JP4992656B2 - Leather-like sheet and method for producing the same - Google Patents

Description

  The present invention relates to a leather-like sheet and a method for producing the same. More specifically, a leather-like sheet that has high-grade front and back surfaces, has high wear resistance, reduces the polymer elastic body, and can be substantially made of a fiber material, and its manufacture Regarding the method.

  Leather-like sheets such as so-called synthetic leather and artificial leather made of ultrafine fibers and a polymer elastic body have excellent characteristics not found in natural leather, and are widely used in various applications. In producing such synthetic leather or artificial leather, after impregnating a fiber sheet material with a polymer elastic body solution such as polyurethane, the fiber sheet material is immersed in water or an organic solvent aqueous solution to polymer elasticity. A method of wet coagulating the body is generally used (for example, see Patent Document 1).

  However, since a large amount of polyurethane is used to obtain strength, dimensional stability, etc., the leather-like sheet is expensive due to the raw material cost of polyurethane and the complicated manufacturing process. In addition, a water-miscible organic solvent such as N, N′-dimethylformamide is used in the step of impregnating the polyurethane, but these organic solvents are generally not preferable from the viewpoint of the working environment.

  Furthermore, it has been pointed out that an increase in the number of polymer elastic bodies tends to give a rubber-like texture, making it difficult to achieve a solid feeling similar to natural leather. In addition, the inclusion of a polymer elastic body is not preferable in terms of recyclability, which has been emphasized not only for these problems in terms of texture but also for the purpose of protecting the environment and resources in recent years. In addition, it has been pointed out that polyurethane and the like are yellowed by NOx gas, and there are various problems such as difficulty in obtaining a white suede-like sheet.

  From these viewpoints, a leather-like sheet in which a polymer elastic body such as polyurethane is reduced or substantially free is desired.

  Here, when the content of a polymer elastic body such as polyurethane is reduced, the physical properties are lowered, and particularly when the content is 5% or less, the wear resistance is significantly lowered, and the substantial It becomes difficult to obtain artificial leather that can withstand practical use. Therefore, the present inventors have found that the problem can be solved by increasing the entanglement in the ultrafine fiber nonwoven fabric (see, for example, Patent Documents 2 to 3). According to this technology, in addition to needle punching, high-pressure fluid processing at a high pressure exceeding 10 MPa can be used to highly entangle ultrafine fibers, and the amount of polymer elastic body used can be greatly reduced. Even if it is made of a fiber material, it is possible to obtain physical properties that can withstand practical use.

  However, when producing a leather-like sheet in which both sides of a woven or knitted fabric are made of non-woven fabric, it is possible to obtain advanced physical properties. On the other hand, random irregularities may be formed on the surface in accordance with the improvement of physical properties. There is a problem of lowering the commercial value of the leather-like sheet that is required.

This phenomenon occurs mainly by performing high-speed fluid treatment, and can be solved by, for example, promoting uniform entanglement with a fiber length of 15 mm or less (see, for example, Patent Document 4). However, when the fiber length is set to 15 mm or less, the fiber easily drops off due to wear, and there is a problem that it cannot contribute to the reduction of the content of the polymer elastic body, which is the original purpose. Further, in order to obtain a high-quality surface having an elegant lighting effect required for a leather-like sheet, the fiber length is preferably 20 mm or more, and thus it is difficult to achieve both.
JP 2000-336581 A JP 2005-226213 A JP 2006-70423 A JP-A-53-78373

  An object of the present invention is to provide a leather-like sheet that is excellent in wear resistance and surface quality, reduces a polymer elastic body, and can be substantially made of a fiber material, and processability in high-speed fluid processing. The object is to provide a method for producing an excellent leather-like sheet.

