JPWO2005106108A1 - Silver-like artificial leather - Google Patents

Abstract

A silver-tone artificial leather comprising a base layer and a coating layer Y formed on one surface of the base layer. The base layer is composed of an entangled nonwoven fabric X composed of a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, and a polymer elastic body A and a polymer elastic body B impregnated therein. The entangled nonwoven fabric X is composed of a lower layer XA and an upper layer XB. The lower layer XA is mainly impregnated with the polymer elastic body A in a state where it is not substantially adhered to the ultrafine fiber bundle, and the upper layer XB Is mainly impregnated in a state where the polymer elastic body B is not substantially adhered to the ultrafine fiber bundle. The coating layer Y includes a coating layer YB made of a polymer elastic body B having a thickness of 1 to 10 μm formed on the upper layer XB, and a coating layer YC made of a polymer elastic body C formed on the coating layer YB. And a finishing layer YE formed on the coating layer YC. The silver-tone artificial leather with the above structure combines a natural leather-like elegant appearance with excellent softness, flexibility and high peel strength.

Description

  The present invention also relates to a silver-like artificial leather having a natural leather-like elegant appearance and excellent softness, flexibility, and high peel strength. The silver-like artificial leather can be widely used for shoes, balls, bags and the like.

  In recent years, synthetic leather and artificial leather are widely used as substitutes for natural leather in various fields such as shoes, clothing, gloves, bags, balls, and interiors. These materials are required to have higher quality, aesthetics and comfortable feeling of use, and in particular, those having both an elegant natural leather-like appearance and flexibility, and particularly a shoe having a peel strength are strongly desired.

Many natural leather-like sheets with flexibility have been proposed. For example, a leather-like sheet produced by attaching a resin film that reproduces a natural leather-like texture to a substrate obtained by impregnating and solidifying a polyurethane resin with an entangled nonwoven fabric made of ultrafine fibers of 0.1 decitex or less has been proposed. . Such leather-like sheets have high peel strength and are suitable for sports shoes, but the surface finish layer is thick, there is no sense of unity with the substrate, and natural leather-like properties cannot be obtained. In addition, it was difficult to form a deep wrinkle pattern.
In addition, a leather-like sheet manufactured by coating a polyurethane solution on the surface of the substrate and wet-coagulating to form a foamed layer, followed by coloring and embossing has been proposed. Such leather-like sheets have a natural leather-like appearance. However, when emphasizing softness and flexibility, it is difficult to obtain sufficient peel strength because a relatively small amount of soft elastic body is filled in the substrate. It was. Further, in order to obtain a sufficient peel strength, it is necessary to fill a large amount of a relatively hard elastic body, and as a result, softness and flexibility are lost. As described above, it has been very difficult to produce a leather-like sheet having all of peel strength, flexibility, softness and natural leather-like appearance.

An entangled nonwoven fabric made of ultrafine fiber-generating fibers is impregnated with a polyurethane resin and wet-solidified, and one component is removed from the ultrafine fiber-generated fibers to obtain a substrate made of ultrafine fiber bundles of 0.1 decitex or less, A leather-like sheet obtained by subjecting a substrate to surface finishing has been proposed (for example, see Patent Document 1). However, the surface of the leather-like sheet has a natural leather-like appearance, but the flexibility and peel strength are not sufficient.
A leather-like sheet made of the same elastic resin as the elastic resin impregnated in the substrate surface layer and having a surface porous layer provided continuously with the substrate surface layer has been proposed (for example, see Patent Document 2). However, when the surface porous layer is formed using a soft resin in order to obtain a natural leather-like appearance, it is difficult to obtain a sufficient peel strength. 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. Furthermore, it is also known to form a porous coating 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 can be obtained, but softness is lowered. On the contrary, when softness is given priority, it becomes difficult to obtain a natural leather-like appearance by embossing. In addition, when a resin with good embossability is used for the surface porous layer and a resin that is difficult to be deformed by embossing is used for the high-density resin layer, the same resin is used for the surface porous layer and the high-density resin layer. Compared with the case, it was difficult to obtain sufficient embossability.

In order to improve the above problems, the present inventors have provided a leather-like sheet impregnated with a polyurethane resin that is less likely to be thermally deformed than the polyurethane resin constituting the surface porous layer on the upper part of the fibrous base layer that is in close contact with the surface porous layer. Proposed (see Patent Document 3). However, in order to have a natural leather-like appearance, it was necessary to emboss after forming a surface porous layer made of a soft polyurethane resin. For this reason, when the surface layer is made thick, a sense of unity may not be obtained as a whole.
As described above, an artificial leather with silver having excellent peel strength, soft surface, flexibility and a clear and elegant appearance similar to that of natural leather has not yet been obtained.

Japanese Patent Publication No. 63-5518 Japanese Patent Laid-Open No. 11-140779 JP 2003-105679 A

  The purpose of the present invention is a natural leather-like artificial leather that combines a natural leather-like graceful appearance with excellent softness, flexibility, and high peel strength. More specifically, it has a soft surface and high peel strength and flexibility. Another object is to provide an artificial leather with silver and a method for producing the same.

