JP3067336B2 - Method for producing leather-like material excellent in napping properties, flexibility and high strength - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a leather-like material using ultrafine acrylic fibers. More specifically, the present invention relates to a method for producing a cashmere-like leather-like material excellent in nap properties such as a feeling of volume, a feeling of sliminess, a resistance to thickness-thickness, a feeling flexibility, and a high strength.

[0002]

2. Description of the Related Art Acrylic fiber has lightness, coloring, heat retention,
The development of apparel materials that take advantage of features such as anti-pill properties and further impart high functionality has been developed mainly for knitted goods, and there are very few leather-like materials based on nonwoven fabrics using acrylic fibers. It is understood that this is due to drawbacks such as the thickness coming from the poor heat resistance of the acrylic fiber, the low strength, the cutting of the fiber during the entanglement treatment coming from the low elongation or the short napping during the raising process, These adverse effects have been promoted in the area of ultrafine fibers, and have made it difficult to develop products based on nonwoven fabrics.

On the other hand, Japanese Patent Application Laid-Open No.
Japanese Patent Application Laid-Open No. 62-78281 proposes a method in which a web of ultrafine acrylic fiber is laminated on a knitted fabric, and entanglement treatment, binder impregnation and brushing treatment are performed. Although this method is effective to obtain a high-strength and soft leather-like material, it has a short nap and lacks the feeling of volume, sliminess, drape, and flexibility. It was leather-like. Further, as an effective method of forming naps, as disclosed in JP-B-56-50031 or JP-B-57-47772,
A method in which the bundle of ultrafine fibers is bound with a curable polymer organic silicone film and the tip is brushed.
As disclosed in JP-A-42749, there is a method of impregnating an entangled sheet of ultrafine fiber bundles with a mixed solution of a high molecular weight organic silicone compound and a binder. Although these methods provide a long nap and have a slimy feeling, because of the entangled body of only acrylic fibers, softening, that is, reducing the amount of the binder applied, reduces the product strength,
In addition, lack of uniformity of the nap caused by the instability of migration of the silicone, and furthermore, it is necessary to provide a silicone film sufficient to bind the fiber bundles. There was a disadvantage that there was. Japanese Patent Publication No. 41-21475 discloses a method of impregnating an acrylic fiber with a water-added binder. This method aims to make the inside of the binder microporous, and the feeling of the product is slightly softened. It is not a technical means sufficient for imparting product characteristics such as a long nap, a nap feeling of volume, a slimy feeling, and a high strength, but is completely different from the technical idea of the present invention.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems caused when forming a leather-like material based on a nonwoven fabric entangled sheet using ultrafine acrylic fiber, and provides a cashmere excellent in product property balance. It is an object of the present invention to provide a method for producing a leather-like material.

[0005]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have finally reached the present invention. The gist of the present invention is as follows.

That is, the method of the present invention comprises laminating an ultrafine acrylic fiber web having a single-fiber fineness of 0.3 to 2.0 denier and a main length of 20 mm or more on at least one surface of a strongly twisted knitted fabric made of strongly twisted yarn. After subjecting them to three-dimensional entanglement, the entangled body is provided with an amino-modified silicone or an epoxy-modified silicone, and after heat treatment,
Applying a form fixing agent, then applying a polymer elastic body, then removing the form fixing agent, and further performing a raising treatment, which is characterized by leather-like properties excellent in napping properties, flexibility and high strength. It is a method of manufacturing a product.

In a preferred embodiment of the method of the present invention, the ultrafine acrylic fiber has a tensile elongation of 30% or more and the fiber has a coefficient of dynamic friction between yarn and yarn of 0.1 to 0.3.
The yarn-gold dynamic friction coefficient is 0.2 to 0.35 and / or the fibers constituting the strongly twisted knitted fabric are basic dyeable fibers, and the number of twists of the strongly twisted yarn is 500 T / m or more. At 4
000 T / m or less, and / or when providing an amino-modified silicone or an epoxy-modified silicone, a mixture of these silicones containing a solvent for ultrafine acrylic fibers and prepared so as not to substantially dissolve the ultrafine acrylic fibers is used. The solids content is 0.5 to 20% by fiber weight and / or the elastic polymer is a polyurethane using hydrogenated DMF as a solvent, and the mixed concentration of the hydrogenated DMF causes the polyurethane to gel. Water and DMF are mixed within a range that does not dissolve the ultrafine acrylic fiber, and / or when the amino-modified silicone or the epoxy-modified silicone is applied, a solvent for the ultrafine acrylic fiber is contained, and the ultrafine acrylic fiber is substantially dissolved. To the silicone liquid prepared in the range not to be added, A solution that can be solved by using a mixed solution and applying the solid content with the silicone / feel adjusting agent such that the solid content is 1 to 25% by weight and the application ratio is 80/20 to 50/50% by weight. It is.