In order to solve the above problems, the present invention has the following configuration. That is,
1. On one surface of the woven or knitted fabric (B) having an air flow rate of 200 cc / cm ² / sec or more, the nonwoven fabric (A) composed of fibers having an average single fiber fineness of 0.0001 to 0.5 decitex constituting the surface is provided on the other side. The leather-like sheet | seat characterized by laminating | stacking the nonwoven fabric (C) of the average single fiber fineness of 0.2-1.0 dtex which comprises a back surface on the surface .
2. 2. The leather-like sheet as described in 1 above, wherein the nonwoven fabric (A) is a short fiber nonwoven fabric having an average fiber length of 2 to 10 cm.
3. 3. The leather-like sheet as described in 1 or 2 above, wherein the nonwoven fabric (C) is a short fiber nonwoven fabric having an average fiber length of 0.1 to 1.5 cm.
4). 4. The leather-like sheet according to any one of 1 to 3 above, wherein the nonwoven fabric (C) has an average single fiber fineness of 0.5 dtex or less and is larger than the average single fiber fineness of the nonwoven fabric (A).
5. 5. The leather-like sheet according to any one of 1 to 4, wherein the nonwoven fabric (A) has a larger fiber basis weight than the nonwoven fabric (C).
6). The leather-like sheet according to any one of 1 to 5, which is substantially made of a fiber material.
7). The leather-like sheet according to any one of 1 to 6, wherein the fibers constituting the nonwoven fabric (A), the woven / knitted fabric (B), and the nonwoven fabric (C) are a single material.
8). The leather-like sheet according to any one of 1 to 7, wherein the woven or knitted fabric (B) is a woven fabric.
9. The leather-like sheet according to any one of 1 to 8, wherein the nonwoven fabric (C) is a paper-made nonwoven fabric having a fiber basis weight of 10 to 50 g / m ² .
10. The leather-like sheet according to any one of the 1 to 9 fibrous basis weight of the nonwoven fabric (A) is characterized in that it is a 30 to 150 g / ^{m 2.}
11. 11. The leather-like sheet as described in any one of 1 to 10 above, wherein the fiber constituting the woven or knitted fabric is a composite fiber in which different kinds of polyester components are joined in a side-by-side type or an eccentric core-sheath type.
12 The leather-like sheet according to any one of 1 to 11 above, wherein the woven or knitted fabric is composed of a twisted yarn of 600 to 3000 T / m.
13. In the abrasion test in the Martindale method, on the surface of the nonwoven fabric (A), the weight loss when it is worn 20000 times is 20 mg or less, and the appearance when it is worn 3000 times and 20000 times is grade 3 or higher. The leather-like sheet according to any one of 1 to 12 above.
14 14. The leather-like sheet as described in any one of 1 to 13 above, comprising an ethylene-vinyl ester copolymer.
15. The manufacturing method of the leather-like sheet | seat characterized by consisting of the process of the following (1)-(3).
(1) An ultrafine fiber that can generate ultrafine fibers having an average single fiber fineness of 0.0001 to 0.5 decitex, entangled with an ultrafine fiber generating short fiber having an average single fiber fineness of 1 to 10 decitex by needle punching, and then (2) A web (A2) is obtained by generating a web (2) A woven or knitted fabric (B) having an air flow rate of 200 cc / cm ² / sec or more and a 0.2 to 1.0 dtex paper web (C2) are laminated to form a composite Step (3) of obtaining the nonwoven fabric (D) The long fiber or short fiber web (A2) and the composite nonwoven fabric (D) are laminated by high-speed fluid treatment so that the woven / knitted fabric side of the composite nonwoven fabric (D) is in the middle, and A2 15. A step of forming a surface layer derived from C and a back layer derived from C2 . 16. The method for producing a leather-like sheet as described in 15 above, wherein the web (A2) is a short fiber web having an average fiber length of 2 to 10 cm.
17. The leather-like sheet according to 15 or 16, wherein the papermaking web (C2) is a short fiber nonwoven fabric having an average fiber length of 0.1 to 1.5 cm.
18 . 18. The method for producing a leather-like sheet according to any one of 15 to 17 , wherein the air permeability of the composite nonwoven fabric (D) is 50 cc / cm ² / sec or more.
19 . 19. The method for producing a leather-like sheet according to any one of 15 to 18 , wherein in the high-speed fluid treatment, at least one treatment flow rate is 15 to 800 L / m ² .

  According to the present invention, there is provided a leather-like sheet that has high wear resistance while having a high-grade front surface and back surface, and that can be made of a fiber material substantially by reducing the polymer elastic body. Can be provided. The leather-like sheet of the present invention can be suitably used for clothing, materials, furniture and the like.

