JPH0214056A - Fiber-entangled nonwoven fabric - Google Patents

Abstract

PURPOSE:To obtain the subject nonwoven fabric having excellent stretchability and suitable as a substrate for artificial leather, etc., by combining a multi- component fiber composed of an elastic fiber of polyurethane elastomer and a specific other non-elastic polymer with a multi-component fiber composed of non-elastic polymers other than the above polymer and entangling the fibers. CONSTITUTION:(A) An elastic polymer composed mainly of a polyurethane and (B) a non-elastic polymer (e.g., polyethylene) having solvent and decomposition agent different from those of the component A are dissolved in e.g., a common solvent and the obtained dope is spun to produce a multi-component fiber I. The ratio of the component A is preferably 30-80wt.%. Separately, a multi-component fiber II is produced by spinning (C) a non-elastic polymer such as polyethylene terephthalate and (D) a polymer (e.g., polystyrene) having solvent solubility and decomposability different from those of the component C in the same manner as above. The produced multi-component fiber II is combined with the above multi-component fiber I, opened e.g., with a carding machine to form a web and subjected to entangling treatment to obtain the objective nonwoven fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a fiber entangled nonwoven fabric with excellent elasticity. More specifically, it has excellent fiber entanglement, has a wide stretching range that does not substantially cause structural deformation or structural destruction even when repeatedly stretched and deformed, and is rich in stretchability, giving a sense of fulfillment. The present invention relates to a fiber-entangled nonwoven fabric that has a certain soft texture and is suitable as a substrate for artificial leather.

<Conventional technology> Conventionally, a fiber entangled nonwoven fabric with excellent elongation mtt was produced by depositing a stream of short fibers obtained by spinning polyurethane in 7 lashes.
Nonwoven fabrics have already been made in which fiber intersection points are bonded together using methods such as self-adhesion. In addition, a spunbond nonwoven fabric obtained by depositing long fibers obtained by spinning polyurethane was published in Japanese Patent Application Laid-Open No. 52
JP-A No. 18579/1989 describes a stretchable and strong nonwoven fabric obtained by mixing 11.5 to 80% by weight of elastic fibers with inelastic fibers. JP-A-52-85575 discloses a method in which composite fibers obtained by composite spinning an inelastic polymer and an elastic polymer are used to form a fiber-entangled nonwoven fabric, and then the composite fibers are peeled into each component. A non-woven fabric is produced by blending a mixed fiber obtained by mixing and spinning a non-elastic polymer with a mixed fiber obtained by mixing-spinning two types of non-elastic polymers, and at least one type of non-elastic polymer in the mixed fiber. dissolve,
Next, a method for manufacturing a leather-like sheet in which the dissolved inelastic polymer solution is directly coagulated into a nonwoven fabric was disclosed in Japanese Patent Publication No. 1973-
This is proposed in Japanese Patent No. 2792.

<Problems to be Solved by the Invention> In the conventional manufacturing method of fiber-entangled nonwoven fabric, in the case of a nonwoven fabric made of fibers that are also inelastic polymers, even a slight elongation, e.g., 10% elongation of the nonwoven fabric, causes the fiber entangled structure to deteriorate. deformation occurs and never recovers to its original state. On the other hand, in the case of nonwoven fabrics made of fibers made of elastic polymers such as polyurethane elastomers, they exhibit stretch behavior up to a certain extent of elongation. It is extremely difficult to perform entanglement processing. Furthermore, fibers made of elastic polymers and fibers made of inelastic polymers have an incomparably large difference in stiffness, elongation, and flexural modulus, so it is necessary to mix both fibers. , it is quite difficult to make a good fiber web, let alone hang it on a card. In addition, there is a method for manufacturing nonwoven fabric in which a fiber-entangled nonwoven fabric is made using composite fibers obtained by composite spinning of an inelastic polymer and an elastic polymer, and then each component is peeled off. The fibers are constrained in the same state and sufficient stretchability cannot be obtained.

Furthermore, as in the past, a fiber-entangled nonwoven fabric of inelastic fibers containing an elastic polymer has elasticity within the range of deformation that occurs between the fixed points of the entangled fibers, and the range is not large.

The present invention has excellent fiber entanglement properties, has a wide stretching range that does not substantially cause structural deformation or structural destruction even when repeatedly stretched and deformed, and has high elasticity and a soft texture with a satisfying feel. Therefore, it is an object of the present invention to provide a fiber-entangled nonwoven fabric suitable as a substrate for artificial leather having elasticity.

Means for Solving the Problems> The present invention comprises an elastic polymer (A) mainly composed of a polyurethane elastomer, and at least one type of inelastic polymer having a different solubility or degradability from the elastic polymer (A). A multicomponent fiber consisting of (C) and at least two types of inelastic polymers with different solubility or degradability (
This fiber-entangled nonwoven fabric is characterized in that short fibers of multicomponent fibers II consisting of B) and (D) are mixed and entangled.