[0008]

Hereinafter, the present invention will be described in detail.

The fineness of the single fiber of the ultrafine acrylic fiber used in the present invention is 0.3 to 2.0 deniers in consideration of appropriate waist of nap, surface touch and web forming property, entanglement property, and the like.
Preferably 0.5 to 1.5 denier, more preferably 0.7 to 1.0 denier. The fiber length of these fibers is mainly 20 mm or more, preferably 32 to 64 mm. A fiber length of less than 20 mm or more than 64 mm may be mixed as long as it does not unduly affect the web-forming property and the entanglement property.

The polymer forming the ultrafine acrylic fiber is preferably an acrylonitrile polymer, preferably 93
Mol% or more of acrylonitrile (AN) and a sulfonic acid group-containing vinyl monomer copolymerizable with the AN are preferably 0.1 to 0.7 mol%, more preferably 0.25 to 0.75 mol%.
A co-aggregate obtained by copolymerizing 0.45 mol and another vinyl group-containing monomer in an amount of preferably 6 mol% or less, more preferably 3 to 4.5 mol% is used. If the amount of the sulfonic acid group-containing vinyl monomer exceeds 0.7 mol%, the spinnability decreases, and if it is less than 0.1 mol%, it tends to be difficult to obtain a sufficient color-forming property, which is not preferable. These fine acrylic fibers may contain an antibacterial agent, a deodorant or an aromatic.

[0011] Such an ultrafine acrylic fiber is formed into a web using a card / cloth wrapper or the like, laminated on at least one side of a strongly twisted knitted fabric, and subjected to a three-dimensional entanglement process such as a needle punch process described later. At this time, the tensile elongation of the acrylic fiber is 30% or more, preferably 35% or more, and the yarn-yarn dynamic friction coefficient is 0.1 to 0.3, preferably 0.15 to 0.25. Kinetic friction coefficient is 0.2
It is important that it is ０．３0.35, preferably 0.2-0.3. When the tensile elongation is less than 30%, the fibers are easily cut by a needle punch or the like, the weight per unit area is remarkably reduced, the entanglement density is hardly increased, and it is difficult to obtain a high-quality entangled sheet. Also, when the yarn-yarn dynamic friction coefficient is less than 0.1 and the yarn-gold dynamic friction coefficient is less than 0.2, the fiber becomes slippery, and the fiber penetrating the knitted fabric is difficult to be entangled as if it covers the knitted fabric, If the yarn-yarn dynamic friction coefficient exceeds 0.3, or
If the gold kinetic friction coefficient exceeds 0.35, the frictional resistance between the fibers and the needles increases, and the fibers are easily cut, so that it is difficult to obtain an entangled sheet of good quality, which is not preferable. In order to maintain such a friction coefficient on the fiber, a combination of a process oil and a finish oil is important. For example, a process oil / finish oil = cationic / weak cationic, cationic / nonionic surfactant, cationic Surfactant / amino-modified silicone is preferably used.

On the other hand, as the knitted fabric used in the present invention, the number of twists of the constituting yarn is 500 T / m or more and 4000 T / m.
/ M or less, preferably 1000 T / m or more, more preferably 1500 T / m or more. At less than 500 T / m, the tightness of the single yarns constituting the yarn is insufficient, so that the single yarn is caught on the barb of the needle during needle punching, and the yarn is cut or damaged.
For this reason, the structure of the knitted fabric is destroyed, and the strength of the knitted fabric decreases as the number of punches increases, which makes it difficult to obtain a high-strength leather-like material, which is not preferable. Further, if the number of twists is too large, the fiber becomes too hard, which is not preferable from the viewpoint of softening the feeling.