That is, the present invention comprises an entangled nonwoven fabric X composed of a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, a base layer composed of a polymer elastic body A and a polymer elastic body B impregnated therein, and There silver with finished artificial leather made of the coating layer Y which is formed on one surface of said substrate layer; entangled nonwoven X consists lower X _a and upper X _B, primarily polymer on the lower layer X _a the elastic body a and the microfine fiber bundle is impregnated in a state not substantially bonded, and not primarily as the microfine fiber bundle elastic polymer B not substantially adhere to the upper layer X _B state is impregnated with; the coating layer Y is formed in the upper layer X _B coating layer having a thickness of 1~10μm elastic polymer B formed on Y _B, the coating layer Y on _B Coating layer Y _{C made of} polymer elastic body C, and finish formed on coating layer Y _C Providing silver with finished artificial leather characterized in that it consists of the lower layer Y _E.

The present invention will be described in detail below.
The silver-finished artificial leather of the present invention was provided on the entangled nonwoven fabric X, the base layer composed of the polymer elastic body A and the polymer elastic body B impregnated therein, and one surface of the base layer. It consists of a coating layer Y. The substrate layer consists of an upper X _B mainly comprising a lower X _A and mainly the elastic polymer B containing the elastic polymer A. The coating layer Y provided on the upper layer X _B is composed of a coating layer Y _{B made of} a polymer elastic body _B , a coating layer Y _{C made of} a polymer elastic body _C, and a finishing layer Y _{E in} order from the bottom. .
The substrate layer used in the present invention has a three-dimensional structure consisting of 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 entangled nonwoven fabric X and the polymer elastic body A and polymer elastic body B contained therein. When the average single fiber fineness exceeds 0.07 dtex, the texture and the smoothness of the substrate layer are inferior, and furthermore, it becomes difficult to form a texture pattern uniformly by embossing. A 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, it can be obtained by dissolving or decomposing and removing at least one component from an ultrafine fiber-generating fiber composed of at least two kinds of polymers, or by peeling at an interface between two components by mechanical or chemical treatment. In order to reduce the single fiber fineness of the ultrafine fiber constituting the ultrafine fiber bundle to 0.07 dtex or less, it is more advantageous in the process to use the sea-island type ultrafine fiber generation type fiber than to use the laminated type ultrafine fiber generation type fiber. It is. It should be noted that the ultrafine fiber bundle and the polymer elastic body constituting the silver-tone artificial leather of the present invention need not be substantially bonded from the viewpoint of a soft texture like natural leather. In order to make it substantially not bonded, it is necessary to form an ultrafine fiber bundle from the ultrafine fiber generating fiber, and it is preferable to form the sea island type ultrafine fiber generating fiber.

Examples of the polymer constituting the ultrafine fiber in the ultrafine fiber generation type fiber include melt spinning such as 6-nylon and 66-nylon, melt-spinnable polyamides, polyethylene terephthalate, polybutylene terephthalate, and cationic dyeable modified polyethylene terephthalate. Examples thereof include at least one polymer selected from possible polyesters.
As the polymer dissolved or decomposed and removed, the polymer constituting the ultrafine fiber is different in solubility in a solvent or decomposable by a decomposing agent, has low compatibility with the polymer constituting the ultrafine fiber, and is under the spinning conditions. The polymer has a lower melt viscosity or a lower surface tension than the polymer constituting the ultrafine fiber. For example, at least one polymer selected from polymers such as polyethylene, polystyrene, polyethylene-propylene copolymer, and modified polyester is used.

The ultrafine fiber generating fiber is defibrated with a card and formed into a web through a webber. The obtained web is laminated so as to have a desired weight and thickness, and then an entangled nonwoven fabric X is obtained by performing an entanglement process by a known method such as needle punching or high-speed water flow. If necessary, a woven or knitted fabric made of a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less can be laminated on the web. In the entangled nonwoven fabric X, the surface smoothening by press treatment or the like before the impregnation of the polymer elastic body improves the surface smoothness of the resulting artificial leather with silver and the point that the texture pattern is uniformly formed. preferable. The thickness of the obtained entangled nonwoven fabric X or the entangled nonwoven fabric X subjected to the press treatment is selected according to the use of the silver-tone artificial leather and is not particularly limited. When the entangled nonwoven fabric X is used as a single layer, the thickness is preferably about 0.2 to 10 mm, and more preferably about 0.4 to 5 mm. Density is preferably ^{0.15~0.60g / cm 3, 0.20~0.40g / cm} 3 is 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 with silver Since artificial leather is obtained, it is preferable.

Next, the entangled nonwoven fabric X is impregnated with a solution or dispersion of the polymer elastic body A and the polymer elastic body B, and then the coating layer Y is formed. The polymer elastic bodies A, B, and C used in the present invention may be those conventionally used in the production of artificial leather, and known polymer elastic bodies can be used. Among them, polyurethane is preferably used in terms of obtaining a natural leather-like texture and physical properties.
Preferred examples of the polymer elastic bodies A to C for impregnating the entangled nonwoven fabric X and forming the multilayer Y are one or more polymer diols such as polyester-based diol, polyether-based diol, and polyester-ether-based diol. An organic polyisocyanate, preferably one or more of an aliphatic, aromatic or alicyclic organic diisocyanate; and a chain extender having two active hydrogen atoms such as a low molecular diol, a low molecular diamine, or hydrazine And polyurethane produced from the above.

