic acid dihydrazide, sebacic acid dihydrazide, terephthalic acid dihydrazide, and isophthalic acid dihydrazide. Examples of lower alkylene glycols having 2 to 6 carbon atoms include ethylene glycol, butanediol, hexanediol, diethylene glycol and dipropylene glycol.Especially, ethylene glycol can form a uniform grain pattern by embossing. Is preferred.

[0017] Thickness of the coating layer Y: 0.02 ~: L 50 mm force S preferred, 0.05 ~: L OOmm force S preferred c

Yes. When the content is within the above range, a smooth surface is obtained, a uniform grain pattern is formed by embossing, and a rubber-like texture can be avoided. [0018] Polymer elasticity to impregnate the base layer, especially the upper layer X of the entangled nonwoven fabric X in contact with the coating layer Y

B

The polymer elastic body that forms the coating layer Y must be the same, that is, the polymer elastic body B.

B

Is necessary. When the elastic polymer forming the upper layer X and the coating layer Y is different,

B B

And the coating layer Y have reduced adhesiveness and are easily peeled off.

The 100% modulus of the elastic polymer B is preferably 20 to: L00 kgZcm ² , more preferably 30 to 70 kgZcm ² . Further, the polymer elastic body B is a polymer constituting the coating layer Y.

C

It is preferable that a dense porous structure having a 100% modulus higher than that of the morphology C by 30 kgZcm ² or more can be formed, and it is difficult to be thermally deformed. 100% modulus of the elastic polymer B is, 30~60kgZcm ² high than that of the high-molecular elastic member C!, And more preferably! /,.

[0019] This is because when the coating layer Y is fixed in a state of being thermally deformed by embossing, the coating layer Y is fixed.

C

In particular, it prevents the elastic polymer B that constitutes the upper layer X

B B

This is because the ultrafine fiber bundle is maintained while being held, and the peel strength is increased. For this purpose, it is preferable that the polymer elastic body B forms a porous structure different from the polymer elastic body C, for example, the polymer elastic body B forms a denser porous structure than the polymer elastic body C. Coating layer Y and coating

B

Layer Y X

When observing the cross section in the thickness direction of C, the coating layer Y

The maximum diameter of the micropores in B and the upper layer B is preferably 1Z2 or less of the maximum diameter of the macropores (water droplet type or bottle type type holes) in the coating layer Y. c

, More preferably 1Z100 to 1Z2, even more preferably 1Z70 to 1Z5. When the content is within the above range, the coating layer Y is formed during embossing.

B and upper layer X

B U ヽ is preferable because it gives a soft and flexible feel that the porous structure does not collapse. If the polymer elastic body B does not form a porous structure, a feeling of unity between the coating layer Y and the base layer by embossing cannot be obtained, and the feeling tends to be poor. The pore diameter ratio can be controlled within the above range by a known method, for example, by appropriately adjusting the viscosity, concentration and type of the elastic polymer.

[0020] The polymer elastic body B is not particularly limited as long as it satisfies the above physical properties, but polyurethane is particularly preferably used in view of the feeling and physical properties of the resulting artificial leather with silver. The type of the polyurethane is not particularly limited, and an ester type, an ether type, a carbonate type, a copolymer type thereof, or a mixture thereof can be used. It is more preferable to use an ether-based soft segment and an aromatic diisocyanate and an aromatic diamine as the hard segment, because they are less likely to be thermally deformed. For example, a soft segment containing 50% or more, more preferably 70% or more of a polyether diol having an average molecular weight of 500 to 3,000, preferably polytetramethylene glycol, and 4,4′-diphenylmethanediisocyanate, p-phenyl- Polyurethanes composed of aromatic diisocyanates of which power is also selected, such as diamine, metaphen-diamine, 4,4'-diaminediphenylmethane, are used.

If necessary, a polyurethane different from the above may be mixed with the polyurethane, or a copolymerized polyurethane having a strong force such as an aethenole-based polymer diol, a polycarbonate-based polymer diol, or a polyesternole-based polymer diol may be used.

[0021] The amount of impregnation of the upper layer X of the polymer elastic body B with respect to the fiber mass Xb of the upper layer X is

B B

Is preferably 0.3 to 3.0 times, more preferably 0.8 to 2.0 times. It is preferable for it to be within the above range since a sufficient binder effect and necessary peel strength can be obtained without impairing the softness of the base layer.