As the kind of the high twist yarn to be used, filament yarn, spun yarn, innovative spun yarn, blended yarn of filament and short fiber, and the like can be used, and are not particularly limited.

The basis weight of the strong twist knitted fabric is 20 to 200 g / m ^2.
And more preferably in the range of 30 to 1
A range of 50 g / m ² is good. If the basis weight is less than 20 g / m ² , the form as a knitted fabric becomes extremely loose, and wrinkles occur during lamination with the web, making it difficult to spread uniformly. On the other hand, if the basis weight exceeds 200 g / m ² , the knitted fabric structure becomes dense, the penetration of the web-forming fibers becomes insufficient, and the knitted fabric and the web-forming fibers do not proceed to a high degree of entanglement. It becomes difficult to make sheets. The types of strong twist knitted fabrics include weft knitting represented by warp knitting and tricot knitting, lace knitting and various types of knitting based on those knitting methods, or plain knitting, twill weaving, satin weaving and their weaving methods. Any of various types of woven fabrics can be adopted, and there is no particular limitation.

Among these woven fabrics, preferred are those in which at least one of the warp and the other side is made of a strongly twisted yarn, and particularly preferred is a woven fabric of which a warp or even a highly twisted yarn is used. Is good for exhibiting high strength. Further, it is preferable that these knitted fabrics have an appropriate latent shrinkage. As a guide to the potential shrinkage,
The area shrinkage difference between the ultrafine acrylic fiber sheet and the knitted fabric in boiling water is 5 to 20%, preferably 5 to 15%. If it is less than 5%, the flexibility of the laminated entangled sheet is insufficient, and
%, Unevenness occurs in the laminated entangled sheet, and the touch on the front and back of the product becomes rough, which is not preferable.

The fibers constituting the knitted fabric include synthetic fibers such as polyesters, polyamides, acryl, polyethylene and polypropylene, and recycled fibers such as rayon and cupra rayon. Among them, polyesters and polyamides are preferably applied. It is particularly preferable to use basic dyeable fibers from the viewpoints of dyeability with ultrafine acrylic fibers and color development on the front and back of the product.

The knitting of the knitted fabric using these fibers may be performed with a single fiber fineness of 0.05 to 5 denier, more preferably 0.1 to 3 denier, and a constituent yarn of 20 to 300 denier.
More preferably, the range is 30 to 150 denier. When the single yarn fineness is less than 0.05 denier, the product strength is hardly obtained, and when the single yarn fineness exceeds 5 denier, the feeling becomes hard, which is not preferable. If the constituent yarn is less than 20 denier, wrinkles are apt to be formed during lamination with the web, and if it exceeds 300 denier, the fiber is insufficiently penetrated during the entanglement treatment, and it is easy to peel off, which is not preferable. The cross-sectional shapes of these single yarn fibers are not particularly limited.

The fibers constituting the knitted fabric may be ultrafine composite fibers such as sea-island composite fibers and splittable composite fibers such as high molecular array type fibers. In this case, it is preferable that the fiber constituting the knitted fabric is made extremely thin by a known thinning means, so that the feeling of the product can be further softened.

As the three-dimensional confounding and unifying process in the present invention, there is a needle punch, a water jet punch, or a combination thereof. In particular, the needle punch method is most suitable. The water-jet punch is capable of reducing the amount of binder and softening the web-forming fibers into the gaps between the yarns constituting the knitted fabric, and the knitted fabric and the fibers are strongly entangled with each other. It is difficult to obtain dropping flexibility with moderate rebound and volume feeling, and if the thickness of the sheet is large, the liquid flow pressure must be increased to cause insufficient entanglement of the fiber layer inside the sheet, and the surface fiber Disconnection occurs. In such a case, it is preferable to increase the entanglement to some extent with a needle punch and to entangle and smooth the surface layer portion with a water jet punch. That is, the entangled sheet of the present invention has no entanglement in which the web-forming fibers have substantially penetrated into the gaps of the knitted fabric, and is entangled as if wrapping the knitted fabric. It is presumed that this will increase the degree of flexibility and promote the flexibility of the product texture.