  Among them, a polyurethane having a mass percentage of isocyanate nitrogen atoms (hereinafter referred to as N%) in an organic polyisocyanate unit present in the polyurethane to 2.5% to 5% based on the total mass of the polyurethane or the polyurethane as a main component. Mixtures are preferred. When N% is within the above range, the physical properties such as the wear resistance and scratch resistance of the coating layer Y and the base layer are good, the bending wrinkles become rough, the texture becomes hard, and the artificial leather becomes cheaper. This is preferable because it can be prevented, and the artificial leather has good physical properties such as resistance to bending fatigue.

As the polymer elastic body C used for the coating layer Y _C of the present invention, it is preferable to use polyurethane capable of forming a natural leather-like texture pattern by embossing. Examples thereof include a polyurethane having a hard segment mainly composed of a polymer glycol having a hydroxyl group at both ends and a molecular weight of 500 to 5000, 4,4'-diphenylmethane diisocyanate, and a lower alkylene glycol having 2 to 6 carbon atoms, or Examples thereof include a polymer glycol having a hydroxyl group at both ends and a molecular weight of 500 to 5000, an aliphatic or alicyclic diisocyanate, and a polyurethane having a hard segment mainly composed of an organic diamine or an organic acid dihydrazide. However, as long as softness, flexibility, durability, workability, porous film forming property, and the like are sufficient, a copolymer or a mixture thereof may be used.

  Examples of polymer glycols having hydroxyl groups at both ends and having a molecular weight of 500 to 5000 include polyester glycols such as polyethylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, and polycaprolactone glycol; polycarbonates such as polyhexamethylene carbonate glycol Glycols; polyether-based glycols such as polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol; and mixtures thereof are used. Particularly preferred are polyester glycols, polycarbonate glycols, mixed glycols of polyester glycols and polycarbonate glycols, mixed glycols of polyester glycols, polycarbonate glycols and polyether glycols.

  Examples of the aliphatic diisocyanate include tetramethylene diisocyanate and hexamethylene diisocyanate, and examples of the alicyclic diisocyanate include cyclohexane diisocyanate and 4,4′-dicyclohexylmethane diisocyanate. Examples of the organic diamine include p-phenylenediamine, metaphenylenediamine, 4,4′-diaminediphenylmethane, ethylenediamine, propylenediamine, diethanolamine, 4,4′-diaminodicyclohexylmethane, isophoronediamine, and the like. Examples include adipic acid dihydrazide, sebacic acid dihydrazide, terephthalic acid dihydrazide, and isophthalic acid dihydrazide. Examples of the lower alkylene glycol having 2 to 6 carbon atoms include ethylene glycol, butanediol, hexanediol, diethylene glycol, dipropylene glycol and the like. Among these, ethylene glycol is preferable in that a uniform texture pattern can be formed by embossing.

The thickness of the coating layer Y _C is preferably 0.02 to 1.50 mm, and more preferably 0.05 to 1.00 mm. Within the above range, a smooth surface can be obtained, a uniform texture pattern can be formed by embossing, and a rubber-like texture can be avoided, which is preferable.

Base layer, in particular, that the elastic polymer for forming the coating layer Y _B and the elastic polymer impregnated into the upper X _B of the entangled nonwoven fabric X in contact with the coating layer Y is the same, that is, the elastic polymer B is required. When the polymer elastic body forming the upper X _B and the coating layer Y _B are different, decrease adhesion between the base layer and the covering layer Y, it tends to peel.
The 100% modulus of the polymer elastic body B is preferably 20 to 100 kg / cm ² , more preferably 30 to 70 kg / cm ² . Further, the polymer elastic body B has a 100% modulus higher than that of the polymer elastic body C constituting the coating layer Y _C by 30 kg / cm ² or more, can form a dense porous structure, and is difficult to be thermally deformed. preferable. The 100% modulus of the polymer elastic body B is more preferably 30 to 60 kg / cm ² higher than that of the polymer elastic body C.

This prevents the elastic layer _B constituting the coating layer Y _B , especially the upper layer X _B from being thermally deformed and fixed when the coating layer Y _C is fixed in a state of being thermally deformed by embossing. This is to maintain the ultrafine fiber bundle while maintaining the properties and increase the peel strength. For this purpose, it is preferable that the polymer elastic body B has 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. When the cross sections in the thickness direction of the coating layer Y _B and the coating layer Y _C are observed, the maximum diameter of the micropores in the coating layer Y _B and the upper layer X _B is a large pore (water droplet type or bottle type in the coating layer Y _C ). The maximum diameter of the hole)) is preferably 1/2 or less, more preferably 1/100 to 1/2, and even more preferably 1/70 to 1/5. Within the above range, the porous structure of the coating layer Y _B and the upper layer X _B is not crushed during embossing, and a soft and flexible texture can be obtained. When the polymer elastic body B does not form a porous structure, the feeling of unity between the coating layer Y and the base layer by embossing cannot be obtained, and the texture tends to be inferior. The pore diameter ratio can be set within the above range by appropriately adjusting the viscosity, concentration, and type of the polymer elastic body as is known.