In addition, the present invention uses modified fibers A, which are ultrafine fiber bundle fibers made of an elastic polymer (A) mainly composed of polyurethane elastomer or fibers having micro spaces, and ultrafine fiber bundle fibers or micro spaces made of an inelastic polymer (B). It is a fiber-entangled nonwoven fabric formed by mixing and entangling short fibers of the modified fibers B, in which the entangled state of the fibers in the nonwoven fabric is such that the modified fibers B are in a tense entangled state. This is a fiber-entangled nonwoven fabric characterized by being formed by bending and bending the modified fibers A and entangling them in a loose tissue structure.

Furthermore, the present invention provides modified fibers that are ultrafine fiber bundle fibers or fibers with micro spaces made of an elastic polymer (A) mainly composed of polyurethane elastomer, and ultrafine fiber bundle fibers or modified fibers containing micro spaces made of an inelastic polymer (B). It is a fiber-entangled nonwoven fabric obtained by mixing and entangling short fibers of modified fibers B, which are fibers with modified fibers B, and the entangled state of the fibers in the nonwoven fabric is such that the modified fibers A fiber characterized by containing a polymer mainly composed of an elastic polymer in the fiber entanglement space of a fiber entangled nonwoven fabric formed by bending and bending and entangling the loosened tissue structure by the modified fibers A. It is an entangled nonwoven fabric.

That is, the highly stretchable fiber-entangled nonwoven fabric of the present invention comprises an elastic polymer (A) mainly composed of a polyurethane elastomer, and a small number of (all one type) having different solubility or degradability from the elastic polymer (A). Short fibers of multicomponent fiber I consisting of an inelastic polymer (C) and at least two types of inelastic polymers (B) and (D) having different solubility or degradability.
) are mixed with short fibers of multicomponent fiber II at a predetermined ratio to form a fiber web, and subjected to fiber entanglement treatment to form a fiber entangled nonwoven fabric, and then the following (1) and (2) and step (3), (1) Multicomponent fiber I shrinks significantly, but multicomponent fiber ■
is a step of shrinking the area of the fiber-entangled nonwoven fabric by 10 to 80% under conditions of low shrinkage or non-shrinkage; (2) at least one type of multicomponent fiber (■) to an inelastic polymer (C) and multicomponent fiber (■); An inelastic polymer (D
) or dividing the multicomponent fibers into their respective components; and (3) impregnating a nonwoven fabric with a solution or dispersion of a polymer mainly composed of an elastic polymer and solidifying it. Processing, that is, step (1) → step (2), step (2) → step (1), step (1) and step 8! (2) at the same time, further, step (1) → step (2) - step (3), step (1) - step (3) - step (2) or step (1) and step (2) simultaneously → Process (3
), and then 8
By heat-treating at a temperature of 0 to 170°C for at least 3 minutes, modified fibers A, which are microfiber bundle fibers made of an elastic polymer (A) mainly composed of polyurethane elastomer or fibers with microscopic spaces, and an inelastic polymer (B) are heated. ) or a fiber entangled nonwoven fabric of modified fiber B, which is an ultrafine fiber bundle fiber or a fiber having microscopic spaces, or a fiber entangled nonwoven fabric containing a polymer mainly composed of an elastic polymer. This is an excellent method for producing fiber-entangled nonwoven fabric.

The raw material fibers constituting the stretchable fiber-entangled nonwoven fabric of the present invention are:
Elastic polymer mainly composed of polyurethane elastomer (
A) and at least one non-elastic polymer (C) having different solubility or degradability from the elastic polymer (A).
A multicomponent fiber obtained by spinning ■ and at least two types of inelastic polymers (B) having different solubility or degradability,
A multicomponent fiber (2) obtained by spinning (D) is used. In the present invention, by using multicomponent fiber I, physical properties such as elongation behavior, stiffness, and flexural modulus of the fiber are similar to or within the same range as multicomponent fiber II, so that the blendability and carding properties of both fibers are improved. A fiber web with good homogeneity can be obtained, and a good fiber entanglement state can be obtained by a fiber entanglement method such as a needle punching method or a high-pressure fluid jetting method.

In addition, in the present invention, the elastic polymer refers to fibers obtained by spinning the elastic polymer, which are stretched by 50% at room temperature,
A polymer with an elongation elastic recovery rate of 90% or more after 1 minute after release of elongation, and an inelastic polymer refers to a polymer with a low elongation elastic recovery rate of 50% or less measured in the same manner or at room temperature. shows a polymer whose critical elongation rate does not reach 50%.

