JPS6075683A - Water-repellent and oil-repellent artificial leather having highly entangled layer - Google Patents

Abstract

PURPOSE:To provide an artificial leather having excellent mechanical strength, surface strength, gas permeability, and water and oil repellency, by applying a fluorine and/or silicone compound to the surface of a highly entangled layer composed of densely entangled ultrafine fibers constituting at least one surface of the leather. CONSTITUTION:At least one surface of the objective artificial leather is composed of a highly entangled layer composed mainly of densely entangled fiber structural materials consisting of ultrafine fibers and/or fiber bundles having a fineness of <=0.2 denier, preferably <0.005 denier to attain the distance between the entangled points of the fiber of <=200mu, especially <=100mu, and is coated with a fluorine-containing polymer and/or a silicone resin such as dimethyl polysiloxane, etc. An artificial leather having a silver layer can be manufactured by filling the void of the fiber structural materials of the highly entangled layer with a polyurethane resin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel artificial leather having a superentangled layer in which ultrafine fibers H and/or bundles thereof are densely entangled, and which has excellent water and oil repellency.

Conventionally, artificial leather based on nonwoven fabric is well known. Since such artificial leather is made of nonwoven fabric processed with an elastic polymer material such as polyurethane resin, it is characterized by being easy to care for, waterproof, and easy to handle. However, on the other hand, polymeric substances such as polyurethane not only make the texture and touch of two-layered skins rubber-like and reduce sensory characteristics, but also reduce air permeability and moisture permeability, making them difficult to function as anti-forming materials. The major drawback was that it caused damage. In an attempt to prevent such drawbacks, the content of polymeric substances was lowered, but properties such as mechanical strength and surface wear deteriorated, making it impractical. Furthermore, with artificial leather that lacks polymeric substances, even if it has high moisture permeability and air permeability, even if it is water- and oil-repellent, the effect is small and water stains may occur. Even in this aspect, it could not be put to practical use. That is, until now, it has been impossible to obtain artificial leather using nonwoven fabric that satisfies all of the following: appearance quality, texture, mechanical strength, surface strength, gas permeability, and waterproof and oil-proof properties.

The object of the present invention is to provide a new water- and oil-repellent artificial leather that has all of these properties.

In order to achieve this object, the present invention has the configuration as described in the claims.

That is, the present invention focuses on the fact that when ultrafine fibers are intertwined extremely densely, water repellency and oil repellency are enhanced, and properties such as air permeability and moisture permeability can be maintained. The water-repellent and oil-repellent artificial leather of the present invention has a distance between fiber entanglement points of ultra-fine m fibers of 2
Fluorine-based, silicon-based, or both compounds are attached to the superentangled layer, which consists of extremely dense entanglements of 00μ or less, so it has the characteristics of extremely high water and oil repellency, and is different from conventional Polyurethane membrane is laminated J: Compared to eel artificial leather, f! It has been discovered that artificial leather has excellent moisture permeability and air permeability, as well as excellent texture and feel, and because of the presence of a superentangled layer in the roughness, it also has excellent mechanical strength and surface strength.

The NJA fiber structure in the superentangled layer of the artificial leather of the present invention requires that ultra-m fibers and/or bundles thereof are densely intertwined with each other. In other words, the fiber entanglement density is high. Although such sheets have high gas permeability, they have low permeability to liquids such as water, which makes them water repellent and I! It is thought that this contributes to enhancing the a-oil effect. One way to measure the fiber entanglement density is to measure the distance between fiber entanglement points, which will be described later.

It is necessary that the value measured by this method has an entanglement density of 200μ or less. Structures with this value greater than 200 μ, for example, 1 with less entanglement, where the fibers are entangled only by needle punching! Fibers have a fiber structure, or have a structure in which ultrafine fibers or their bundles are simply arranged in a plane, or have a structure in which ultrafine fibers or their bundles are densely grown in a fluff-like manner on the surface of a base material and are kneaded to form blood. Since there is little or no entanglement, the surface tends to fluff or crack when subjected to abrasion, rubbing, repeated shearing force, etc., which is undesirable.

In order to eliminate these drawbacks, the distance between fiber entanglement points must be set to 2.
It is necessary that the thickness be 00μ or less. More preferable results can be obtained when the thickness is 100μ or less.