The polymer elastic body B is not particularly limited as long as the above physical properties are satisfied, but polyurethane is particularly preferably used from the viewpoint of the texture and physical properties of the resulting silver-tone artificial leather. The kind of polyurethane is not particularly limited, and ester, ether, carbonate, or a copolymer thereof, or a mixture thereof can be used. It is more preferable that the soft segment is mainly composed of ether and the hard segment is mainly composed of aromatic diisocyanate and aromatic diamine because it is difficult to be thermally deformed.
For example, a soft segment containing polyether diol having an average molecular weight of 500 to 3000, preferably polytetramethylene glycol of 50% or more, more preferably 70% or more, 4,4'-diphenylmethane diisocyanate, p-phenylenediamine, metaphenylenediamine, A polyurethane made of an aromatic diisocyanate selected from 4,4'-diaminediphenylmethane and the like is used.
If necessary, this polyurethane may be mixed with a polyurethane different from the above, or may be a copolymer polyurethane comprising an ether polymer diol, a polycarbonate polymer diol, a polyester polymer diol, or the like.

Impregnation of the upper X _B of the elastic polymer B is the fiber weight Xb of the upper X _B, preferably 0.3 to 3.0 times the solid content, more preferably 0.8 to 2.0 Is double. Within the above range, a sufficient binder effect and necessary peel strength can be obtained without impairing the softness of the substrate layer.

The lower layer X _A of the entangled nonwoven fabric X is impregnated with the polymer elastic body A. Although there is no restriction | limiting in particular as the polymeric elastic body A, A polyurethane is preferably used at the point which combines the soft texture and physical property of the natural leather-like artificial leather with silver. The polymer elastic body B constituting the upper layer of the substrate is affected by heat through the coating layer Y _C during embossing, so it is necessary that it is difficult to be thermally deformed. However base layer (layer elastic polymer A to the lower X _A is impregnated), the effect of heat at the time of embossing than the base layer (a layer in the upper layer X _B is the elastic polymer B is impregnated) It is hard to receive. Therefore, in order to impart softness and flexibility to the base layer, the polymer elastic body A may be more easily thermally deformed than the polymer elastic body B, and it is preferable to use soft polyurethane. 100% modulus of the elastic polymer A is preferably 10 kg / cm ² or more lower than that of the elastic polymer B, it is more preferable 10~60kg / cm ² low.
The polymer elastic body A places importance on softness and impregnates the amount in a range that does not impair the overall texture balance. For example, as a solid content relative to the fiber weight Xa of the underlying X _A, preferably 0.1 to 1.5 times, more preferably impregnating 0.3 to 1.0 times. When the impregnation amount is within the above range, it is preferable that a rubber-like texture is avoided, the overall texture balance is good, and a natural leather-like high-quality texture with a sense of fulfillment is obtained.

Elastic polymer impregnated into the elastic polymer B and a lower X _A to impregnate the upper layer X _B A preferred since a graceful appearance of natural leather-like can be uniformly imparted by embossing the only impregnated in layers can be.
Layer of the upper X _B to impregnate the elastic polymer B, depending on the thickness of the substrate layer, preferably 0.01Mm～1.0Mm, more preferably 0.05Mm～0.6Mm. Within the above range, a sufficient peel strength can be obtained without impairing the softness by embossing, and the rubber elasticity does not become stronger than necessary, and a natural leather-like low resilience texture can be obtained. .

Furthermore, the silver-tone artificial leather of the present invention has the following formula 1:
[B / (Xb + b)] / [(a / (Xa + a))] ≧ 1.2 (1)
(Wherein, b is the mass of the elastic polymer B impregnated into the upper X _B, Xb is the mass of the entangled nonwoven fabric constituting the upper layer X _B, a is the elastic polymer A impregnated into the lower layer X _A enough mass, Xa is to satisfy the mass) of the entangled nonwoven fabric constituting the lower layer X _a, resulting in the desired peel strength, also sufficiently withstand deformation during embossing, even when embossed softness It is preferable because it can be maintained. The upper limit of Formula 1 is more preferable in terms of the balance of the texture of the artificial leather with silver that can be obtained as 5.0.

The impregnation of the polymer elastic body into the substrate layer may be performed by a known processing method, and is not particularly limited. For example, a predetermined amount of the polymer elastic body B solution or dispersion is applied to the upper surface of the entangled nonwoven fabric X and allowed to permeate naturally or by rubbing with a roll or a knife. There is a method in which the solution or dispersion of the molecular elastic body A is permeated so as to be rubbed with a roll or a knife, and the excess is scraped off with a knife or the like.
Alternatively, once the entire entangled nonwoven fabric X is impregnated 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 applied. In addition, a method in which the entangled nonwoven fabric X is infiltrated using the recovery force and then the excess portion protruding from the entangled nonwoven fabric X is scraped with a knife can be used. Incidentally, after impregnating coagulated elastic polymer B in the upper X _B, the elastic polymer B on the surface of the entangled nonwoven fabric X, so that the thickness after embossing is 1~10μm layer The scraping coating layer Y _B and the substrate layer can be simultaneously produced with a knife or the like. The coating layer Y _B and the substrate layer may be manufactured separately as described below. It is preferable for the thickness of the coating layer Y _B to be in the above-mentioned range since the texture is prevented from being rubber-like and sufficient peel strength and good smoothness can be obtained.