  The leather-like sheet of the present invention comprises a non-woven fabric (A) laminated on one surface of a woven or knitted fabric (B) (in the present invention, the woven fabric and the knitted fabric are collectively referred to as “woven / knitted fabric”). A nonwoven fabric (C) is laminated on the other surface. By laying the nonwoven fabric (A) and the nonwoven fabric (C) directly on the woven or knitted fabric (B), it is possible to obtain good surface quality, which is an object of the present invention. In addition, although it does not restrict | limit superimposing other nonwoven fabrics etc. on a nonwoven fabric (A) (C), it is not this limitation when the surface quality and abrasion resistance which are the objective of this invention and an effect are impaired.

  In the present invention, the nonwoven fabric (A) is preferably composed of short fibers having an average fiber length of 2 to 10 cm, but may be composed of long fibers, and is not particularly limited. Speaking only in the case of a short fiber nonwoven fabric, the average fiber length is preferably 3 cm or more, and more preferably 4 cm or more. Moreover, it is preferable that it is 8 cm or less, and it is more preferable that it is 6 cm or less. If the average fiber length exceeds 10 cm, the surface quality may be deteriorated due to the occurrence of unevenness in the short fiber nonwoven fabric manufacturing process, which may be undesirable. On the other hand, when the average fiber length is less than 2 cm, the lighting effect of the nonwoven fabric and the suede-like leather-like sheet are deteriorated. In addition, the fiber whose fiber length exceeds 10 cm or the fiber whose fiber length is less than 2 cm may be included as long as the effect of the present invention is not impaired. The content of fibers having a fiber length of more than 10 cm and fibers having a fiber length of less than 2 cm is preferably 30% or less of the fibers constituting the nonwoven fabric (A), more preferably 10% or less, and not contained at all. Most preferred.

  The average fiber length as used in the present invention refers to the number average of 300 measured fiber lengths by measuring 100 fiber lengths from each of three arbitrary locations.

  In the case of a long-fiber nonwoven fabric, the average fiber length usually exceeds 10 cm. However, a high-quality leather-like sheet can be obtained by forming a uniform nonwoven fabric by a spunbond method. However, short fiber nonwoven fabrics are preferred in terms of superior quality.

  Moreover, a nonwoven fabric (A) consists of an ultrafine fiber whose average single fiber fineness is 0.0001-0.5 dtex. The average single fiber fineness is preferably 0.001 dtex or more, more preferably 0.005 dtex or more. Moreover, Preferably it is 0.3 decitex or less, More preferably, it is 0.15 decitex or less. An average single fiber fineness of less than 0.0001 dtex is not preferable because the strength of the leather-like sheet decreases. If the average single fiber fineness exceeds 0.5 dtex, the texture of the leather-like sheet becomes stiff, the fiber entanglement becomes insufficient, the surface quality of the leather-like sheet deteriorates, and the abrasion resistance This is not preferable because a problem such as a decrease in the thickness occurs. In addition, a fiber having a single fiber fineness of less than 0.0001 dtex or a fiber having a single fiber fineness of more than 0.5 dtex may be included as long as the effects of the present invention are not impaired. The content of fibers having a single fiber fineness of less than 0.0001 dtex and fibers having a single fiber fineness of more than 0.5 dtex is preferably 30% or less of the fibers constituting the nonwoven fabric (A) in terms of numbers. Is more preferred and most preferred is not included at all.

  The average single fiber fineness referred to in the present invention is a value obtained by calculating the number average of 100 cross sections of fibers and calculating the fineness from the specific gravity of the fibers after measuring the cross section by randomly selecting 100 fiber cross sections. Is used. In addition, the value calculated | required according to JISL1015 8.14.2 (1999) is used for the specific gravity of a fiber.

  In the present invention, it is preferable that these ultrafine fibers are intertwined with each other in order to improve the wear resistance of the leather-like sheet. Most of the conventional leather-like sheets made of ultrafine fibers have a structure in which ultrafine fibers are entangled in a bundle of fibers. However, when the ultrafine fibers have a structure in which they are intertwined with each other, the form is stabilized and the wear resistance can be improved. In addition, the structure which was entangled in the state of the fiber bundle may be included in the range which does not impair the effect of this invention.

The fiber basis weight of the nonwoven fabric (A) is preferably 30 g / m ² or more, more preferably 50 g / m ² or more, and further preferably 70 g / m ² or more. Further, it is preferably 150 g / m ² or less, more preferably 120 g / m ² or less, and further preferably 100 g / m ² or less. If it is 30 g / m ² or more, the surface of the woven or knitted fabric is not conspicuously exposed, and a high-quality surface can be easily obtained. Moreover, if it is 150 g / m < ² > or less, an unevenness | corrugation is hard to be formed in the surface, and while being able to obtain a high quality surface similarly, higher abrasion resistance can be obtained.