[0020] Before the ultrafine acrylic fiber web was laminated to a knitted or woven fabric performing needle punching, only the needle density from 50 to 800 present ultrafine acrylic fiber web / cm ^2, so that preferably the 100 to 500 present / cm ² Needle punching from one side or both sides, and then laminating on a knitted fabric, 1000-3000 needles / cm ² , preferably 1000, so that the needle density ratio of the web surface: the knitted fabric surface is 5: 1 to 1: 1.
Needle punching with a density of ２０００2000 / cm ² is preferred for integrating the knitted fabric and web, preventing wrinkles, exhibiting the napped properties of the fine acrylic fiber, and exhibiting the feeling of volume of the product. In addition, at least two sheets of the entangled sheet obtained in this way are further laminated so that the knitted fabrics are on the outside of each other, needle punching is performed, and finally a means for half-cutting is naturally considered from the viewpoint of product cost. It is.

The sheet in which the ultrafine acrylic fiber and the knitted fabric are integrated may be subjected to a shrinking treatment as required. By raising the fiber density of the ultrafine acrylic fiber and utilizing the torque restoring force and latent shrinkage of the strongly twisted knitted fabric, it is possible to further improve the nap quality and flexibility. As another case, needle punching using a knitted fabric in which a torque has been developed in advance may substantially increase the elongation of the knitted fabric and may be advantageous in imparting stretchability and the like.

In the present invention, it is more important to apply an amino-modified silicone or an epoxy-modified silicone to these entangled bodies before applying the form solid agent and the polymer elastic body. 0.5 to 2 for solid content
0% by weight, preferably 1 to 15% by weight, more preferably 4 to 10% by weight. If the coating amount is less than 0.5% by weight, the napping properties and flexibility of the product are lacking, and if it exceeds 20% by weight, the slimming feeling is excessively produced, the napping comes off, and the adhesion of the polymer elastic body becomes uneven. Absent.

In order to more effectively impart the napped properties, drapability, flexibility, and voluminous feel of the product, the silicone is mixed using a solvent for the fine acrylic fiber, and the silicone is swollen without dissolving the fine acrylic fiber. The purpose is to apply the silicone within the above-mentioned range by using a mixed solution prepared in the above range. In addition, in order to further improve the thickness resistance and napping properties of the product, the silicone is mixed using a solvent for ultrafine acrylic fiber, and the mixed liquid is prepared so as to be able to swell without dissolving the ultrafine acrylic fiber. It is preferable to use a preparation liquid further added with a feeling adjusting agent.

As the feel adjusting agent, for example, at least one kind of an acrylic resin, a melamine resin, an aqueous polyurethane resin or the like is used. It is preferable to give 25% by weight, and the application ratio is 80/20 to 50/50% by weight. If the weight ratio deviates from this range, the thickness resistance of the product and the balance of the napped properties are undesirably lost. This effect is presumed to be due to the swelling of the acrylic fiber and the effective attachment of the silicone and the hand controlling agent to the surface of the fiber.

The solvent for the acrylic fiber is not limited as long as it has a function of swelling the acrylic fiber and is compatible with water. For example, dimethylformamide, dimethylacetamide, dimethylsulfoxide, nitric acid, potassium bromide, And maleic acid. An amino-modified silicone or an epoxy-modified silicone solution is mixed using one or two or more kinds appropriately selected from these solvents,
Further, use those diluted with water. What is important here is the solvent concentration in the mixed solution. It is necessary to dissolve the acrylic fiber in the gelling point of the acrylic fiber, that is, dissolve the acrylic fiber in the above-mentioned solvent, stir while adding water therein, and treat the mixture at a solvent / water mixing ratio at the time when the solution becomes cloudy, The solvent concentration is 5 to 30%, preferably 10 to 20%.
If it is less than 5%, the durability of the softness is lacking, and if it exceeds 30%, the solvent concentration on the surface of the ultrafine acrylic fiber is temporarily increased due to the evaporation of moisture during drying, which undesirably induces the dissolution of the acrylic fiber. Therefore, a solvent having a boiling point difference not too large from water is preferable as the solvent. An amino-modified silicone or epoxy-modified silicone solution may be mixed with the mixed solution to a target amount, and the concentration may be adjusted.