As a method for forming the coating layer Y _B and the coating layer Y _C , before the polymer elastic body A and the polymer elastic body B impregnated in the entangled nonwoven fabric X are solidified, the polymer is continuously formed on the upper layer X _B. A method of sequentially applying a solution or dispersion of elastic body B and polymer elastic body C, and finally coagulating all the polymer elastic bodies in a coagulation liquid, and a polymer elastic body impregnated with entangled nonwoven fabric X coagulated a and the elastic polymer B in coagulation liquid, dried, sequentially applying a solution or dispersion of the elastic polymer B and the elastic polymer C on the upper X _B, then applied There is a method of coagulating the polymer elastic body B and the polymer elastic body C in a coagulating liquid. Considering the adhesion between the base layer and the coating layer Y, the former method is preferable. The adhesion between the substrate layer and the coating layer Y means that the surface of the substrate layer (the surface of the upper layer X _B ) and the surface of the coating layer Y _B are bonded together entirely and continuously without any other layers or substances. It is distinguished from the state of being in partial contact. The partially contacted state means that the surface of the base layer and the coating layer are point-bonded as in the case where a gravure roll 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 cross-linked polymer elastic body.

  The polymer elastic body can be solidified by dipping in a liquid containing a non-solvent of the polymer elastic body to wet-solidify, or gelled and then heat-dried. The wet coagulation method is preferable in that a porous structure is formed on the surface and a porous structure having a uniform pore size and distribution is obtained. Moreover, you may mix | blend additives, such as a coloring agent, a coagulation regulator, antioxidant, and a dispersing agent, with a polymeric elastic body as needed. As long as the effects of the invention are obtained, a small amount of a resin such as another polymer elastic body may be added.

  When the entangled nonwoven fabric X is formed of ultrafine fiber generating fibers, after coagulating the polymer elastic body, the ultrafine fiber generating fibers are extremely thinned and modified into ultrafine fiber bundles. Ultrathinning is carried out by removing at least one component by treatment with a solubilizer or decomposition agent, or by peeling at the interface of two components by mechanical or chemical treatment. In the silver-tone artificial leather of the present invention, it is preferable that the ultrafine fiber bundle and the polymer elastic body are not substantially bonded. When the polymer elastic body is impregnated and solidified after being ultrafine, the polymer elastic body adheres to the ultrafine fiber bundle and the texture tends to become hard. Therefore, it is preferable to make the polymer elastic body fine after applying the polymer elastic body. When ultrafine before applying the polymer elastic body, after applying a temporary filler that can be dissolved and removed such as polyvinyl alcohol so that the ultrafine fiber and the polymer elastic body do not adhere, apply the polymer elastic body, It is preferable to remove the temporary filler. “The state in which the ultrafine fiber bundle and the polymer elastic body are not substantially bonded” means that the solidified polymer elastic body around the ultrafine fiber bundle has an ultrafine fiber bundle at the intersection and non-intersection of the ultrafine fiber bundle. A state in which voids exist between the ultrafine fiber bundle and the solidified polymer elastic body without adhering to the fiber.

After forming the coating layer Y _B and the coating layer Y _C on the surface of the base layer, the finish layer Y _E is formed on the coating layer Y _C by the following method, whereby the silver having the natural leather-like appearance of the present invention A tart artificial leather is obtained. Pigments, known a colorant dye such as finishing ink gravure roll comprising a resin, is coated with a reverse roll method such as a screen to color the coating layer Y _C surface, the natural leather-like due embossing roll processing Gives a wrinkle pattern. In order to give a natural leather-like appearance by embossing, the heating temperature of the embossing roll is preferably 100 to 230 ° C. Within the above range, a uniform texture pattern is formed, and the polymer elastic body in the base layer is not thermally deformed, which is preferable. Pressing pressure of the emboss roll is preferably in the range of 0.5~15kg / cm ^2. Within the above range, uniform grain patterns are formed, also, since the lower X _A can be prevented from feeling is compressed becomes harder preferred. Since the obtained artificial leather combines softness, flexibility and natural leather-like appearance, the heating temperature is 120 to 190 ° C., and the press pressure is 1 to 6 kg / cm ² , but more preferable. The silver-tone artificial leather thus obtained has a natural leather-like clear wrinkle pattern, a high-grade appearance and excellent softness, flexibility, and fulfillment.

After embossing, a mechanical sag treatment or a relaxation process using a liquid-type dyeing machine or the like allows natural stagnation wrinkles to enter and further improve the softness and natural leather-like luxury. Also, by applying a resin that can be dyed during gravure coloring and dyeing with a dyeing machine after embossing, a transparent appearance, natural shrink, etc. can be obtained, and flexibility is also increased, so a higher luxury feeling can get.
In the silver-coated artificial leather of the present invention obtained as described above, the base layer has a thickness of 0.2 to 10 mm, the upper layer X _{B has} a thickness of 0.01 to 1.0 mm, and the covering layer Y _B has It is preferable that the thickness is 1 to 10 μm, the thickness of the coating layer Y _C is 0.02 to 1.50 mm, and the thickness of the finishing layer Y _E is 1 to 100 μm.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, unless otherwise indicated, the part and% in an Example are mass references | standards.