Here, the distance between mNN intersection points is a value determined by the following method, and is a measure of the denseness of the entanglement of m-fibers.A small value indicates that the entanglement is dense. It is. FIG. 1 is an enlarged schematic diagram of the constituent fibers in the grain layer when observed from the surface side. The constituent fibers are f
l, f2゜f3. ......and any 2 of them
Let al be the point where 4Hfff1°f2 of the book intertwines, and al
Trace the U & navy blue ``2'' on top to the point where they intersect, below the other fibers, and connect the intersecting point to a2(f
Take the intersecting point of 2 and f3. Similarly a3. a4. a5・
......... Next, the straight horizontal holes 1111'a1a2. a2a3. a3a
4゜a4a5. asa6. a6a7. a7a3. a3a
s, asar, a7a(1, a9a(,...
... is measured, and the average value of these many measured values is taken as the distance between the fiber entanglement points.

One of the characteristics of the artificial leather of the present invention, which has such a superentangled layer, is that even though it has high moisture permeability and air permeability, it has a low water permeability, which is related to its extremely high water and oil repellent effects. Although it seems that there is, the mechanism and cause are not clear. The water permeability referred to here is 120 mm. Artificial leather 1 under HQ pressure.
It refers to the amount of water (1) that passes per minute per d. 2 of the present invention
Artificial leather having a super-entangled layer with a distance between 11i fiber entanglement points of 00μ or less often has this value of 10100O or less, 10
In many cases, the distance between fiber entanglement points is 500 m1 or less in the case of a distance between fiber entanglement points of 0 μ or less. However, this (IYl) is only a guideline, and if a large amount of resin is applied or impregnated, this value will decrease, so it is only used as a measure of the density of the fibers. Conventional nonwoven fabrics are transparent. Materials with high moisture and breathability must also have high water permeability, and even if treated with water or oil repellency, it would not be very effective.Also, the lower layer of the superentangled layer The ultrafine fiber bundles are mainly intertwined, and the ultram fibers and/or their bundles in the superentangled layer are branched ultrafine fiber bundles in the lower layer and intertwined more densely.

A fiber structure in which the fibers are substantially continuous in the superentangled layer and the lower layer, and the degree of branching changes continuously at the boundary between the two layers is an artificial layer with a sense of unity. It is preferably used because leather is obtained and the superentangled layer and the lower layer do not peel off. Here, the thickness of the ultrafine fiber bundles in the superentangled layer does not need to be the same for all bundles, but is as thin as possible compared to the thickness of the bundle in the lower layer (the number of fibers included in the bundle is smaller than that in the lower layer). It is preferable to have as little as possible since it is less likely to cause unevenness on the surface of the artificial leather.

Furthermore, the lower layer of the superentangled layer has a structure in which the ultrafine lIi bundle and the ultrafine fibers branched from it are intertwined, and the ultrafine fibers 13 and/or their bundles in the superentangled layer are the same as the ultrafine fiber bundles in the lower layer. It is also preferable to have a fiber structure in which the fibers are branched or are continuous with the ultrafine fibers in the lower layer, and these fibers are densely intertwined with each other.

Furthermore, the lower layer of the superentangled layer is 411i l m lit
It is also preferable to use a fiber structure in which the ultrafine fibers are randomly intertwined, and the superentangled layer is mainly composed of ultrafine fibers that are substantially continuous from the ultrafine fibers in the lower layer.

However, in this case, the distance between fiber entanglement points in the superentangled layer tends to be slightly larger than in the case where the ultrafine lJ and fiber bundles are separated, so the density of the superentangled layer and the water- and oil-repellent effects are affected. It is particularly preferable to branch out the ultra-fine fibers.

In such a preferred embodiment, uA constituting the nonwoven fabric
N has a structure in which a single ultrafine fiber forms a bundle in some parts and is branched in other parts, so that it cannot be separated into single fibers and bundles. These preferred embodiments of the present invention are illustrated in FIG.

The ultrafine fiber used in the present invention may be an ultrafine fiber directly produced by a method such as melt blowing or super draw. It is also preferable to use ultra-s, tiii-shaped fibers and transform them into ultra-fine fibers at an appropriate time during the processing process. For example, use Okegawa fibers immediately after spinning. Converge and partially glue 1
Book fibers, mta with a chrysanthemum-shaped cross section in which one component is interposed radially between other components, multilayer bimetal fibers, multilayer bimetal fibers with donut-shaped cross sections, sea islands made by melt-mixing and spinning two or more components. These are polymeric mutually arranged fibers in which a large number of ultra-fine 1Ii111 continuous in the fiber axis direction are assembled and bonded with other components and/or partially bonded to form one shoulder t. More than a species! 1i
Ilt may be used as a mixture or in combination.