The entangled sheet to which the silicone is applied adheres firmly to the fiber surface by heat treatment, and the entangled sheet is more flexible and slimy than the one simply impregnated with an amino-modified silicone or epoxy-modified silicone solution. It can give a feeling. The heat treatment temperature and the treatment time are not particularly limited as long as they are temperatures necessary for forming a film.

Thereafter, it is important to apply a morphological fixing agent to the entangled sheet. When this treatment step is reversed, the silicone adheres to the surface of the morphological fixative, the silicone falls off in the morphological fixative removal step described below, and the drape property and flexibility intended for the present invention are hardly exhibited. The nap length is shortened, and uneven adhesion of the polymer elastic body occurs due to the water repellency of the silicone.

The form-fixing agent used in the present invention includes:
For example, carboxymethylcellulose, polyvinyl alcohol, or a mixture thereof, water-soluble starches, natural pastes, and the like can be mentioned, and may be appropriately selected from the properties of the polymer elastic solution to be combined. The amount of the shape fixing agent may be determined by the balance between the amount of the silicone and the amount of the elastic polymer in the subsequent step. As a guide, the solid content is 5 to 35% by weight, preferably 5 to 35% by weight, based on the entangled sheet. 10
30% by weight. If it is less than 5% by weight, it lacks flexibility, and if it is more than 35% by weight, it causes undesired piloerection.

As the polymer elastic body, water-based polyurethane and solvent-based polyurethane used for processing general cloths and artificial leather are used. Particularly, a solvent-based polyurethane, particularly a DMF-based polyurethane, is preferably used. When using DMF-based polyurethane, D
It is important to use an MF / water mixed solvent. DMF
In the case of a single system, the ultrafine acrylic fiber is dissolved, the adhesive force between the fiber and the polymer elastic body becomes strong, and the softening of the feeling of the product is hindered. The hydrogenation rate of the solvent in the DMF / water mixture system is lower than the gelation point of polyurethane, that is, less than the hydrogenation rate at the time when water is added to a dilute solution of polyurethane dissolved in DMF to become cloudy, and the gelling of ultrafine acrylic fibers. It is important to adjust the concentration within the range above the point in order to improve the nap property and soften the texture of the product. As the polyurethane, an ester type, an ether type or a mixed type thereof is preferable.
Among them, ester type is preferred in that the range of concentration adjustment can be widened. Further, in view of the dyeability of the fine acrylic fiber, the above-mentioned polymer elastic body may be colored with a dyeable type or a pigment or the like in order to exhibit more coloring properties and a deep color feeling on the product surface. .

When impregnating the entangled sheet with the polyurethane of the DMF / water mixed solvent system, in particular, the temperature of the impregnating solution is set to 30 ° C.
Hereafter, it is necessary to carry out the reaction at preferably 25 ° C. or lower. Even in such a mixed solvent, the solubility of the ultrafine acrylic fiber is highly temperature-dependent, and is important for obtaining the product balance aimed at by the present invention.

When the elastic polymer is water-based polyurethane, it is difficult to dissolve at room temperature, for example, as a shape fixing agent.
This is achieved by using polyvinyl alcohol whose degree of saponification is adjusted so as to dissolve in the hot water range. The amount of the polymer elastic material is 5 to 25 as a solid content with respect to the entangled sheet from the viewpoint of softening the feeling of the product and the napped properties.
% By weight, preferably 10 to 20% by weight.

The entangled sheet provided with the elastic polymer is subjected to a coagulation treatment by a dry or wet method depending on the type of polyurethane, and then the morphological fixative is dissolved and removed. As a dissolving and removing method, the solution is removed by using a mangle device or a liquid jetting device in which hot water is interposed, dried, and then subjected to a raising treatment. As the means for raising the brush, those used in the production of general artificial leather can be used, and in particular, buffing with sandpaper or a combination of re-raising with a needle cloth after buffing is preferable. Further, a release resin may be slightly applied in order to adjust the nap length before performing the raising process.

The brushed product is preferably used for further enhancing the effect of the present invention by performing dyeing with a circular dyeing machine, rubbing treatment or rubbing treatment with a tumbler dryer.