The lower layer X of the entangled nonwoven fabric X is impregnated with a polymer elastic body A. As the elastic polymer A,

A

Although there is no particular limitation, polyurethane is preferably used in that it has a soft feeling and physical properties similar to those of artificial leather with silver tone. The polymer elastic body B constituting the upper layer of the base is affected by heat through the coating layer Y at the time of embossing, and therefore is not easily thermally deformed.

C

It is necessary. However, the lower layer (the lower layer X is impregnated with the polymer elastic body A)

A

Layer) is more embossed than the upper layer of the base (the layer in which the upper layer X is impregnated with the elastic polymer B).

B

It is less susceptible to heat during operation. Therefore, in order to impart softness and flexibility to the base layer, it is preferable to use a polyurethane which is more easily elastically deformable than the elastic polymer B and which is softer. The 100% modulus of the elastic polymer A is preferably 10 kg / cm ² or less lower than that of the elastic polymer B, more preferably 10 to 60 kgZcm ² .

The elastic polymer A is impregnated with an amount that emphasizes softness and does not impair the overall texture balance. For example, as a solid content with respect to the fiber mass Xa of the lower layer X, preferably 0.1

A

Impregnation of up to 1.5 times, more preferably 0.3 to 1.0 times. When the impregnation amount is within the above range, a rubber-like texture can be avoided, a good overall texture balance can be obtained, and a high-quality natural leather-like texture with a sense of fulfillment can be obtained. . [0023] The polymer elastic body B impregnating the upper layer X and the polymer elastic body A impregnating the lower layer X can be formed.

B A

It is preferable to impregnate only in a layered form because embossing can impart a natural leather-like elegant appearance uniformly.

The layer of the polymer elastic body B impregnated in the upper layer X has a force preferably depending on the thickness of the base layer.

B

It is 0.01 mm to 1.0 mm, more preferably 0.05 mm to 0.6 mm. When it is within the above range, sufficient peel strength can be obtained without impairing the softness by embossing, and rubber elasticity does not become unnecessarily strong and a natural leather-like low resilience texture can be obtained. preferable.

Further, the artificial leather with silver of the present invention has the following formula 1:

[b / (Xb + b)] / [(a / (Xa + a))] ≥l. 2 (1)

(Where b is the mass of the polymer elastic body B impregnated in the upper layer X, and Xb is the entanglement forming the upper layer X.

B B

Mass of synthetic nonwoven fabric, a is mass of polymer elastic body A impregnated in lower layer X, Xa is lower layer X

A A

(Mass of the entangled nonwoven fabric constituting), the required peel strength can be obtained, it can withstand deformation during embossing sufficiently, and it can maintain sufficient softness even when embossed. preferable. The upper limit of Equation 1 is more preferable in terms of the balance of the texture of the artificial leather with silver tone obtained to be 5.0.

[0025] Impregnation of the base material layer with the elastic polymer is not particularly limited as long as it is performed by a known treatment method. For example, a predetermined amount of a solution or a dispersion of the polymer elastic body B is applied to the upper surface of the entangled nonwoven fabric X and allowed to naturally penetrate or penetrate by rubbing with a roll or a knife. There is a method in which a solution or a dispersion of the polymer elastic body A is penetrated by rubbing with a roll or a knife or the like, and the excess is rubbed with a knife or the like.

Alternatively, after impregnating the entirety of the entangled nonwoven fabric X with the solution or dispersion of the polymer elastic body A, the entangled nonwoven fabric X is compressed in the thickness direction, and immediately thereafter, the solution or dispersion of the polymer elastic body B is impregnated. Can be used by applying a dispersion liquid and infiltrating it using the recovery force of the entangled nonwoven fabric X, and then using a knife to remove excess material that has protruded from the entangled nonwoven fabric X. Note that the upper layer X

B

After impregnating and solidifying the molecular elastic body B, the polymer elastic body B on the surface of the entangled nonwoven fabric X is scraped with a knife or the like so that the thickness after embossing is 1 to: LO m layer. Coating layer Y And the base layer can be manufactured simultaneously. Coating layer Y

B and the substrate layer may be manufactured separately as described below. When the thickness of the coating layer Y is within the above range, the texture becomes rubber-like.