Ultrafine fiber-forming fibers having a cross section in which a plurality of cores are interveningly bonded and/or partially bonded by other components can be relatively easily obtained by applying physical action or removing bonding components. Therefore, it is preferably used.

FIG. 3 shows an example of the cross-sectional shape of the ultra-fine 11M fiber that is preferably used.

Furthermore, when at least one component is dissolved and removed, a bundle of fibers consisting mainly of ultrafine 11 fibers of 0.2 denier or less, preferably 0.05 denier or less, more preferably 0.005 denier or less, is formed from a multicomponent. Super thin! &! String-forming fibers are particularly preferable because they have a highly dense superentangled layer and can produce artificial leather with high water and oil repellency, a supple texture, and a smooth surface. used. In addition, the ultrafine fibers according to the present invention are made of a polymeric substance having U and band-forming ability, such as nylon 6.
, nylon 66, nylon 12. Polyamides such as copolymerized nylon, polyethylene terephthalate 1-1, polyesters such as polybutylene terephthalate, copolymerized polybutylene terenotale-1-1, polyolefins such as polyethylene and polypropylene, polyurethane, polyacrylonitrile, and Examples include vinyl polymers. In addition, the binding components or components to be dissolved and removed of the microfiber-forming fibers include polystyrene, polyethylene, polypropylene, polyamide, polyurethane, copolymerized polyethylene terephthalate easily soluble in alkaline solutions, polyvinyl alcohol, copolymerized polyvinyl alcohol, etc. Used are styrene-acrylonitrile copolymer, styrene-acrylic acid higher alcohol ester J3, and/or methacrylic acid copolymer with higher alcohol Nisdel. Polystyrene, styrene-acrylonitrile copolymers, higher alcohol esters of styrene and acrylic acid, and copolymers of methacrylic acid and higher alcohol Nisdel are preferred in terms of flexibility in spinning and ease of dissolution and removal. Preferably used. Further, a copolymer of styrene and a higher alcohol ester of acrylic acid and/or a higher alcohol Nisdel of methacrylic acid is more preferably used because it can obtain a high stretching ratio and a fiber with high strength. In addition, in terms of branching the polar layer single strand, it is possible to mix 0.5 to 30 weight percent of a polymer such as polyethylene glycol as a bonding component or a dissolving and removing component. The fineness of the Gagaru Gokuden 1 machine string and the forming type Tsuzuma 11 is not particularly limited, but Q, 5 -
10 denier is preferred. Of course, the binding component may also be used as a super-layer fiber component.

J) l) A11 The binding cord included in the superentangled layer of the present invention preferably has a fineness of 0.2 denier or less. If it is thicker than 0.2 denier, the stiffness of the fiber is too high, and the flexibility of the supercross/I8 layer and the wrinkle form on the surface are not only distorted, but also
Even if a water-repellent or oil-repellent agent is applied, its effectiveness will be reduced, and furthermore, cracks will occur due to rubbing, etc., and the surface will become uneven, making it difficult to form a dense and supple superentangled layer. By using ultrafine fibers of 0.2 denier or less, preferably 0.05 denier or more, and more preferably 0.005 denier or less, the fibers can be tightly intertwined, resulting in high water repellency, l'iim, and effects. is obtained,
Human skin leather has a #8 supercross layer that is smooth, flexible, hard to crack, and feels good in the hand.

Typical fluorine-based compounds used in the present invention are perfluoroalkyl, perfluoroalkenyl allyl ether, and perfluoro-4:sacenyl.

It has a full primary carbon group such as perfluorononenyl in its side chain, and its main chain is Nisder polyacrylate or methacrylic acid ester polymer.

It is a fluorine-containing polymer, and for example, polymers and copolymers of the following monomers are commonly used.

(R1 represents hydrogen or a methyl group, R2 represents a methyl group or an ethyl group. n is an integer of 3 to 21) Also, the silicon-based compounds used in the present invention [silicon compounds such as dimethylborisiloxane and its copolymers] It is a type resin.