As described above, the special surface modification of the fine acrylic fiber and the production method of the present invention in which the properties of the elastic polymer and the properties of the acrylic fiber are skillfully combined are employed to obtain a nonwoven fabric based on the fine acrylic fiber. It is possible to produce a cashmere-like leather-like material which is excellent not only in color development but also in napping properties, flexibility and high strength.

The coefficient of friction of the microfine acrylic fiber in the examples was measured by a radar-type friction coefficient measuring instrument according to JIS L-1015 Chemical Fiber Staple Test Method. A stainless mirror surface was used as the metal roller when measuring the yarn-gold friction coefficient.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Reference Example (Production of Entangled Sheet) Using a spinning stock solution obtained by solution-polymerizing a monomer of acrylonitrile / methyl acrylate / sodium methallylsulfonate in dimethyl sulfoxide, an ultrafine acryl having the properties shown in Table 1 Fiber staples (A), (B) and (C) were prepared.

[0038]

[Table 1]

The staples were separately passed through a card cross wrapper to produce a web having a basis weight of about 450 g / m ² . Next, the web was alternately needle-punched so that the needle density became 2000 needles / cm ² .

The obtained entangled sheet has a basis weight retention ratio of:
Staple (A) is the smallest at 64% and (B) is 75%
%, Particularly (C), showed a very high value of 96%.

In particular, the entangled sheet using the staple (A) had a large thickness because the short fibers fell off when the surface was rubbed by hand and the ultrafine acrylic fibers were cut in the punch. The entangled sheet using staples (B)
Although the basis weight retention was slightly improved, other properties were close to those of the entangled sheet using staples (A).
On the other hand, the entangled sheet using the staple (C) has no short fibers falling off, has an extremely high basis weight retention, has elasticity in the thickness direction, and is excellent as a leather-like sheet base material. Was. In addition, it was found that the effects of the tensile elongation and the dynamic friction coefficient of the ultrafine acrylic fiber were extremely large.

Example 1 A web having a basis weight of about 200 g / m ² was prepared using the ultrafine acrylic fiber staple (C) shown in the reference example. Next, this web was treated with a filament of intrinsic viscosity 0.58, 2.43 mol% of 5-sodium sulfoisophthalate (total acid content) copolymerized polyethylene terephthalate, both 50D-48F in length and width, 2500 T / twist. m
A plain woven fabric (basis weight 49 g / m ² , greige density 94 pieces / in, width 78 pieces / in) made of raw yarn with high twist yarn is uniformly spread and laminated, and the needle density on the front and back sides is 2,000 pieces / cm ^2. Needle punching was performed to obtain an entangled sheet.
The entangled sheet was subjected to a latent torque unwinding treatment in hot water at 98 ° C. and dried. Then, it is immersed in a preparation solution of an amino-modified silicone aqueous solution (manufactured by Toray Silicone Co., Ltd., product number SM8702), adjusted with a mangle so that the solid content becomes 7% by weight, dried to a constant weight, and dried at 120 ° C. Heat treatment. Next, polyvinyl alcohol (P
VA) Immerse in an aqueous solution, adjust with a mangle so that the solid content is 20% by weight with respect to the entangled sheet;
And dried to constant weight.

Next, the DMF-based polyurethane was prepared so that the mixing ratio of DMF / water was 92/8% by weight, and the liquid temperature was 24 ° C., and the solid content of the entangled sheet was 15% by weight. After being immersed in water and solidified, PVA and DMF were removed and dried in warm water. Next, the surface of the ultrafine acrylic fiber layer was raised using a sandpaper buffing apparatus, and the surface of the woven fabric layer was further rubbed to give a basis weight of 255 g / m ² , a thickness of 1.3 mm, and an apparent density of 0.196.
g / cm ³ of the green fabric was obtained. The greige was dyed with a brown dye using a jet dyeing machine.

The leather-like material thus obtained has a sharp and uniform brown raised surface and a slightly lighter brown color on the reverse side of the strongly twisted fabric on the back side. It was a cashmere-like leather-like material that was rich and sexual.