B

This is preferable because sufficient peel strength and good smoothness can be obtained.

[0026] The coating layer Y and the method of forming the coating layer Y include a high-density impregnated into the entangled nonwoven fabric X.

B C

Before solidifying the polymer elastic bodies A and B, the polymer

B

A solution or dispersion of the polymer B and the polymer elastic body C in order, and finally solidifying all the polymer elastic bodies in the coagulating liquid, and a polymer impregnated in the entangled nonwoven fabric X After coagulating the elastic body A and the polymer elastic body B in the coagulating liquid and drying,

B

There is a method of sequentially applying a solution or dispersion of the polymer elastic body B and the polymer elastic body C, and then solidifying the applied polymer elastic body B and the polymer elastic body C in a coagulating liquid. Considering the close contact between the base layer and the coating layer Y, the former method is preferable. The adhesion between the base layer and the coating layer Y is defined as the surface of the base layer (other layers of the upper layer X).

B surface) and coating layer Y

B A state in which the surface is bonded completely and continuously without a layer or substance in between, and is distinguished from a state where the surface is partially in contact. The partial contact state means that the surface of the base layer and the coating layer are point-adhered, for example, when a gravure roll of a polymer elastic solution is applied to the surface of the base layer and the coating layer is bonded. Or a state in which the surface of the base layer and the coating layer are dry-bonded with an adhesive made of a crosslinked type polymer elastic body.

[0027] Examples of the method of solidifying the polymer elastic body include a method of immersing in a liquid containing a non-solvent of the polymer elastic body and wet-solidifying, or a method of gelling and then heating and drying. The wet coagulation method is preferred in that the porous body easily forms a porous structure and a porous structure having a uniform pore size and distribution can be obtained. In addition, additives such as a coloring agent, a coagulation regulator, an antioxidant, and a dispersant may be added to the polymer elastic body as needed. A small amount of another resin such as an elastic polymer may be added as long as the effects of the invention can be obtained.

[0028] When the entangled nonwoven fabric X is formed of ultrafine fiber-generating fibers, after solidifying the polymer elastic body, the ultrafine fiber-generating fibers are ultrafine and modified into ultrafine fiber bundles. Ultrafineness is achieved by treating with a dissolving agent or a decomposing agent to remove at least one component, or by exfoliating at the interface between the two components by mechanical or chemical treatment. In the case of the silver-finished leather of the present invention, the ultrafine fiber bundle and the polymer elastic body are substantially adhered to each other in a state. Preferably it is. If the polymer elastic body is impregnated and coagulated after the ultrafine-graining, the polymer elastic body adheres to the microfine fiber bundle and the texture tends to be hard. In the case where the ultrafine fibers are thinned before the application of the polymer elastic body, the polymer elastic body is applied after the dissolvable temporary filler such as polybutyl alcohol is applied so that the ultrafine fibers do not adhere to the polymer elastic body. Preferably, the temporary filler is subsequently removed. "A state in which the microfine fiber bundle and the polymer elastic body are not substantially bonded to each other" means that the solidified polymer elastic body around the microfine fiber bundle has the microfibers at the intersection and non-intersection of the microfiber bundle. This refers to a state in which voids exist between the ultrafine fiber bundle that does not adhere to the bundle and the solidified polymer elastic body.

[0029] After forming the coating layer Y and the coating layer Y on the surface of the base layer, the coating layer Y is formed by the following method.

B C C

By forming the finishing layer Y on the surface, it is possible to add silver having the appearance of the natural leather of the present invention.

E

Toned artificial leather is obtained. An ink composed of a coloring agent such as a pigment or a dye and a known finishing resin is applied by a gravure roll, a reverse roll, a screen, or the like, and the surface of the coating layer Y is coated.

C

To give a natural leather-like grain pattern with embossed rolls. The heating temperature of the embossing roll is preferably from 100 to 230 ° C. in order to give a natural leather-like appearance by embossing. It is preferable for it to be within the above range, since a uniform grain pattern is formed and the polymer elastic body in the base layer is not thermally deformed. The pressing pressure of the embossing roll is preferably in the range of 0.5 to 15 kgZcm ² . Within the above range, a uniform grain pattern is formed and the lower layer X

It is preferable because A can be prevented from being compressed and the texture becomes hard. The heating temperature is 120 to 190 ° C. and the pressing pressure is 1 to 6 kg / cm ² , more preferably, because the obtained artificial leather has softness, flexibility, and natural leather appearance. The thus obtained artificial leather with silver tone has a clear grain pattern of natural leather tone, a high-grade appearance and excellent softness, flexibility and fulfillment.