The ultrafine fiber of the present invention and/or a bundle thereof has a superentangled layer mainly formed from a fiber structure in which the distance between fiber entanglement points is 200 microns or less, and at least the surface of the superentangled layer has a fluorine-based and/or ．． : [Water-repellent and oil-repellent with silicone compound attached] - Leather can be specifically obtained by the following method.

For example, by each method described above, a web is formed using directly spun ultra-am coarse fibers, ultra-fine fiber bundles bundled and temporarily bonded, or filaments or cut ultra-fine fiber-forming fibers, and then needle punched. After forming an entangled structure, if a high-speed fluid stream such as a columnar water stream is applied to one or both sides, the energy of the jet stream will cause the ultra-fine Iji fibers in the two surface layers to become entangled or branched. As a result, a superentangled layer is formed. Even in microfiber-forming fibers in which a large number of micro-m1 components are surrounded by a binding component, the exposed micro-III fibers can be entangled as the high-speed fluid flow splits the binding component. Of course, the bonded components may be dissolved and removed to form an ultra-fine fiber bundle before application of the high-speed fluid flow. Such a superentangled layer may, of course, be formed on both the front and back surfaces, and a material like this 6 can be put to practical use as an artificial leather even without containing a resin such as a binder. Of course, it is a preferable method to combine techniques such as impregnation with a binder such as polyurethane and temporary fixing treatment using a temporary fixing agent such as polyvinyl alcohol with the above-mentioned "7 culms."

Furthermore, if you want to obtain a superentangled layer with a silver surface layer, reverse roll coating a resin solution or dispersion on the surface that has been sprayed with a high-speed fluid stream.

Apply by gravure coating, knife coating, slit coating, spraying, etc., coagulate wet or dry with nails, overlap the roll surface or seam 1~ surface, pressurize, heat as necessary, and combine the fibers and resin. At the same time, the surface is smoothed. here,
Before applying the resin, the fiber sheet is subjected to processing such as pressing, and Table I! i'LΩ smoothing is also a preferred method. It is preferable to integrate the fibers and resin using an embossing roll or a textured sheet with a textured surface because integration, smoothing, and texture can be performed at the same time.

The resin used for the silver layer is, for example, polyamide.

Polyester, polyvinyl chloride, polyacrylate copolymer, polyurethane, neoprene.

These include synthetic resins or natural polymer resins such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, polyamino acids, polyamino acid polyurethane copolymers, silicone resins, or mixtures of these resins. Furthermore, if necessary, J, plasticizers, fillers, stabilizers, pigments, dyes, crosslinking agents, etc. may be added. Polyurethane resins or polyurethane resins to which other resins and additives are added are preferably used because they provide a grain layer with a particularly soft texture and feel and good bending resistance.

The artificial leather holding the super-entangled layer thus formed is further coated with a finishing agent and dyed, if necessary.

Processing such as rubbing may also be performed.

In the present invention, the above-mentioned fluorine-based compound, silicon-based compound, or both are applied to at least the superentangled surface of such artificial leather. The timing can be any period after the formation of the superconfused layer.

If there is a step of dissolving the ultrafine fiber-forming w4 navy blue having a binding component, the subsequent step is preferable. Usually, a process near the final stage, such as after dyeing, is preferred. (=J This method is carried out by impregnation, pad method, coating method, etc., followed by drying. If necessary, heat treatment at a constant temperature for 9 hours may be performed thereafter.

Heat pressing such as calendering may also be performed. Further, the fluorine-based compound and the silicon-based compound may be used alone or in combination, or both may be used in separate steps. Moreover, both compounds can be given f=J in the form of an emulsion, and trichloroethane,
1 ~ Lichlorethylene.

It can also be applied as a solution such as perchlorethylene. If emulsion form C is first applied and then heat treated, if it is applied again in the form of a solution, the water repellency will not be affected by the initial application.

The solution can penetrate inside. It is also possible to use antistatic agents, penetrants, etc.

The thus obtained water- and oil-repellent artificial leather of the present invention has high water- and oil-repellency, a supple texture, and a smooth surface feel, and has good bending resistance, shear fatigue resistance, and scratch resistance. From artificial leather for clothing to shoe uppers, handbags, bags, and Bell 1.

It is preferably used for various purposes such as bags, gloves, and ball leather.