  The fibers constituting the nonwoven fabric (A) are preferably made of an inelastic polymer. Specifically, fibers made of polyester, polyamide, polypropylene, polyethylene or the like are preferably used. Fibers excellent in rubber-like elasticity such as polyether ester fibers and polyurethane fibers such as so-called spandex are not preferable.

  The polyester is not particularly limited as long as it can be fiberized. Specifically, for example, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1,2-bis (2- Chlorophenoxy) ethane-4,4′-dicarboxylate and the like. Of these, the most commonly used polyethylene terephthalate or a polyester copolymer mainly containing ethylene terephthalate units is preferably used.

  Examples of the polyamide include polymers having an amide bond such as nylon 6, nylon 66, nylon 610, and nylon 12.

  To these polymers, inorganic particles such as titanium oxide particles may be added to the polymer in order to improve the concealability, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage materials, Antibacterial agents and the like can be added according to various purposes.

  In the present invention, the woven or knitted fabric (B) is used. Although good shape stability can be obtained by a woven fabric or a knitted fabric, a woven fabric is more preferable because the shape stability is further improved. Further, although the knitted fabric is excellent in drape, the woven fabric has better texture such as tension, waist and resilience, and therefore the leather-like sheet composed of the woven fabric has more preferable uses.

  The fiber used for the woven or knitted fabric (B) is not particularly limited, and can be used according to necessary properties such as strength, stretchability, resilience, and drapeability. Moreover, in order to prevent the irritation | stimulation by the exposure to the surface, it is preferable that it is an inelastic fiber. Here, in the leather-like sheet substantially made of a fiber material, which is a preferred embodiment in the present invention, the resilience tends to be insufficient, and in this case, different polyester components are joined to the side-by-side type or the eccentric core-sheath type. It is preferable that the composite fiber is included.

  Different polyester components mean that two or more polyesters having different physical and / or chemical properties are used. That is, the composite fiber in which different types of polyester components are joined in a side-by-side type or an eccentric core-sheath type means that two or more polyesters having different physical and / or chemical properties are side-by-side type along the fiber length direction. Or the composite fiber joined to the eccentric core-sheath type | mold is meant. Thereby, crimp can be expressed in the composite fiber due to physical or chemical factors. In view of easy expression of crimps, it is preferable to use two or more polyesters having different heat shrinkability. Thereby, crimp can be easily expressed by carrying out the relaxation process of the said composite fiber. A leather-like sheet with excellent resilience can be obtained by crimping the composite fiber. Examples of polyesters having different heat shrinkability include those having different degrees of polymerization of polymers and blends of different polymers. In the present invention, in particular, a low-viscosity polyester having an intrinsic viscosity of 0.35 to 0.45 and a high-viscosity polyester having an intrinsic viscosity of 0.65 to 0.85 are obtained in that a leather-like sheet having excellent resilience is obtained. A composite fiber is preferable. In this case, in general, the high-viscosity polyester has higher heat shrinkability than the low-viscosity polyester. If the intrinsic viscosity of the low-viscosity polyester is less than 0.35, the spinning stability is lowered, which is not preferable. On the other hand, if the intrinsic viscosity of the low-viscosity polyester exceeds 0.45, the resilience of the leather-like sheet is lowered, which is not preferable. Further, if the intrinsic viscosity of the high-viscosity polyester exceeds 0.85, the spinning stability is lowered, which is not preferable. When the intrinsic viscosity of the high-viscosity polyester is less than 0.65, the resilience of the leather-like sheet is lowered, which is not preferable. In order to obtain a leather-like sheet having excellent resilience, the intrinsic viscosity difference between the low-viscosity polyester and the high-viscosity polyester is preferably in the range of 0.20 to 0.40. As the intrinsic viscosity [η], a value measured as an orthochlorophenol solution at a temperature of 25 ° C. is used.

  The composite ratio in the case of combining two polyester components is high shrinkage component: low shrinkage component = 75 in terms of yarn-making property and dimensional homogeneity of the coil in the fiber length direction when crimping is manifested. : The range of 25-35: 65 (weight%) is preferable, and the range of 65: 35-45: 55 is more preferable.