(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. A value obtained by dividing the total fineness of the fiber bundle by the number was defined as the single fiber fineness.

(2) was cut in the thickness the thickness direction of artificial leather of the coating layer Y _B, were taken cut surface under a scanning electron microscope. Upper end lower end portion (portion closest to the coating layer Y _B of the average of (closest to the cover layer Y _B) 10 points from the line connecting the coating layer Y _C of the fibers constituting the upper layer X _B of the entangled nonwoven fabric X ) The distance to the line connecting the average of 10 points was the thickness of the coating layer Y _B.

(3) Porous structure of covering layer Y _B and upper layer X _B and covering layer Y _C The artificial leather is cut in the thickness direction, and each of the porous layers of covering layer Y _B, upper layer X _B and covering layer Y _C The cross section was photographed with a scanning electron microscope. Coating layer Y _B and the upper X microporous and the coating layer Y _C of macropores in _B (e.g., water-or liquor bottle shape) Check the diameter and their dispersion state of the coating layer Y _B and the upper X _It was determined whether or not the porous structures of _B and coating layer Y _C were different. Also, from scanning electron micrographs, the fine holes in the coating layer Y _B and the upper layer X _B and the large holes in the coating layer Y _C (in the case of non-circular holes such as a water drop type or a bottle type) are perpendicular to the thickness direction. The diameter (minor axis) in the direction is measured.) 10 points were selected for each and the average value thereof was defined as the maximum pore size.

(4) Calculation of [b / (Xb + b)] / [(a / (Xa + a)] The covering layer Y of the toned artificial leather with silver was sliced and removed, and the remaining base layer was observed with an electron microscope. The interface between the polymer elastic body A and the polymer elastic body B was confirmed, and the base layer was sliced along the interface and separated into an upper layer and a lower layer, and the mass of each slice, the upper layer (Xb + b), and the lower layer (Xa + a) was measured, and then the slice pieces were washed separately with a solvent for polymer elastic body A and polymer elastic body B (DMF in the case of polyurethane), the polymer elastic body was removed, and dried, Mass (Xb and Xa) was measured, and Xb and Xa were subtracted from Xb + b and Xa + a measured in advance to obtain b and a. The value of the above formula was calculated from the obtained mass.

(5) Peel strength The artificial leather with silver is cut to a width of 2.5 cm, attached to a rubber plate with a polyurethane adhesive containing a crosslinking agent, pressed, dried, and cured at 25 ° C. for 24 hours. . The artificial leather and rubber plate were gripped and pulled by a tensile tester (tensile speed 100 mm / min, recording paper speed 50 mm / min), and the average peel strength was read from the recording paper. This average value was divided by 2.5 and displayed in kg / cm.

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 melt system to produce a composite fiber having a fineness of 10 dtex. The composite fiber was stretched 3.0 times to give crimps, and then cut into a fiber length of 51 mm to obtain a staple. After the staples were defibrated with cards, they were made into a web with a cross wrapper webber. Next, needle punching was performed to obtain an intertwined nonwoven fabric X1 having a basis weight of 650 g / m ² .
A 13% dimethylformamide solution (polyurethane A solution; 100% modulus of mixed polyurethane: 40 kg / cm ² ) of a mixture of polyether polyurethane and polyester polyurethane is impregnated into the entangled nonwoven fabric X1, and then the knife is pressed to adjust the thickness of the nonwoven fabric. Compressed to 90%. Immediately thereafter, 25% of the polyester polyurethane having an N% of 4.0 obtained by polymerizing polyethylene propylene adipate glycol, 4,4'-diphenylmethane diisocyanate (MDI), and ethylene glycol (EG) on the surface of the entangled nonwoven fabric X1. A dimethylformamide solution (polyurethane B solution; 100% modulus of polyurethane: 70 kg / cm ² ) is applied, and the upper layer of the entangled nonwoven fabric X1 is impregnated by using the permeability of the solution and the suction force accompanying recovery from the compressed state. It was. A part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric X1 was scraped off with a knife so that the thickness after solidification was 12 μm, and the coating layer Y _B was formed. In order to form the coating layer Y _C , the surface of the coating layer Y _B includes polyhexacarbonate glycol, polymethylenepropylene adipate, and methylenediamine in a mass ratio of 5: 2: 3, and includes n-hexane diisocyanate, MDI, EG After applying 18% dimethylformamide solution (polyurethane C solution: 100% modulus of polyurethane: 40 kg / cm ² ) of polycarbonate polyurethane copolymerized with polyurethane, each polyurethane was placed in a coagulation bath of DMF / water = 30/70. Solidified to form each layer having a porous structure. Subsequently, after washing with water, polyethylene was extracted and removed, and the composite fiber was converted into a 6-nylon ultrafine fiber bundle made of ultrafine fibers having an average single fiber fineness of 0.007 dtex.