The elastic polymer (A) of the multicomponent fibers I used in the invention can be selected from the group of polymer diols, such as polyester diols, polyether diols, polyester ether diols, polylactone diols, polycarbonate diols, etc., with an average molecular weight of 500 to 3500. At least one selected from the group of organic diisocyanates such as diisocyanates having an aromatic ring, aliphatic or alicyclic diisocyanates, and low molecular weight diols, aliphatic or alicyclic diisocyanates. At least one type of polyurethane elastomer selected from polyurethane elastomers obtained by reacting with at least one type selected from the group of chain extenders having two active hydrogen atoms such as diamine, hydrazine, and diamine having an aromatic ring. be. Further, the elastic polymer is mainly composed of a polyurethane elastomer mixed with a conjugated diene polymer such as polyisoprene or polybutadiene, or other spinnable elastic polymers as required.

On the other hand, the inelastic polymer (C) of the multicomponent fiber (2) is a polymer that can be removed by treatment with a solvent or decomposition agent different from that of the elastic polymer (A), such as polyethylene and ethylene. Combined, polypropylene,
Selected from the group of polyolefins such as polybutene, ethylene vinyl acetate copolymer, polystyrene or styrene copolymer, polyvinyl chloride or vinyl chloride copolymer, polyester, polyamide, polycarbonate, etc.
: At least one type of polymer.

The method for producing multicomponent fiber I is based on an elastic polymer (A).
and the elastic polymer is an inelastic polymer (C) in a different solvent or decomposition agent, and the polymers with overlapping aging ffi temperature ranges can be combined, or they can be dissolved in a common solvent or a compatible solvent, and a combination of polymers that remains dissolved during the time required for spinning and does not cause reactions or interactions that would interfere with spinning or removal of inelastic polymers from the fibers, such as polyurethane/polyolefin or sintered fins. Examples include copolymers, polyurethane/polystyrene or styrene copolymers, polyurethane/polyolefin/polystyrene, polyurethane/polyamides or polyesters, polyurethane/conjugated diene polymers/polystyrene or styrene copolymers. The proportion of the elastic polymer (A) in the multicomponent fiber is 30 to 80% by weight, preferably 40 to 70% by weight. The selected elastic polymer (A) and inelastic polymer (C) are dissolved in a common solvent and spun by a wet spinning method or a dry spinning method, or melt spun at a common melting temperature. That is, the elastic polymer (A) and the inelastic polymer (C) are melted in the same melting system or melted in the same melting system and spun, or alternatively by melting them in different melting systems or melting them in different melting systems. Multi-layer fibers can be spun by laminating multiple layers together, or by combining them in a spinning head or spinneret with a structure that forms a seabird-shaped or composite fiber cross-sectional shape, with one side serving as a dispersion medium component and the other as a large number of dispersion components. Manufacture component fiber I (in addition,
The production of multicomponent fiber II described below is also a similar spinning method).
Next, it is preferable to draw the multicomponent fiber (2) under conditions such as dry heat, wet heat, or heated water to at least twice the amount of the spun raw fiber.If the drawing ratio is high, a high shrinkage fiber will be obtained, and the fiber entangled nonwoven fabric will be produced. Even if you do this, you can get something with a high sense of fulfillment and great elasticity. The drawn fibers are crimped and the fiber length is 2.
Cut into 0 to 100 m+m to obtain short fibers of multicomponent fiber (2). This multi-acid fiber! #I has an elastic behavior suppressed by an elastic polymer, and is a normal inelastic fiber, especially a multicomponent fiber I
Since it falls within the range of fiber physical properties such as stiffness and elongation behavior of I, it can be handled in the same way as multicomponent fiber (■).

In the other multicomponent fiber (2) constituting the fiber-entangled nonwoven fabric, the inelastic polymer (B) used as a fiber component is, for example, polyethylene terephthalate or ethylene terephthalate copolymer, polybutylene terephthalate or butylene terephthalate copolymer. Polyester such as coalescence, nylon-6, nylon-66, nylon-
610, length iron-12, polyamides such as polyamides containing aromatic rings, polyolefins such as polyethylene and polypropylene, saponified products of ethylene vinyl acetate copolymers,
It is at least one type of polymer selected from the group such as polyvinyl alcohol and acrylic copolymers. on the other hand,
The polymer (D) to be finally removed is a polymer that is soluble in a solvent or decomposed with a decomposing agent, such as polyethylene or ethylene copolymer, ethylene vinyl acetate copolymer or its partially saponified product, polystyrene or styrene copolymer, etc. It is at least one type of polymer selected from the group of polymers, polyesters, polyamides, polyvinyl alcohols, polyvinyl chlorides, and vinyl chloride copolymers. Then, the inelastic polymer (B) used as the fiber component and the inelastic polymer (D) as the removed component are combined and spun. However, when the multicomponent fiber (1) is a splittable fiber, at least two types of inelastic polymers (B) having low or no compatibility and different physical properties are combined and spun. Specific polymer combinations include, for example, polyethylene terephthalate/polyethylene or ethylene copolymer, polyethylene terephthalate/polystyrene or styrene copolymer, polybutylene terephthalate/polyethylene or ethylene copolymer, polybutylene terephthalate/polystyrene or styrene copolymer. Examples include nylon-6 or nylon-610/polyethylene or ethylene copolymer, polyethylene terephthalate or polybutylene terephthalate/nylon-6 or nylon-61O, polypropylene/polystyrene, or polyethylene.