[0030] By performing a mechanical kneading treatment or a relaxation treatment with a liquid jet dyeing machine or the like after embossing, a natural kneading screen is formed, and the flexibility and the sense of quality of natural leather can be further improved. . If a dyeable resin is applied during gravure coloring and dyed with a dyeing machine after embossing, a transparent appearance, natural shrink, etc. can be obtained, and the flexibility is further increased. Luxury feeling is obtained. In the silver-finished artificial leather of the present invention obtained as described above, the thickness of the base layer is 0.2 to: LOmm, the thickness of the upper layer X is 0.01 to, and: the thickness of the coating layer Y is 0.01 mm or more. Is 1 ~: ίΟ / ζ πι,

Β Β

The thickness of the covering layer Υ should be 0.02 ~: L 50mm, and the thickness of the finishing layer Y should be 1 ~ 100m.

C E

preferable.

Example

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The parts and percentages in the examples are on a mass basis unless otherwise specified.

[0032] (1) Single fiber fineness

From the micrograph of the cross section of the fiber bundle, the number of ultrafine fibers constituting the fiber bundle was counted. The value obtained by dividing the total fineness of the fiber bundle by the number was defined as the single fiber fineness.

(2) Thickness of coating layer Y

B

The artificial leather was cut in the thickness direction, and the cut surface was photographed with a scanning electron microscope. Entangled Non-woven fabric X Upper end of fiber constituting X (the part closest to coating layer Y)

B B

Linear force connecting the averages Lower end of coating layer Y (the part closest to coating layer Y) Average of 10 points

C B

The distance to the line connecting is defined as the thickness of the coating layer Y.

B

(3) Porous Structure of Coating Layer Y, Upper Layer X, and Coating Layer Y

B B C

Cut the artificial leather in the thickness direction and apply the coating layer Y

B and upper layer X

B and coating layer Y

The cross section of each porous layer of C was photographed with a scanning electron microscope. Coating layer Y

B and upper layer X

Micropores in B and coating layer Y

C Check the diameters of the macropores (for example, water drop type or bottle type shape) and their dispersion state, and

B and upper layer X

B and coating layer Y

C It was determined whether the porous structure was different. In addition, from the scanning electron micrograph, the fineness of the coating layer Y and the upper layer X was determined.

B B

Pores and Coating Layers Giant pores (Y is not circular like a water drop type or bottle type)

C

In this case, the diameter (minor diameter) in the direction perpendicular to the thickness direction is measured. ) Were selected for each of the 10 points, and their average value was taken as the maximum pore diameter.

[0035] (4) Calculation of [b / (Xb + b)] / [(a / (Xa + a)]

The coating layer Y of the artificial leather with silver was sliced off. The remaining base layer was observed with an electron microscope, and the interface between the polymer elastic bodies A and B inside the base layer was confirmed. The substrate layer was sliced along the interface and separated into an upper layer and a lower layer. And each slice The mass of the piece, the upper layer (Xb + b) and the lower layer (Xa + a) were measured. Next, the sliced pieces are separately washed with a solvent for the polymer elastic body A and a polymer elastic body B (DMF in the case of polyurethane), the polymer elastic body is removed, and the mass is dried (Xb and Xa). Was measured. Then, Xb and Xa were subtracted from Xb + b and Xa + a measured in advance to obtain b and a. The value of the above equation was calculated from the obtained mass.

(0036) Peel strength

The artificial leather with silver was cut to a width of 2.5 cm, affixed to a rubber plate using a polyurethane adhesive containing a crosslinking agent, pressed, dried, and then cured at 25 ° C for 24 hours. The artificial leather and rubber plate were gripped and pulled by a tensile tester (pulling speed 100 mmZ, recording paper speed 50 mmZ), and the average peel strength was read from the recording paper. This average was divided by 2.5 and expressed in kgZcm.