The following Examples are provided to clarify the present invention more clearly, and the present invention is not limited thereto.

In the examples, 9 parts and % are by weight unless otherwise specified. Moreover, the value of the average intercrossing point distance was taken as the average value of 100 measured values.

Example 1 20 parts of 2-ethylhexyl acrylate, 80 parts of styrene
60 parts of vinyl polymer (hereinafter referred to as As resin) copolymerized in a proportion of 60 parts as a bonding component and 40 parts of nylon 6 as an ultrafine fiber component, with 16 island components in one filament, Furthermore, the third island component contains many ultrafine fiber components with an average size of 0.001 denier.
4. Polymer mutual array ill as shown in figure (Y).
0 denier, 51 m stable to form a web through the card cross wrapper, and then needle punched with 1 hook - U2000 pieces/d to form the polymeric inter-array m The fibers were entangled to produce a nonwoven fabric (A). Nonwoven fabric (Δ) mesh A] is 405g
/m”, and the apparent density was 0.180/a+t.

A hole with a hole diameter of 0.1mm has a center opening of 1tlIO, 6mm.
9/d in 100 from injection nozzles lined up in a row with a pitch of
While shaking the nozzle, apply water under pressure.

J3 makes contact with the surface at high speed for a total of 5 times under the same conditions.
and 10 times, then increase the pressure to 50 kg/or
The same process was carried out once for each of the 5-times treatment and the 10-times treatment while activating the nozzle to produce a nonwoven fabric (B) J5 and a nonwoven fabric (C). In the obtained nonwoven fabrics (B) and (C), the surface layer polymeric mutually arranged fibers are branched into polar all fibers or bundles thereof, and there is a superentangled layer that has a fiber structure in which the fibers are densely intertwined with each other. They were yelling.

The obtained nonwoven fabric ([3), (C) and the nonwoven fabric (Δ) without a superentangled layer were dissolved in 1 to 100% dichloroethylene (
The AS resin was almost completely extracted and removed by repeating dipping, dipping, and squeezing, and then drying was performed to evaporate and remove the remaining chlorethylene. Non-woven fabric (B).

The water-treated side of the sheet obtained from (C) had an extremely smooth surface with few irregularities.

Table I of the sheet obtained from the nonwoven fabric (A) was unfavorable, as unevenness was observed along the unbranched ultrafine fiber bundles.

The three types of sheets obtained are molded into a 1:2 mold at normal pressure! Dyeing was carried out using A#fi salt dye. Furthermore, on these sheets,
Impregnate and bud (Pickup 35
%)L, after drying at 100°C, heat treatment was performed at 150°C for 1 minute.

Prescription 1 Anahigard AG-710 (Fluorine-based water repellent emulsion manufactured by Asahi Glass Co., Ltd.) 3 parts AG Accel 700 (Kisei Chemical Co., Ltd., antistatic agent) 1 part Isopropanol 3 parts Water 93 parts Next, apply the solution of prescription 2 below to the pad (pick up 30%
), and after drying at 100°C, heat treatment was performed at 30°C for 1 minute.

Formulation 2: Boronko-1 (silicone-based water-soluble solvent solution manufactured by Shin-Etsu Chemical Co., Ltd.) IOO part Trichloride 400 parts The distance between fiber entanglement points and physical properties of the surface layer of fC (artificial leather) obtained are as shown in Table 1. Yes, nonwoven fabric (B) and (C)
Artificial leather from CB), (C).

It had a smooth and high-quality appearance, was soft and had a formal texture, and had excellent breathability and transparency, and also showed high water repellency. Artificial leather <A> from nonwoven fabric (A>) in which the distance between fiber entanglement points is larger than the scope of the present invention does not have a good appearance or use, it easily tears, and the water repellency is also poor. 1] objective of the invention was not achieved.

Table 1 Example 2 20 parts of 2-ethylhexyl acrylate, 80 parts of styrene
Vinyl polymer copolymerized at a ratio of
Figure 3 shows the ratio of 60 parts of S@ fat) as a binding component and 40 parts of nylon 6 as an ultrafine fiber component.
4.0 denier of mixed spun fibers having the form as shown in b.
Using ln+m staples, the card and cloth wrapper were passed through to form a garment with a fabric weight of 480Q/-. There were variations in the thickness of the ultrafine fiber component, but the average was 0.00.
It was 2 denier. Using this wear, in the same manner as in Example 1, a needle punch of 2,000 pieces/J was performed and water treatment was performed four times at 100 = t10+f from one side to 9. As a result, approximately 175 pieces of polar smart hair were branched from the surface layer. A nonwoven fabric (D) having a superentangled layer consisting of the bundles was obtained.