And the ratio of the inelastic polymer (B) as a fiber component is 40 to 85! is the amount%. The spinning method is the same as that for multicomponent fiber (1) described above, followed by stretching, crimping, and cutting to obtain short fibers of multicomponent fiber II.

Next, the multicomponent fiber I and the multicomponent &1ilff are mixed.

The blending ratio is determined depending on the desired physical properties of the fiber-entangled nonwoven fabric, but generally the multicomponent fibers are 15 to 80% by weight,
Preferably it is in the range of 20 to 70% by weight. If there is less multicomponent fiber I, the product will have less elasticity but will be more flexible, and if there is more multicomponent fiber (I), the product will have greater elasticity and a greater sense of fulfillment. Furthermore, if necessary, regenerated cellulose fibers, natural fibers, and chemical fibers may be mixed in an amount of approximately 25% by weight or less, within a range that does not impede stretchability.

After mixing multicomponent fibers I and multicomponent fibers (2), they are defibrated using a card and passed through Univer to form a random web or a cross-wrap web, and the resulting fiber webs are laminated to a desired weight and thickness. The weight of the fibrous web is generally 100
-2000 g/m''. Next, the fiber web is subjected to fiber entanglement treatment by a known method to form a fiber entangled nonwoven fabric.

A preferable method for entangling the fibers is to use a needle punching method or a high-pressure water jet method alone or in combination. Generally, in the needle punching method, the number of punches is 200.
In the high-pressure water jet method, treatment is performed in the range of 3 to 10 times using a columnar flow with a water pressure of 15 to 100 kg/cm, and the entanglement of the fibers is sufficiently achieved. It is preferable for it to be flexible and fulfilling.

I imparts sufficient stretchability to the obtained fiber-entangled nonwoven fabric;
In order to achieve this, the fiber-entangled nonwoven fabric must be caused to shrink. The shrinkage treatment method is performed in a dry heat atmosphere, a moist heat atmosphere, or hot water under conditions in which the multicomponent fibers I are sufficiently shrunk, but the multicomponent fibers are low or non-shrinkable. Shrink the area by 10-80%. This shrinking treatment of the fiber-entangled nonwoven fabric may be performed before or after removing the inelastic polymer component from the multicomponent fibers, or while the nonwoven fabric contains an elastic polymer, but in each case, By setting the conditions, the desired shrinkage range can be obtained. Through this shrinkage treatment, the modified fiber A made of the multi-component 1a fiber (1) or the elastic polymer (A) obtained therefrom shrinks significantly, and the modified fiber A made of the multi-component fiber (1) or the inelastic polymer (B) obtained therefrom shrinks significantly. The fibers B are folded or bent and have a loose mJ1 structure within the nonwoven fabric.

The shrinkage rate of this fiber-entangled nonwoven fabric is determined by the shrinkage treatment conditions (e.g.
(temperature, time, tension, etc.), but the potential shrinkage (maximum shrinkage rate) of a fiber-entangled nonwoven fabric depends on the type of elastic polymer of the multicomponent fiber I that makes up the nonwoven fabric, the molecular structure of the polymer, the spinning conditions, It is controlled by the draw ratio, fineness, etc.
On the other hand, it is mainly determined by the bending rigidity of the fiber based on the type of inelastic polymer of the multicomponent fiber II, the degree of orientation, the fineness, etc., and the blending ratio of the multicomponent fiber I and the multicomponent fiber II. Therefore, by changing these conditions, the shrinkage rate of the fiber-entangled nonwoven fabric can be changed arbitrarily.

In addition, in order to impart elasticity to the fiber-entangled nonwoven fabric, it is necessary to remove the inelastic polymer fiber component of the multicomponent fiber I and modify the ultrafine fiber bundle fibers or the modified fibers A of fibers with microscopic spaces.
I have to do it. On the other hand, at least one kind of inelastic polymer fiber component of the multicomponent fiber II is removed to change the fiber form to a modified fiber B, which is an ultrafine fiber bundle fiber or a fiber having microscopic spaces, or the multicomponent fibers N are each By peeling and dividing the fibers into modified fibers B, which are ultrafine fiber bundle fibers, a fiber-entangled nonwoven fabric with greater flexibility and stretchability can be obtained. The method for removing the inelastic polymer fiber component is carried out by treating the elastic polymer fiber component and the used inelastic polymer fiber mfg: with a non-solvent or non-degrading agent, and a solvent or a decomposing agent for other fiber components. For example, toluene, trichlorethylene, perchlorethylene, etc. are used for polyurethane/polyolefin or polystyrene fibers, calcium chloride/methanol solution is used for polyurethane/polyamide fibers, and cyclohexanone is used for polylanthane/polyvinyl chloride fibers.