A polyurethane liquid containing a brown pigment was applied to the surface of the coating layer Y _C with a gravure roll to form a finishing layer Y _E having a solid content of 5 g / m ² . Subsequently, embossing was performed at 150 ° C. for 30 seconds with a press pressure of 2 kg / cm ² to give a natural leather-like texture pattern. Furthermore, by squeezing with a kneading machine, a natural leather-like artificial leather with a natural appearance and soft texture was obtained.
The resulting thickness of the substrate layer of silver with finished artificial leather 1.3 mm, the upper X _B is the thickness 0.15 mm, Xb / b is 50/50, Xa / a is 60/40, the value of formula 1 2.5. The thickness of the coating layer Y was 0.2 mm, the thickness of the coating layer Y _B was 8 μm, and the thickness of the coating layer Y _C was 0.18 mm. The ratio of the maximum pore diameter of the coating layer Y _B and the upper layer X _{B to} the maximum pore diameter of the coating layer Y _C was 1/25.
Moreover, the peel strength of the artificial leather with silver was 3.3 kg / cm, significantly exceeding the required peel strength. When a sports shoe was produced using the above-mentioned artificial leather with silver, it had a natural leather-like elegant appearance, excellent softness, flexibility and high peel strength.

Example 2
An ultra-fine fiber generation type with a fiber length of 51 mm and a fineness of 4.0 dtex from a composite spun fiber consisting of 35 parts of polyethylene (sea component) and 65 parts of nylon (island component) and 50 islands. Fiber A was produced. Also, 50 parts of polyethylene (sea component) and 50 parts of 6-nylon (island component) are melt-spun in the same melt system, drawn and cut to generate ultrafine fibers with a fiber length of 51 mm and a fineness of 4.0 dtex. Mold fiber B was produced. After the ultrafine fiber generating fiber A and the ultrafine fiber generating fiber B were defibrillated, a web Wa and a web Wb each having a basis weight of 350 g / m ² were produced with a cross wrapper webber. The web Wa and the web Wb were overlapped and needle punched using a 1 barb needle to obtain an entangled nonwoven fabric having a basis weight of 650 g / m ² and a density of 0.15 g / cm ³ . After heating this nonwoven fabric at 150 ° C., the surface was smoothed with a hot roll to obtain a heat-fixed entangled nonwoven fabric X2 having a basis weight of 600 g / m ² , a density of 0.30 g / cm ³ and a thickness of 2.0 mm. Both surfaces of the entangled nonwoven fabric X2 are mainly composed of the ultrafine fiber generating fiber A and the ultrafine fiber generated fiber B, respectively, and the inside of the nonwoven fabric has a structure in which the respective ultrafine fiber generated fibers are entangled.

After impregnating the entangled nonwoven fabric X2 with the polyurethane A solution used in Example 1, the knife was pressed against the web Wa side and compressed to 90% of the nonwoven fabric thickness. Immediately thereafter, the polyurethane B solution used in Example 1 was applied to the web Wb side, and the upper layer portion (mainly the web) of the entangled nonwoven fabric X2 by utilizing the permeability of the polyurethane B solution and the suction force accompanying recovery from the compressed state. Formed from Wb). Part of the polyurethane B solution layer covering the surface of the entangled nonwoven fabric X2 was scraped off with a knife so that the thickness after solidification was 12 μm, and the coating layer Y _B was formed. In order to form the coating layer Y _C , the polyurethane C solution used in Example 1 was applied to the surface of the coating layer Y _B , and then each polyurethane was coagulated in a coagulation bath of DMF / water = 30/70. Each layer having a porous structure was formed. The upper layer portion (web Wb side) of the obtained substrate was mainly impregnated with polyurethane B, and the lower layer side (web Wa side) was mainly impregnated with polyurethane A.
After washing with water, polyethylene is extracted and removed from the composite fiber, and a 6-nylon ultrafine fiber bundle (upper layer X _B ) made of ultrafine fibers having a single fiber fineness of 0.0001 dtex and an ultrafine fiber having a single fiber fineness of 0.07 dtex 6-nylon ultrafine fiber bundle (lower layer X _A ) was converted.

Next, in the same manner as in Example 1, a natural leather-like artificial leather having a natural leather-like natural appearance and a soft texture was obtained.
The thickness of the base layer of the obtained artificial leather with silver is 1.4 mm, the thickness of the upper layer X _B is 0.3 mm, Xb / b is 50/50, Xa / a is 60/40, and the value of Equation 1 is 2.5. The thickness of the coating layer Y was 0.15 mm, the thickness of the coating layer Y _B was 7 μm, and the thickness of the coating layer Y _C was 0.13 mm. The ratio of the maximum pore diameter of the fine pore diameter of the coating layer Y _B and the upper layer X _B to the maximum pore diameter of the coating layer Y _C was 1/20.
Further, the peel strength of the silver-finished artificial leather was 2.8 kg / cm, significantly exceeding the required peel strength. The creases were fine and close to natural leather. When a sports shoe was produced using the above-mentioned artificial leather with silver, it had a natural leather-like elegant appearance, excellent softness, flexibility and high peel strength.