The distance between the l4Ii string entanglement points was about 80 microns.

On the other hand, in the melt blow method, J: about 0°00 of re-nylon 6
Spun and aggregated 5 denier ultrafine ml.

Forms a random web of about 410 g/m2, 2500 g/m2
Tree/Ci needle punch was performed. After shrinking this needle-punch nonwoven fabric with hot water, it was subjected to high-speed water jet treatment from 9 to 100 on one side four times at -j/c IK using the same nozzle as in Example 1, and dried. %, and the inside is a nonwoven fabric (E
) was blue. In addition, polyethylene terephthalate 5 having a cross-sectional structure as shown in Fig. 3 of 2.4 denier and 38 length
Hollow multilayer bimetal type I with 100 layers consisting of 0 parts and 6650 parts of nylon! A web was formed using random uniform fibers. The thickness of one layer in the fiber is approximately 0.
It was 005 denier. The web was needle-punched and subjected to high-speed water jet treatment on one side for shrinkage under the same conditions as those used to obtain the nonwoven fabric (2018).The surface layer 1 had a distance between fiber entanglement points of approximately 150 microns, and the interior was continuous from the surface layer. A nonwoven fabric (F) was obtained in which thick l1iIft, which was a bundle of fibers, were randomly entangled.

Next, these three types of nonwoven fabrics ([)) and (E).

A mixed diol of polyethylene adipate, polybutylene adipate, and polyethylene glycol (mixing ratio 60:20:20) is placed on each superentangled surface of ([).
A 10% solution of polyurethane obtained by chain-extending a prepolymer of p,p'-diphenylmethane diisocyanate with ethylene glycol and a pigment added thereto was applied with a gravure coater, dried, and then heated and embossed [through a J-ru]. It was pressed and embossed with a leather-like grain pattern. Furthermore, the sheet made from the nonwoven fabric (D) was immersed in trichlorethylene, and the AS resin was almost completely extracted and removed by repeating dipping and squeezing, followed by drying to remove residual trichlorethylene by evaporation.

The sheets 1~ from the non-woven fabric (2018) were thoroughly rubbed to form polyethylene terephthalate 1~ and nylon 66 and to separate them.

Further, the sheets (D), (E) and (F) of the present invention were obtained by dyeing with a 1:2 type metal salt dye under normal pressure. The superentangled layers of both C1~ were filled with polyurethane resin and had a beautiful grain layer similar to natural leather.

Next, these inventive sheets (D), ([:l and (
F) Add a pad (Pickup 30
%)L, after drying at 100°C, heat treatment was performed at 160°C for 1 minute.

Prescription 1 Allihigard AG-710 (Fluorine-based water repellent emulsion manufactured by Asahi Glass Co., Ltd.) 5 parts AG Accel 700 (Antistatic agent manufactured by Nishikawa Chemical Co., Ltd.)
1 part isopropanol 2 parts water 92 parts Furthermore, add a pad (pickup 35
%)t, After drying at 100°C, heat treatment was performed at 160°C for 1 minute.

Prescription 2 Asahi Guard AG-650 (solvent type fluorine-based water repellent made by Asahi Glass) 2 parts Boron coat (solvent type silicone water repellent made by Shin-Etsu Chemical 2 parts 1 Helichlor T-dilene 96 parts A book with the resulting silver surface layer) The artificial leather of the invention has a sheepskin-like, extremely supple feel to the touch, and when examined using a microscope, it was found that the super entangled layer (silver surface 1i?j) is densely entangled with extremely mwX strings. In addition, in (D) and (F) it was connected to the internal ultrafine fiber bundle, and in (F) it was connected to a loose intertwined layer with minimal wear.

The polyurethane and finishing agent applied to these leather-like sheets were extracted and removed with a solvent, and the distance between fiber entanglement points of the constituent fibers on the surface of the grain layer was measured. The average distance between fiber entanglement points for artificial leather <D) is 77μ1, and for artificial leather (E) it is 1
For 93μ9 artificial leather (F), it was 150μ.