In this invention, fibers obtained by removing one component from a multicomponent fiber or fibers obtained by processing a multicomponent fiber and dividing it into a large number of ultrafine fibers are referred to as "modified fibers" in the present invention. Modified fibers are used in the final product, even if they are fibers that do not take the form of glued and distinct microfiber bundle fibers or fibers with microscopic spaces, such as polyurethane fibers.
Any fiber that is clearly denatured may be used.

The process of converting multicomponent fibers into modified fibers may be performed in the same process or in separate processes for producing multicomponent fibers 1 and multicomponent fibers (2). You can do it after doing so. However, due to the simplicity of the steps, it is preferable to carry out the steps in the same step.

In the fiber-entangled nonwoven fabric of the present invention, when stretching force is applied to the fiber-entangled nonwoven fabric, the force initially stretches only the modified fibers A, so a large force is not required. As fiber B begins to deform, a larger force is gradually required. Therefore, the range until the fixation due to the entanglement of the fiber-entangled nonwoven fabric, the fixation between fibers due to the adhesion of the modified fiber A, or the fixation due to the binder comes off, that is, the range until structural destruction occurs, is wide.
During this period, stretchability can be imparted without substantially causing structural destruction.

Further, the fiber-entangled nonwoven fabric of the present invention may contain a binder resin made of an elastic polymer within a range that does not impede stretchability. The elastic polymer used as the binder resin is, for example, at least one type selected from the group of polymer diols such as polyester diol, polyether diol, polyester ether diol, polylactone diol, and polycarbonate diol, and at least one type of organic diisocyanate. and polyurethane obtained by reacting a low-molecular compound having at least two active hydrogen atoms as a chain extender, a polymer or copolymer of acrylic acid or acrylic ester, a conjugated diene polymer such as polyisoprene, polybutadiene, etc. , styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, and the like. The elastomeric polymer is impregnated into a nonwoven fabric using a solution dissolved in a solvent that does not attack the fibers or a dispersion in a dispersant. It is solidified by processing or by evaporating the solvent or dispersant. By incorporating an elastic polymer into the fiber-entangled nonwoven fabric,
It is possible to widen the range of performance such as flexibility, stretchability, and texture of the fiber-entangled nonwoven fabric.

The fiber-entangled nonwoven fabric of the present invention can be sliced into desired thicknesses to have a constant thickness, or the fiber-entangled nonwoven fabric can be made to a constant thickness by puffing the negative side or both sides with sandpaper, or the fiber-entangled nonwoven fabric can be left as is. is used as a product. The fiber-entangled nonwoven fabric of the present invention is made by almost uniformly mixing short fibers of modified fiber A made of an elastic polymer and modified fiber B made of an inelastic polymer, and the entangled state of the fibers is such that the modified fiber B has tension. This is a nonwoven fabric that is bent and bent by the modified fibers A in an entangled state and intertwined with each other to form a loose tissue structure as a whole, or a nonwoven fabric that contains an elastic polymer in the nonwoven fabric. One way to check the state of this tissue structure is to check the shape of the nonwoven fabric after removing one of the fibers from the fiber-entangled nonwoven fabric. That is,
When the elastic polymer modified fibers A are dissolved or decomposed and removed, the fiber-entangled nonwoven fabric of the inelastic polymer modified fibers B is released from tension and expands to an area close to that before the shrinkage treatment. On the other hand, when the non-elastic polymer modified fibers B of the non-woven fabric are removed by dissolving or decomposing, the area of the non-woven fabric entangled with the elastic polymer modified fibers is known to hardly change or only to a small extent. be able to. Due to the structure of the above-mentioned fiber-entangled nonwoven fabric, it has a large elongation range that does not substantially cause structural deformation or structural destruction even if it is repeatedly elongated.
It has an elongation of ~50%, is highly stretchable, and has a soft and fulfilling texture.

The fiber-entangled nonwoven fabric of the present invention can be made into a bank leather-like sheet by ironing the surface to make it smooth, forming an elastic polymer film on the surface or adding a film to give it a silver surface finish. The surface can be finished with fiber raising treatment to produce a suede-like leather-like sheet.

The fiber-entangled nonwoven fabric of the present invention has many useful uses such as supports, bands, medical supplies, clothing or parts for clothing, leather-like sheets for interior use, outer clothing, car seats, and many others.

<Examples> Next, embodiments of the present invention will be described using specific examples, but the present invention is not limited to these examples. Note that parts and percentages in the examples are by weight unless otherwise specified.

Examples 1 to 4, Comparative Examples 1 and 2 Polyester polyurethane (elongation elastic recovery rate 100%
) 60 parts and low density polyethylene (50% unstretched) 40 parts
A bicomponent fiber with a sea component of polyethylene is made using a melt spinning method, stretched 2.8 times, crimped, and cut into fiber lengths of 51 mm to obtain staple fibers with a fineness of 6 denier (
A fiber (hereinafter referred to as fiber I□) was obtained. On the other hand, the bicomponent fiber is made of 50 parts of nylon-6 (with an elongation elastic recovery rate of less than 50%) and 50 parts of low-density polyethylene, with polyethylene as the sea component; it is made by a melt-spinning method, stretched, heat treated, and crimped. The fiber was cut into a fiber length of 511IIIa to obtain a stable fiber with a fineness of 4 denier (hereinafter referred to as fiber Ⅰ1).