Example 2 Using the entangled sheet subjected to the latent torque unwinding treatment in Example 1, DMF and water were added to the amino-modified silicone aqueous solution used in Example 1 and the DMF / water After impregnating with a solution prepared to have a mixing ratio of 15/85% by weight and a solid concentration of 5% by weight, adjusting with a mangle so that the amount of solids adhered to the sheet becomes 6% by weight, and then drying, 120
Heat treatment was performed at 2 ° C. for 2 minutes. Next, the P used in Example 1
Immersion in VA aqueous solution, the solid content amount to the sheet is 20
The weight was adjusted with a mangle so as to obtain a weight%, and dried at 100 ° C. to a constant weight.

Next, the DMF-based polyurethane was prepared so that the mixing ratio of DMF / water was 92/8% by weight, and the liquid temperature was 24 ° C., and the solid content of the entangled sheet was 15% by weight. After being immersed in water and solidified, PVA and DMF were removed and dried in warm water. Next, the surface of the ultrafine acrylic fiber layer was raised using a sandpaper buffing apparatus, and the surface of the woven fabric layer was further rubbed to give a basis weight of 250 g / m ² , a thickness of 1.25 mm, and an apparent density of 0.2 g.
/ Cm ³ of the green fabric was obtained. This greige was dyed under the same conditions as in Example 1, dehydrated, and dried with a tumbler dryer.

The leather-like material thus obtained has a more drapeable and softer nap, the nap surface having a sharp and uniform brown surface, and the strongly twisted fabric on the back surface having a slightly lighter brown color than that of Example 1. It was a high-powered cashmere-like leather with rich nap properties such as volume and sliminess.

Example 3 Using the entangled sheet subjected to the latent torque unwinding treatment in Example 1, DMF and water were added to the mixture of the amino-modified silicone aqueous solution and the acrylic resin aqueous solution used in Example 1 for the sheet. And the mixing ratio with DMF / water is 15/85% by weight,
After impregnating with a solution prepared by adjusting the amino-modified silicone / acrylic resin solid content ratio to 60/40% by weight, adjusting the solid content to 10% by weight with respect to the sheet with a mangle, and then drying. Heat treatment was performed at 120 ° C. for 2 minutes.

Next, PVA and polyurethane were applied under the same conditions as in Example 2, and PVA and DMF were removed and dried. Next, the surface of the ultrafine acrylic fiber layer was brushed using a sandpaper buffing device, and the surface of the woven fabric layer was further rubbed to give a basis weight of 260 g / m ² , a thickness of 1.32 mm, and an apparent density of 0.19.
A greige of 7 g / cm ³ was obtained. This greige was dyed under the same conditions as in Example 1, dehydrated, and dried with a tumbler dryer.

The leather-like product thus obtained is a uniform-brown brushed surface having a drape property, flexibility, and a slimy feeling, which is richer in napping volume than in Example 2, and has a strongly twisted fabric on the back surface. It was a light cashmere-like leather with a slightly lighter brown color and less thickness.

Comparative Example 1 Using the entangled sheet subjected to the latent torque unwinding treatment in Example 1, the sheet was immersed in the same PVA aqueous solution as in Example 1, and the solid content of the sheet was 20% by weight. The mixture was adjusted with a mangle so as to be dried at 100 ° C. to a constant weight.

Next, the DMF-based polyurethane used in Example 1 was impregnated under the same conditions, immersed in water and coagulated, and then PVA and DMF were removed and dried in warm water. Next, the surface of the ultrafine acrylic fiber layer was raised using a sandpaper buffing device, and the surface of the woven fabric layer was further rubbed to give a basis weight of 250 g /
A green fabric having m ² , a thickness of 1.31 mm and an apparent density of 0.19 g / cm ³ was obtained. The greige was dyed under the same conditions as in Example 1 and dried.

The leather-like material thus obtained is similar to Examples 1, 2, and 3 in color development and strength, but has short napped hair, lacks napped properties such as sliminess and volume, and has drape and softness. It was a suede-like leather with inferior properties.

Comparative Example 2 Using the entangled sheet subjected to the latent torque unwinding treatment in Example 1, the sheet was not dissolved at a water temperature near room temperature but was immersed in a PVA solution having a high degree of saponification, which was dissolved in hot water. Then, adjust the solid content to 20% by weight with a mangle,
Dried at 0 ° C. Next, the sheet was immersed in the amino-modified silicone aqueous solution used in Example 1, adjusted with a mangle so that the solid content adhered to the sheet was 7% by weight, and dried.
Heat treatment was performed at 120 ° C. for 2 minutes.