  The composite form may be either a side-by-side type or an eccentric core-sheath type, but the side-by-side type is preferred in that a leather-like sheet having excellent resilience can be obtained.

  The average single fiber fineness of the composite fiber is not particularly limited, but is preferably 1 to 15 dtex. If it is less than 1 dtex, it is difficult to obtain a good rebound, and if it exceeds 15 dtex, the texture of the leather-like sheet tends to be hard.

  Furthermore, it is preferable that the number of twists of the multifilament used in the woven or knitted fabric is twisted to 600 T / m or more, and more preferably 800 T / m or more. It is preferably 3000 T / m or less, and more preferably 2000 T / m or less. If it is 600 T / m or more, good resilience can be obtained, but if it exceeds 3000 T / m, the texture becomes hard, which is not preferable.

  The structure of the woven or knitted fabric (B) is not particularly limited. Examples of the woven fabric include plain weave, twill weave and satin weave. In the case of knitted fabric, weft knitting and warp knitting are exemplified. Of these, a plain weave is preferable from the viewpoint of cost and smoothness, but various structures such as leno weave can be appropriately selected from the viewpoint of improving air permeability.

Further, the basis weight of the woven or knitted fabric (B) can be appropriately adjusted in accordance with the basis weight of the intended leather-like sheet, but generally, the higher the basis weight, the lower the air permeability. Therefore, within the air permeability range of the present invention. It needs to be adjusted. From the viewpoint of use, it is preferably 10 g / m ² or more and more preferably 30 g / m ² or more in the case of clothing. It is more preferably preferably at 150 g / ^{m 2} or less, 100 g / ^{m 2} or less. If the basis weight of the woven or knitted fabric (B) is less than 10 g / m ² , the form of the woven or knitted fabric (B) is unstable, the handleability deteriorates, and if it exceeds 150 g / m ² , the leather-like sheet drape is obtained. This is not preferable because the properties are lowered. Moreover, when using for furniture, a car seat, etc., it is preferable that it is 50-400 g / m < ² >. If it is less than 50 g / m ² , the sense of fulfillment is poor, and if it exceeds 400 g / m ² , the moldability tends to decrease, such being undesirable.

It is important that the air permeability of the woven or knitted fabric (B) of the present invention is 200 cc / cm ² / sec or more. It is preferably 250 cc / cm ² / sec or more, more preferably 300 cc / cm ² / sec or more, and further preferably 350 cc / cm ² / sec or more. When it is 200 cc / cm ² / sec or more, the leather-like sheet of the present invention can have a high-grade surface having high wear resistance and suppressing surface irregularities. Since the nonwoven fabric (A) having an average single fiber fineness of 0.0001 to 0.5 dtex of the present invention has low water permeability, when it is laminated, the high-speed fluid treatment preferably used for producing the leather-like sheet of the present invention is used. At this time, it is presumed that stagnant water due to poor water flow affects wear resistance and surface irregularity formation, so it is important that the woven or knitted fabric (B) is in the above-described air flow rate range. In particular, this tendency becomes more prominent as the fiber length of the non-woven fabric (A) becomes longer. For example, when the fiber length is 4 cm or more, the air permeability of the woven or knitted fabric is preferably 300 cc / cm ² / sec or more.

The upper limit of the air flow rate is not particularly limited, and is preferably as high as possible from the viewpoint of quality, but the strength of the leather-like sheet tends to decrease. Therefore, it is preferable to set the air flow rate with the required strength corresponding to the purpose of use as the upper limit. That is, the upper limit is appropriately set depending on the required strength of the composite nonwoven fabric, but is usually 1000 cc / cm ² / sec or less, for example.

  The value obtained by the JIS L 1096 8.27.1 (1999) A method (fragile type) is used as the air flow rate here. Although the upper limit of the air flow rate obtained by the method can be limited by a measuring device, the nonwoven fabric lamination knitted or knitted fabric of the present invention does not have this value as the upper limit and may exceed the measurement limit.

  The weight ratio of the woven or knitted fabric (B) in the leather-like sheet is preferably 5 to 50%, more preferably 10 to 40% of the entire leather-like sheet. When the weight ratio is 5% or more, it becomes easy to reflect the form stability and the characteristics of the woven or knitted fabric on the leather-like sheet. However, when the weight ratio exceeds 50%, the obtained leather-like sheet has a texture like a woven or knitted fabric, and it is difficult to obtain a high-grade feeling as a leather-like sheet.