Next, the fibers (1) and (2) were mixed in the ratio shown in Table 1, spread on a card, and then a random web was formed using a random univer, and the fiber web was formed using a needle with a needle size of #40. A total of 560 punches/cm'' of needle punching was performed alternately on both sides to produce a fiber-entangled nonwoven fabric weighing approximately 400 g/cm. This fiber-entangled nonwoven fabric was placed on a Teflon-coated sheet, and then untensioned. 135℃ in condition
The fiber-entangled nonwoven fabric was heat-treated in hot air to give shrinkage.

The shrink-treated fiber-entangled nonwoven fabric was dipped in hot perchlorethylene at about 80°C and repeatedly squeezed to dissolve and remove the polyethylene, then air-dried to remove the solvent, and then subjected to dry heat treatment in hot air at about 130°C. Then, adhesive points were formed by adhesion in the areas where the polyurethane fibers were in contact with each other. The obtained fiber-entangled nonwoven fabric is composed of polyurethane modified fibers and nylon.
6 ultra-fine fibers are present in a good mixed fiber state, and the fibers dissolved in polyethylene become flexible and have many intertwining nodes, resulting in good elasticity and no structural deformation even after 30% elongation. did not occur. Table 1 shows the state of the obtained fiber-entangled nonwoven fabric.

The fiber entangled nonwoven fabric of the present invention was flexible and had little or no fiber texture peculiar to fiber entangled nonwoven fabrics.

The surfaces of the thick samples of Examples 1 and 2 were ironed to make them smooth, and the colored samples were materials that could be used for casual shoes. It is also a thin material that can be used as a supporter. The surfaces of the samples of Examples 3 and 4 were treated with a fuzz chamber to obtain a suede-like material.

Table 1 As a result of enlarging and observing the fiber-entangled nonwoven fabrics obtained in the above examples, it was found that the modified polyurethane fibers were in a tensed state, whereas the nylon-6 ultrafine fibers were in a relaxed state. Was. On the other hand, such a state was not observed in the fiber entangled nonwoven fabric of the comparative example.

Examples 5 to 7, Comparative Example 3 Polyester polyurethane (elongation elastic recovery rate 100%
) and 40 parts of styrene copolymer (50% unstretched) were made by melt spinning, drawn to 2.5@, crimped, and cut to a fiber length of 51 mm to obtain a fineness of 6 denier. A staple fiber (hereinafter referred to as fiber I) was obtained. On the other hand, a two-component m-fiber consisting of 50 parts of polyethylene terephthalate (with an elongation elastic recovery rate of less than 50%) and 50 parts of low-density polyethylene, with polyethylene as the sea component, was produced using a melt-spinning method, and then stretched, heat treated, crimped, and lengthened. Non-shrinkable staple fiber with a fineness of 4 denier cut into 51 mm pieces (hereinafter referred to as fiber ■2)
) was obtained.

Next, fiber 1 and fiber 2 are mixed in the ratio shown in Table 2, and after defibration by carding, a cross-wrap web is formed, and the fiber web is summed alternately from both sides using a needle with a needle size of #4o. Needle punching was performed at a rate of 700 punches/cm" to produce a fiber-entangled nonwoven fabric weighing approximately 750 g/m". Approximately 85aC of this fiber-entangled nonwoven fabric! The styrene copolymer and polyethylene in the fibers were dissolved and removed, and the fiber-entangled nonwoven fabric was shrunk in the same treatment step. After squeezing out the solution, it was pressed and dried in hot air at about 80°C. Obtained T: The fiber-entangled nonwoven fabric forms adhesion points due to adhesion in the areas where the polyurethane fibers are in contact with each other, and the polyurethane fibers and ultra-fine polyester fibers are in a good mixed state and are flexible. Therefore, it had many fiber entanglement nodes and exhibited good elasticity, and no structural deformation occurred even after 30% elongation. The state of the obtained fiber-entangled nonwoven fabric was
Shown in the table.

When the state of the fibers of the fiber-entangled nonwoven fabrics obtained in these Examples was observed under magnification, it was the same as in Examples 1 to 4.

(Left space below) Kaya 2 table Examples 8 to 11. Comparative Example 4 Polyester polyurethane (elongation elastic recovery rate 100%)
) 50 parts and low density polyethylene (50% unstretched) 50 parts
A bicomponent fiber with polyethylene as the sea component is made by a melt spinning method, stretched 2.8 times, crimped, and cut to obtain raw cotton with a fineness of 6 denier and a fiber length of 5 mm (hereinafter referred to as fiber).
) was obtained.