These people of the present invention] leather and commercially available artificial leather for clothing (
The properties of the polyurethane coating (type with polyurethane coating) are secondary.
As shown in the table, the artificial leather of the present invention has good gas permeability such as moisture permeability, 1 breathability, and excellent water repellency, whereas commercially available artificial leather has virtually no gas permeability. Ta. Further, in the present invention, the water repellency of the types (D> and (F)) in which the ultrafine fiber bundles were branched was superior to the type (E) in which the microfiber bundles were randomly intertwined.

Note) The strength of the grain layer was determined by holding the grain surface with your fingers in a convex shape and rubbing it rapidly with pants to judge the state of the scratches.

[Brief explanation of the drawing]

FIG. 1 is an enlarged schematic diagram of the constituent fibers when the structure vaH in J3 of the supercross M layer is observed from the surface side. FIG. 2 is a cross-sectional view of a model showing a preferred embodiment of the fiber N structure of the artificial leather of the present invention. In the figure, B indicates a superentangled layer, and 8 indicates an interlaced layer of ultrafine fiber bundles or an interlaced layer of ultrafine fibers. FIG. 3 illustrates the cross-sectional structure of the polar 11I dark blue forming type fiber preferably used in the present invention. 1 and 1' in the figure are ultrafine fibers; 2 and 2' in the figure are bonding components. Patent applicant Toshi Co., Ltd. Figure 1 Figure 2 - En (A) (B) Figure 3

Claims (9)

[Claims] (1) At least one side has a superentangled layer mainly formed from a fiber structure in which the distance between fiber entanglements of ultrafine fibers and/or bundles thereof is 200 microns or less, and at least the surface of the superentangled layer has Water-repellent and oil-repellent artificial skin 7i' having a superentangled layer characterized by adhering a fluorine-based compound J3 and/or a silicon-based compound! . (2) The superentangled layer is formed by a composite mainly consisting of a fiber structure in which the distance between IJi navy blue entangled points of lff1l11 fibers and/or bundles thereof is 200 microns or less, and a resin existing in the voids thereof. A water-repellent and oil-repellent artificial leather comprising a superentangled layer according to claim 1, which is a silver surface layer. (3) The lower layer of the ultra-entangled layer is mainly composed of ultra-m fiber bundles, and the super-interwoven #8 layer is made up of ultra-fine fibers and/or bundles branched from the ultra-fine fiber bundles in the lower layer. J3 takes the lead,
Claim (1) characterized in that the fibers in the lower layer and the superentangled layer are substantially continuous, and the degree of branching at the boundary between the two layers continuously changes. A water-repellent and oil-repellent artificial leather having a superentangled layer according to item (2) or item (2). (4) The lower layer of the ultra-entangled layer is made up of ultra-fine fiber bundles and ultra-fine fibers branched from the ultra-fine fiber bundles, and the super-entangled layer is made up of ultra-fine fibers and/or bundles thereof branched from the ultra-fine m string bundles in the lower layer. Claim No. 1, characterized in that the ultrafine fibers that are continuous with the ultrafine layer 1 of the lower layer are the main components.
) or (2), a water repellent having a superentangled layer according to item (2);
Oil-repellent artificial leather. (5) Claim (1) characterized in that the lower layer of the superentangled layer is mainly entangled with ultrafine II miscellaneous fibers, and the superentangled layer is substantially continuous with the ultrafine fibers in the lower layer. A water repellent having a superentangled layer according to item (2) or item (2). Oil-repellent artificial leather. (6) Superfine II miscellaneous bundles are polymer mutual array stratification 1 to 1
The spring water and oil repellent artificial leather having a supercross of 18 m according to any one of claims (1) to (4), wherein (7) Pole 1 ifi Ilg, the bundle is obtained from U gold thread fiber (Claim No. 1)
A water repellent having a superentangled layer according to any one of items 1) to 4). Oil-repellent artificial leather. (8) The superentangled layer according to claims 1 to 5, characterized in that the super-m fiber bundles are obtained from multicomponent fibers that can be chemically or physically split and peeled. Water- and oil-repellent artificial leather. (9) Claims 1 to 1, characterized in that the ultra-fine 111ft is manufactured by a melt blowing method.
Water-repellent and oil-repellent artificial leather forming the superentangled layer described in item 5.