Next, the DMF-based polyurethane used in Example 1 was impregnated under the same conditions and solidified.
VA and DMF were removed and dried. Next, the ultrafine acrylic fiber layer surface is brushed using a sandpaper buff device,
Further, the fabric layer surface was rubbed to obtain a greige fabric having a basis weight of 248 g / m ² , a thickness of 1.28 mm, and an apparent density of 0.193 g / cm ³ . The nap properties on the surface of the greige machine were such that unevenness of the nap length was partially observed. This phenomenon is presumed to be due to the fact that the surface of the ultrafine acrylic fiber when impregnated with polyurethane was not hydrophilic and was affected by the water repellency of the amino-modified silicone film. The greige was dyed under the same conditions as in Example 1 and dried.

The leather-like product thus obtained is similar in color development to Examples 1, 2, and 3, but the nap length is short overall and unevenness is generated, resulting in a feeling of sliminess and volume. It was a suede-like leather with poor nap properties, poor drape and flexibility.

[0057]

According to the present invention, the light-weight, color-forming property, heat-retaining property of acrylic fiber can be obtained by surface-modifying a highly twisted knitted fabric and ultrafine acrylic fiber and skillfully combining the properties of the acrylic fiber with the elastic polymer. Taking advantage of features such as anti-pill properties, the nonwoven fabric structure has higher strength, drapability, flexible long nap, excellent napping properties such as volume feeling and slimy feeling, and improved cashmere style with improved thickness resistance It is possible to obtain a leather-like material.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI D06M 15/643 (58) Field surveyed (Int.Cl. ⁷ , DB name) D06N 3/00-3/18 D03D 1/00 D06M 15 / 643

Claims (6)

(57) [Claims] An ultrafine acrylic fiber web having a single-fiber fineness of 0.3 to 2.0 denier and a main length of 20 mm or more is laminated on at least one surface of a strongly twisted knitted woven fabric composed of strongly twisted yarns, and three-dimensionally laminated thereon. After performing the confounding processing, the confounding processing body,
After applying amino-modified silicone or epoxy-modified silicone and heat-treating, applying a shape fixing agent, then applying a polymer elastic body, removing the shape fixing agent, and further performing a raising treatment. A method for producing a leather-like material having excellent nap properties, flexibility and high strength. 2. An ultrafine acrylic fiber having a tensile elongation of 30% or more,
And the yarn-yarn dynamic coefficient of friction of the fiber is 0.1 to 0.3;
2. The method for producing a leather-like material according to claim 1, wherein the coefficient of dynamic friction is 0.2 to 0.35. 3. The fiber constituting the strongly twisted knitted fabric is a basic dyeable fiber, and the number of twists of the strongly twisted yarn is 500 T / m or more and 4000 T / m or less. 1
Or the method for producing a leather-like product excellent in napping properties, flexibility and high strength according to item 2. 4. When applying the amino-modified silicone or the epoxy-modified silicone, use a mixed liquid of the silicone containing a solvent for the ultrafine acrylic fiber and prepared so as not to substantially dissolve the ultrafine acrylic fiber. 4. The method for producing a leather-like material according to claim 1, wherein the content is 0.5 to 20% by weight of fiber, and the napping property, flexibility and high strength are excellent. 5. The polymer elastic body is a polyurethane using hydrogenated DMF as a solvent, and water and DMF are mixed within a range where the mixed concentration of the hydrogenated DMF does not cause gelation of the polyurethane and dissolution of ultrafine acrylic fibers. 5. The method for producing a leather-like material according to claim 1, 2, 3 or 4, wherein the leather-like material is excellent in napping properties, flexibility and high strength. 6. The method of applying an amino-modified silicone or an epoxy-modified silicone, comprising a solvent for ultra-fine acrylic fibers, and further adding a feeling adjusting agent to the silicone liquid prepared so as not to substantially dissolve the ultra-fine acrylic fibers. Using the added liquid mixture, the solid content with the silicone / feel adjusting agent is 1 to 25% by weight, and the coating ratio is 80/20.
The method for producing a leather-like material according to claim 1, 2, 3, 4, or 5, which is excellent in napped properties, flexibility and high strength.