On the other hand, nylon-6 (elongation elastic recovery rate less than 50%) 50
and 50 parts of the above-mentioned low-density polyethylene, using a melt-spinning method to make two-branch fibers with polyethylene as the sea component,
Stretched, crimped and cut, fineness 4 denier, fiber length 51m
m raw cotton (hereinafter referred to as fiber ■).

) was obtained.

Next, 40 parts of fiber I3 and 60 parts of fiber 1 were mixed,
Make a random web with a random univer through the card, and use a #40 needle to alternately run the web from both sides for a total of 4
A fiber-entangled nonwoven fabric weighing approximately 500 g/m was produced by needle punching at a rate of 20 punches/c+s. This fiber-entangled nonwoven fabric was immersed in an aqueous polyurethane dispersion having a solid content concentration of 4%, and then squeezed to a liquid content of 80% using a squeezing roll. Then, it was placed on a Teflon-coated sheet and dried in a hot air dryer at 130° C. under substantially no tension. The dried fiber-entangled nonwoven fabric had shrunk by about 35% in length (area shrinkage rate about 57%) in both the longitudinal and transverse directions.

Next, the fiber entangled nonwoven fabric was immersed in perchlorethylene at 80°C to form fibers I and I! The polyethylene in 3 was dissolved and removed and dried in a hot air dryer at about 80°C. The obtained polyurethane-containing fiber-entangled nonwoven fabric has polyurethane and convergent fibers of fine denier fibers of nylon-6 well entangled, has a weight of about 630 g/1112, and a final area shrinkage rate of about 60.
% sheet-like material. After slicing approximately the center of the sheet material's thickness with a band machine knife and dividing it into two parts, the sheet material is impregnated with a 5% aqueous solution of polyvinyl alcohol and dried to prevent elongation during subsequent processing of the sheet material. Ta. Then, use sandpaper to puff the sliced surface to make the thickness uniform, then puff the surface to make it 0.611 thick! It has a suede-like surface with 1 fiber nap. The obtained sheet-like material was dyed with a metal complex dye concentration of 2% ov.
f. After dyeing at a temperature of 90°C for 60 minutes and drying,
A suede-like artificial leather was obtained by kneading and brushing the surface (sample of Example 8). This artificial leather had a lighting effect, had high elasticity in both directions, was extremely flexible, and was resistant to wrinkles.

Using the same manufacturing method as above, suede-like artificial leather was produced by varying the blending ratio of fiber I3 and fiber 1 as shown in Table 3. The properties of the obtained artificial leather are shown in Table 3. Furthermore, the samples of each example and the sample of comparative example were stretched by 30%.
After repeating the recovery 10 times, the recovery rate was determined after being left for 3 hours. As a result, the samples of Examples 8 to 11 recovered by 99 to 100%, while the sample of Comparative Example 4 recovered by 58%.

Table 3 In addition, the artificial leather of Example IO has a very rich feeling, with 5
Even at 0% elongation, the elastic recovery rate was 95%. However, this artificial leather has too little nap to be made into so-called suede-like artificial leather, so after smoothing the surface by contacting it with a flat roll surface at 120°C,
A 0% moisture teaching solution was applied with a gravure roll, and a 10% polyurethane solution was further applied with a gravure roll. and,
The polyurethane coated surface was embossed with a heated embossing roll to obtain silver-covered artificial leather. This artificial leather had a solid feel and excellent elasticity, making it suitable as a material for shoe uppers.

As a result of enlarging and observing the state of the fibers inside the artificial leather obtained in these examples, it was found that the fibers (bundle) made of polyester polyurethane were in a tension state between the points fixed by the binder resin or the points fixed by entanglement. In contrast, it was confirmed that the seed net fiber bundle fibers made of nylon-6 were in a loose state.

Example 12 Polyester polyurethane (elongation elastic recovery rate 100%)
) and 40 parts of polystyrene (without 50% elongation) were melt-spun to obtain a bicomponent fiber with a fineness of 6 denier (hereinafter referred to as fiber I4), and polyethylene terephthalate (
Polyethylene obtained by melt-spinning 50 parts of elongated elastic recovery (less than 50%) and 50 parts of the low-density polyethylene has a sea component t') and has a fineness of 4 denier.
), 30 parts of this fiber I4 and fiber ■.

After mixing 7θ parts of the fibers to make a random web and needle punching to make a fiber-entangled nonwoven fabric, polystyrene and polyethylene in the fibers were dissolved and removed with perchlorethylene at a temperature of 90°C, and dried in a hot air dryer at about 80°C. It was dried. The obtained fiber-entangled nonwoven fabric had an area shrinkage rate of about 30%. Approximately 100% polyurethane moisture content with a solid content concentration of 4% is added to the obtained fiber-entangled nonwoven fabric as a binder resin.
It was impregnated and placed on a Teflon-coated sheet, and dried in a hot air dryer at a temperature of 130° C. under no tension. The obtained fiber-entangled nonwoven fabric was subjected to the same surface treatment, hematopoiesis, and finishing as in Example IO to produce silver-covered artificial leather.