Example 1

50 parts of polyethylene as a sea component and 50 parts of 6-nylon as an island component were melt-spun in the same melting system to produce a conjugate fiber with a fineness of 10 dtex. This composite fiber was drawn 3.0 times, crimped, and then cut to a fiber length of 5 lmm to obtain a stable. After the staple was opened with a card, the web was formed with a cross wrapper webber. Next, needle punching was performed to obtain an entangled nonwoven fabric XI having a basis weight of 650 g / m ² .

A 13% dimethylformamide solution of a mixture of a polyether-based polyurethane and a polyester-based polyurethane (polyurethane A solution; 100% modulus of the mixed polyurethane: 40 kg Zcm ² ) is impregnated into the entangled non-woven fabric XI, and a knife is pressed against the non-woven fabric to a thickness of 90%. % Compressed. Immediately thereafter, the N% obtained by polymerizing polyethylene propylene adipate glycol, 4,4'-diphenylmethane diisocyanate (MDI), and ethylene glycol (EG) on the surface of the entangled nonwoven fabric XI was 4.0%. A 25% dimethylformamide solution of polyester-based polyurethane (polyurethane B solution; 100% modulus of polyurethane: 70 kgZcm ² ) is applied, and the entangled non-woven fabric XI is formed by utilizing the permeability of the solution and the suction force accompanying the recovery of the compressed state force. The upper layer was impregnated. A part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric XI was rubbed with a knife so that the thickness after coagulation became 12 / zm to form a coating layer Y. To form the coating layer Y

B C

The surface of the coating layer Y is coated with polyhexacarbonate glycol and polymethylene propylene. 18% dimethylformamide solution of polycarbonate polyurethane containing n-hexanediisocyanate, MDI, and EG in a mass ratio of 5: 2: 3 containing adipate and methylenediamine (polyurethane C solution: polyurethane After applying 100% modulus: 40 kgZcm ² ), each polyurethane was coagulated in a coagulation bath of DMFZ water = 30Z70 to form each layer having a porous structure. Subsequently, after washing with water, the polyethylene was extracted and removed, and the conjugate fiber was converted into a 6-nylon ultrafine fiber bundle made of ultrafine fiber carpet having an average single fiber fineness of 0.007 decitex.

[0038] A polyurethane liquid containing a brown pigment was applied to the surface of the

C

In 5 minutes, a finished layer 5 of 5 gZm ² was formed. Then 150. Pressing pressure of 2kgZcm for 30 seconds at C

E

² embossed to give a natural leather-like grain pattern. By further rubbing with a rubbing machine, a silver-tone artificial leather with a natural appearance and a soft feel like natural leather was obtained.

The thickness of the base layer of the obtained artificial leather with silver is 1.3 mm, and the thickness of the upper layer X is 0.15 m.

B

m, XbZb was 50Z50, Xa / a «60/40, and the value of Equation 1 was 2.5. The thickness of the coating layer Y was 0.2 mm, the thickness of the coating layer Y was 8 m, and the thickness of the coating layer Y was 0.18 mm. Coating

B C

The ratio of the maximum pore size of the layer Y and the upper layer X to the maximum pore size of the coating layer Y was 1Z25.

B B C

The peel strength of silver-toned artificial leather was 3.3 kgZcm, far exceeding the required peel strength. When sports shoes were produced using the above-mentioned artificial leather with silver, it was found to have a natural leather-like elegant appearance, excellent softness, flexibility and high peel strength.

Example 2

From composite spun fiber composed of 35 parts of polyethylene (sea component) and 65 parts of 6-nylon (island component), and the number of island components is 50 islands, ultrafine fiber with a fiber length of 51 mm and a fineness of 4.0 decitex Generated fiber A was prepared. In addition, 50 parts of polyethylene (sea component) and 50 parts of 6-nainone (island component) are melt-spun in the same melting system, stretched and cut, and the fiber length is 51 mm and the fineness is 4.0 dtex. Fiber-generating fiber B was produced. After the microfine fiber-generating fiber A and the microfine fiber-generating fiber B were respectively defibrated into a card, a web Wa and a web Wb each having a basis weight of 350 g / m ² were produced using a cross wrapper @ Eva. Web Wa and Web Wb are superimposed and punched with 1 parb-1 dollar needle-1 dollar. An entangled nonwoven fabric having Zm ² and a density of 0.15 gZcm ³ was obtained. After heating this non-woven fabric at 150 ° C, the surface was smoothed with a hot roll, and the basis weight was 600 gZm ² and density. A heat-set entangled nonwoven fabric X2 having a thickness of ³⁰ gZcm ³ and a thickness of 2. Omm was obtained. Both surfaces of the entangled nonwoven fabric X2 were mainly composed of microfine fiber-generating fibers A and microfine fiber-generating fibers B, respectively, and the inside of the nonwoven fabric had a structure in which the respective microfine fiber-generating fibers were entangled.