Example 3
So that the thickness after solidification is 4 [mu] m, with silver in the same manner as in Example 1 except that a portion of the polyurethane B solution layer to form a scraper coating layer Y _B with a knife to cover the surface of the entangled nonwoven fabric X1 An artificial leather was obtained. The obtained silver-tone artificial leather had a natural appearance and soft texture of natural leather, and the thickness of the coating layer Y _B was 1 μm. The peel strength was 2.9 kg / cm, significantly exceeding the required peel strength. When a sports shoe was produced using the above-mentioned artificial leather with silver, it had 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 coating layer Y _B entangled so as not to form a nonwoven fabric X1 scraped with a knife, except for forming a coating layer consisting only of coating layer Y _C and finishing layer Y _E from Example 1 A silver-tone artificial leather was obtained in the same manner. The base layer consists of a bundle of 0.007 dtex 6-nylon ultrafine fibers, polyurethane A and polyurethane B, and the upper layer X _B has a thickness of 0.15 mm, and Xb / b and Xa / a are both 60/40. Yes, the value of Equation 1 was 1.

  Moreover, although the external appearance was a natural leather tone, the fiber of the surface part was fixed with the polyurethane, and it was hard texture. In order to improve the feeling, the squeezing process was further carried out with a squeezing machine. However, wrinkles were formed and the feeling of integration between the coating layer and the base layer was obtained. The peel strength was low (2.2 kg / cm), and it was not suitable for sports shoes.

Comparative Example 2
Except that the coating layer Y _C was formed using a polyurethane B solution, a silver-tone artificial leather was obtained in the same manner as in Example 1. The peel strength of the obtained artificial leather with silver was 2.8 kg / cm or more, and the texture was soft, but the textured pattern of natural leather was not obtained and the sense of quality was poor. When a sports shoe was produced using the above-mentioned artificial leather with silver, the flexibility and peel strength were sufficient, but there was no elegant appearance of natural leather and the quality was poor.

Comparative Example 3
The silver entangled nonwoven fabric X2 obtained in Example 2 was impregnated with polyurethane A solution, the polyurethane A solution covering the surface was removed using a knife, and the polyurethane C solution was applied to the surface. A tart artificial leather was obtained. When the obtained artificial leather with silver is further rubbed with a kneading machine, it shows a natural appearance and flexibility of natural leather, but the peel strength is low (1.8 kg / cm) and it cannot be used for sports shoes. It was a thing.

Comparative Example 4
So that the thickness after solidification is 18 [mu] m, with silver in the same manner as in Example 1 except that a portion of the polyurethane B solution layer to form a scraper coating layer Y _B with a knife to cover the surface of the entangled nonwoven fabric X1 An artificial leather was obtained. The thickness of the coating layer Y _B of the obtained silver-tone artificial leather was 14 μm. A natural leather-like natural appearance was obtained, but it had a rubber-like texture. The required peel strength was not obtained, and the coating layer Y _B and the coating layer Y _C were delaminated.

The silver-like artificial leather of the present invention has a natural leather-like elegant appearance, a soft surface, excellent flexibility, and high peel strength. The silver-like artificial leather of the present invention has a natural leather-like high-grade appearance with a clear texture, a soft and unity feel, and excellent peel strength, such as sports shoes, balls and bags. Widely applicable to applications.

Claims (6)

An entangled nonwoven fabric X composed of a bundle of ultrafine fibers having an average single fiber fineness of 0.07 dtex or less, a base layer composed of a polymer elastic body A and a polymer elastic body B impregnated therein, and the base layer It is an artificial leather with silver that consists of a coating layer Y formed on one side,
The entangled nonwoven fabric X comprises a lower layer X _A and an upper layer X _B , and the lower layer X _A is mainly impregnated with the polymer elastic body A in a state in which the polymer elastic body A is not substantially adhered to the ultrafine fiber bundle, and the upper layer X _B are mainly impregnated in a state where the elastic polymer B is not the microfine fiber bundles are substantially bonded;
The coating layer Y is composed of a coating layer Y _{B made} of a polymer elastic body B having a thickness of 1 to 10 μm formed on the upper layer X _B and a polymer elastic body C formed on the coating layer Y _B. coating layer Y _C, and silver with finished artificial leather characterized in that it consists of the finishing layer Y _E formed on the coating layer Y _C. Coating layer Y _B and the coating layer Y _C silver with finished artificial leather according to claim 1, which is a porous structure. Coating layer Y _B and the coating layer Y _C of porous silver with finished artificial leather structures according to different claims 2. The following formula 1:
[B / (Xb + b)] / [(a / (Xa + a)] ≧ 1.2 (1)
(Wherein, b is the mass of the elastic polymer B impregnated into the upper X _B, Xb is the mass of the entangled nonwoven fabric constituting the upper layer X _B, a is the elastic polymer A impregnated into the lower layer X _A mass, Xa is the mass of the entangled nonwoven fabric constituting the lower layer X _a)
The artificial leather with a silver tone according to any one of claims 1 to 3, which is satisfied. Following formula 2:
MD _B -MD _C ≧ 30 kg / cm ² (2)
(Wherein, MD _B 100% modulus of the elastic polymer B, the MD _C 100% modulus of the elastic polymer C)
The artificial leather with a silver tone according to any one of claims 1 to 4, which satisfies the following conditions. Formula 3 below:
MD _B -MD _A ≧ 10 kg / cm ² (3)
(Wherein, MD _B is 100% modulus, MD _A elastic polymer B is 100% modulus of the elastic polymer A)
The artificial leather with silver tone according to any one of claims 1 to 5, which satisfies the following conditions.