Although this artificial leather had a rather large rebound, it was a material that was highly flexible and stretchable. Further, as in Examples 8 to 11, the state of the fibers inside this artificial leather was such that the polyurethane fibers were in a taut state, whereas the polyethylene terephthalate ultrafine fiber bundle fibers were in a loose state.

Comparative Example 5 For comparison, the fibers (1) obtained in Example 12 were passed through a hot water bath for free shrinkage, and then made into a random web in the same manner as in Example 12, and a fiber-entangled nonwoven fabric was prepared. After the polyethylene was dissolved and removed and treated under hot air, binder resin was applied. The obtained fiber-entangled nonwoven fabric was substantially free from shrinkage.

The artificial leather obtained from this fiber-entangled nonwoven fabric had high resilience but low elasticity, and the recovery rate after 30% elongation was only 68%, resulting in structural destruction. In addition, when we enlarged and observed the state of the fibers in this fiber-entangled nonwoven fabric, we found that
There was almost no difference in tension between the fibers made of polyurethane and the fibers made of polyethylene terephthalate.

Example 13 Bicomponent fiber with a fineness of 6 denier (hereinafter referred to as fiber 1) obtained by melt-spinning 40 parts of low-density polyethylene and 60 parts of polyester polyurethane (100% elongation elastic recovery).
, and 50 parts of low density polyethylene and 5 parts of nylon-6.
Using a bicomponent fiber with a fineness of 4 denier (hereinafter referred to as fiber ■) whose sea component is polyethylene obtained by melt spinning 0 parts, 20 parts of this fiber ■ and 8 parts of fiber T1s were used.
0 parts were blended to make a cross-wrap web, which was needle-punched to obtain a fiber-entangled nonwoven fabric, which was placed on a fabric and heat-treated by passing it through a hot air dryer at 135°C. The obtained fiber-entangled nonwoven fabric has an area shrinkage rate of about 20% and an apparent density of 0.
．． 40. A part of the fiber-constituting polyethylene was fused at the fiber intersection points, resulting in a somewhat plate-like hardness. This heat-treated fiber-entangled nonwoven fabric is coated with a polyether-based polyurethane solution containing 10% dimethylformamide (however, this solution contains 1% water. By containing 1% water, the fibers are formed. The polyurethane in the solution is not attacked by the dimethylformamide solvent, and the polyurethane in the solution does not substantially coagulate. The polyethylene was dissolved and removed.

The obtained fiber-entangled nonwoven fabric was puffed with sandpaper and subjected to finishing treatments such as dyeing, softening, and brushing to obtain suede-like artificial leather.

This artificial leather has excellent napping properties and a high fluff density.
It has a great lighting effect, and is also rich in flexibility, stretchability, and a sense of fulfillment, making it a material suitable for clothing, especially sports clothing. Moreover, the condition of the internal fibers of this artificial leather was the same as in Examples 8 to 11.

<Effects of the Invention> The fiber-entangled nonwoven fabric of the present invention is composed of ultrafine fiber bundle fibers and/or modified fibers modified into fibers having micro spaces, and has excellent fiber entanglement properties and is resistant to repeated elongation deformation. A fiber that has a wide elongation range that does not substantially cause structural deformation or structural destruction even when it is stretched, and has a rich and flexible texture that is rich in elongation and is suitable as a base material for artificial leather. It is an entangled nonwoven fabric.

Furthermore, by subjecting the fiber-entangled nonwoven fabric of the present invention to a napped treatment on the surface, a highly elastic artificial leather with a suede-like surface with a high density of napped microfibers is created, and a film layer of an elastic polymer is added to the surface. By finishing with a grain layer, highly elastic silver-coated artificial leather can be obtained.

Patent applicant: RiRashi Co., Ltd. Representative Patent Attorney Ken Honda

Claims (2)

[Claims] (1) Multicomponent fiber I consisting of an elastic polymer (A) mainly composed of polyurethane elastomer and at least one type of inelastic polymer (C) that has a different solubility or degradability from the elastic polymer (A), and At least two types of inelastic polymers (B
A fiber entangled nonwoven fabric characterized in that each short fiber of multicomponent fiber II consisting of ) and (D) is mixed and entangled. (2) Modified fibers A, which are microfiber bundle fibers made of an elastic polymer (A) mainly composed of polyurethane elastomer or fibers with microscopic spaces, and modified fibers A, which are fibers with microscopic spaces, and an inelastic polymer (B).
) is a fiber-entangled nonwoven fabric formed by mixing and entangling short fibers of modified fibers B, which are ultrafine fiber bundle fibers or fibers with microscopic spaces, and in which the entangled state of the fibers in the nonwoven fabric is , a fiber entangled nonwoven fabric characterized in that modified fibers B are bent and bent by modified fibers A in a tense entangled state and entangled in a loose tissue structure.