[0040] After the polyurethane A solution used in Example 1 was impregnated into the entangled nonwoven fabric X2, a knife was pressed against the web Wa side to compress to 90% of the thickness of the nonwoven fabric. Immediately thereafter, the polyurethane B solution used in Example 1 was applied to the web Wb side, and the upper layer of the entangled nonwoven fabric X2 was used by utilizing the permeability of the polyurethane B solution and the suction force associated with the recovery of the force. (Mainly formed from web Wb). A part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric X2 was scraped with a knife to form a coating layer Y such that the thickness after solidification became 12 m. Coating

B

To form layer Y, cover layer Y

B Polyurethane C used in Example 1 on the surface

After applying the C solution, each polyurethane was coagulated in a coagulation bath of DMFZ water = 30Z70 to form each layer having a porous structure. The upper layer (web Wb side) of the obtained substrate was mainly impregnated with polyurethane B, and the lower layer (web Wa side) was mainly impregnated with polyurethane A.

After washing with water, the polyethylene of the composite fiber is extracted and removed to obtain a 6-nylon ultrafine fiber bundle (upper layer X) having a single fiber fineness of 0.0001 deciters, and a single fiber fineness of 0.07 deci.

B

This was converted into a 6-nylon ultrafine fiber bundle (lower layer X) that also produced Tex's ultrafine fiber strength.

A

Then, in the same manner as in Example 1, a silver-tone artificial leather having a natural appearance and a soft feeling like a natural leather was obtained.

The thickness of the base layer of the obtained artificial leather with silver is 1.4 mm, and the thickness of the upper layer X is 0.3 mm.

B

, XbZb was 50Z50, XaZa was 60Ζ40, and the value of Equation 1 was 2.5. The thickness of the coating layer 0 was 0.15 mm, the thickness of the coating layer Y was 7 m, and the thickness of the coating layer Y was 0.13 mm. Coating

B C

The ratio of the maximum pore diameter of the fine pore diameter of layer Y and upper layer X to the maximum pore diameter of coating layer Y is 1Z20.

B B c

For

The peel strength of artificial leather with silver tone was 2.8 kgZcm, which was much higher than the required peel strength. It was close to a natural leather with a fine crease. Above silver tone When sports shoes were manufactured using artificial leather, it was found to have a natural leather-like elegant appearance, excellent softness, flexibility and high peel strength.

Example 3

A portion of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric XI was scraped with a knife so that the thickness after solidification was 4 m, and a coating layer Y was formed in the same manner as in Example 1 except that the coating layer Y was formed.

B

An artificial leather was obtained. The obtained artificial leather with silver tone had a natural appearance of natural leather tone and soft feeling, and the thickness of the coating layer Y was 1 μm. Peel strength is 2.9kgZcm

B

And greatly exceeded the required peel strength. When the shoe was manufactured using the above-mentioned artificial leather with silver, it was found to have a natural leather-like elegant appearance, excellent softness, flexibility and high peel strength.

Comparative Example 1

All of the polyurethane B solution covering the surface of the entangled non-woven fabric XI without forming the coating layer Y

B

With a knife and cover layer Y

C and finishing layer Y

A silver-finished artificial leather was obtained in the same manner as in Example 1 except that a coating layer consisting only of E was formed. The base layer consists of a bundle of 0.007 dtex 6-nylon microfibers, polyurethane A and polyurethane B, and the upper layer X is

B

The difference between the thickness of 0.151111111, 1) 715 and & 7 & was 60740, and the value of Equation 1 was 1.

[0044] The fibers on the surface of the surface, which had an appearance similar to that of natural leather, were fixed with polyurethane, giving a hard feel. In order to improve the feeling, kneading was further performed with a kneading machine.

However, the texture was wrinkled without a sense of unity between the coating layer and the base layer. Low peel strength (2.2 kg

/ cm), not suitable for sports shoes.

[0045] Comparative Example 2

Silver coating was performed in the same manner as in Example 1 except that the coating layer Y was formed using a polyurethane B solution.

C

An artificial leather was obtained. The peeling strength of the obtained artificial leather with silver was 2.8 kgZcm or more, and the texture was soft. A natural leather-like grain pattern was not obtained, and the sense of quality was poor. When sports shoes were manufactured using the above-mentioned artificial leather with silver tone, it was satisfactory in flexibility and exfoliation strength, but lacked the luxurious appearance without natural leather-like elegant appearance.o

Comparative Example 3 The entangled non-woven fabric X2 obtained in Example 2 was impregnated with the polyurethane A solution, the polyurethane A solution covering the surface was removed with a knife, and the polyurethane C solution was applied to the surface in the same manner as in Example 2 except that the polyurethane C solution was applied. An artificial leather with silver tone was obtained. When the obtained artificial leather with silver tone was further rubbed with a kneader, it exhibited natural leather-like natural appearance and flexibility, but its peeling strength was low (1.8 kg / cm), and it was used for sports shoes. It was impossible.

Comparative Example 4

A silver layer was formed in the same manner as in Example 1 except that a part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric XI was scraped off with a knife so that the thickness after solidification became 18 m, and the coating layer Y was formed.

B

A sticky artificial leather was obtained. The obtained artificial leather with silver tone is 14 m thick.

B

Met. It had a natural rubber-like natural appearance and a rubber-like feel. The required peel strength was not obtained, and the coating layer Y and the coating layer Y were delaminated.

B C

Industrial applicability

[0048] The artificial leather with silver of the present invention has an elegant appearance of a natural leather, a soft surface, excellent flexibility, and high peel strength. The artificial leather with silver tone of the present invention has a high-quality appearance of a natural leather tone with a clear grain pattern, a soft and cohesive feeling, and excellent peeling strength. It can be widely applied to applications.

Claims

The scope of the claims

[1] An entangled nonwoven fabric X consisting of bundles of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, and a base layer comprising a polymer elastic body A and a polymer elastic body B impregnated therein. And a silver-tone artificial leather comprising a coating layer Y formed on one surface of the base layer, wherein the entangled nonwoven fabric X is a lower layer X

A and upper layer X

B, the lower layer X

A is mainly impregnated with the polymer elastic body A in a state where the polymer elastic body A is not substantially adhered to the microfine fiber bundle, and the polymer elastic body B is mainly formed in the upper layer X as the microfine fiber bundle. With virtually no adhesion

B

Impregnated;

The coating layer Y is formed of a polymer elastic body B having a thickness of 1 to 10 / ζπι formed on the upper layer X.

Β

A coating layer Υ, a coating layer 高分子 made of the elastic polymer C formed on the coating layer Υ, and

B B C

, The coating layer Υ

Finish layer formed on C Υ

付き artificial leather with silver, characterized by being made of Ε.

[2] Coating layer Υ

B and coating layer Υ

2. The artificial leather with silver tone according to claim 1, wherein C has a porous structure.

[3] The artificial leather with silver tone according to claim 2, wherein the coating layer Υ and the coating layer が have different porous structures.

B C

[4] Equation 1:

[b / (Xb + b)] / [(a / (Xa + a)] ≥l. 2 (1)

B B

A A

It is the mass of the entangled nonwoven fabric that composes)

The artificial leather with silver tone according to any one of claims 1 to 3, which satisfies.

[5] Equation 2 below:

(Where MD is the 100% modulus of the elastic polymer B, and MD is 100% modulus of the elastic polymer C.

B C

% Modulus)

The artificial leather with silver tone according to any one of claims 1 to 4, which satisfies the following.

[6] Equation 3 below:

MD -MD≥10kg / cm ² (3) (Where MD is the 100% modulus of the elastic polymer B, and MD is 100% modulus of the elastic polymer A.

B A

% Modulus)

The artificial leather with silver tone according to any one of claims 1 to 5, which satisfies the following.