  The leather-like sheet of the present invention can also be characterized as having excellent back surface quality. The nonwoven fabric (C) disposed on the back surface may be long fibers or short fibers, and examples thereof include melt blown nonwoven fabrics, spunbond nonwoven fabrics, papermaking nonwoven fabrics, and needle punched nonwoven fabrics. Among these, the nonwoven fabric (C) is preferably a short fiber nonwoven fabric in terms of excellent quality and uniformity. In this case, the average fiber length is preferably 0.1 to 1.5 cm. If the average fiber length is less than 0.1 cm, the woven or knitted fabric is likely to be exposed due to falling off, which is not preferable. On the other hand, if it exceeds 1.5 cm, it is not preferable because irregularities are easily formed on the surface and the quality is lowered.

  The fibers constituting the nonwoven fabric (C) have an average single fiber fineness in the range of 0.2 to 1.0 dtex. 0.25 dtex or more is preferable, and 0.3 dtex or more is more preferable. Moreover, 0.8 dtex or less is preferable, 0.6 dtex or less is more preferable, and 0.5 dtex or less is more preferable. If it is less than 0.2 decitex, it is difficult to obtain good surface quality, which is the effect of the present invention, even when the air permeability of the woven or knitted fabric is within the scope of the present invention. On the other hand, if it exceeds 1.0 dtex, it is not preferable because the touch becomes defective, and the entanglement defect causes peach staining and the like. When it is 0.5 dtex or less, it is more preferable in terms of excellent quality.

  Here, the average single fiber fineness of the non-woven fabric (C) is 0.5 dtex or less and is preferably larger than the non-woven fabric (A) in order to further improve the surface quality, and more preferably 1/2 or less. preferable. For example, when the average single fiber fineness of the non-woven fabric (C) is 0.2 dtex, the short fiber fineness of the non-woven fabric (A) is preferably less than 0.2 dtex, and more preferably 0.1 dtex or less. preferable. In general, there is a tendency that surface quality deterioration due to unevenness tends to occur with a decrease in fiber fineness, and therefore, the above balance is preferable from the relationship in which the surface is more important than the back surface.

  In the leather-like sheet of the present invention, the non-woven fabric (A) is present on the surface serving as the surface layer in normal applications. Conventionally, there has been a problem that this nonwoven fabric (A) tends to form irregularities in the high-speed fluid treatment preferably applied when producing the leather-like sheet of the present invention. A leather-like sheet is required to have a particularly high surface appearance quality, and if there are irregularities, its commercial value is significantly impaired. However, this problem can be solved by combining a woven or knitted fabric having an air permeability within the range of the present invention with a specific nonwoven fabric (C) within the range of the present invention. Even if any of the nonwoven fabrics (A) and (C) is missing, it is difficult to obtain a high-quality surface appearance that is an object of the present invention. For example, a leather-like sheet in which a nonwoven fabric (C) having a fineness of less than 0.2 dtex is laminated on a woven or knitted fabric having a high air flow rate laminated with a nonwoven fabric (A) is compared with the leather-like sheet of the present invention. Unevenness is formed and the surface quality is clearly inferior.

The fiber basis weight of the nonwoven fabric (C) is preferably 5 g / m ² or more, more preferably 10 g / m ² or more, and further preferably 20 g / m ² or more. Further, it is preferably 100 g / m ² or less, more preferably 50 g / m ² or less, and further preferably 40 g / m ² or less. If it is 5 g / m ² or more, the woven or knitted fabric (B) is not clear in the appearance of the back surface, and the high-grade feeling is improved. Moreover, since it becomes easy to form an unevenness | corrugation on the surface in the high-speed fluid process preferably applied when manufacturing the leather-like sheet | seat of this invention, so that the fabric weight is high, 100 g / m < ² > or less is preferable. Although the basis weight has less influence on the quality than the fineness described above, setting both the fineness and the basis weight within the preferred range of the present invention is a preferable aspect in that a higher-quality surface appearance can be obtained.

  Moreover, it is preferable that the fiber basis weight of the nonwoven fabric (A) is larger than that of the nonwoven fabric (C) in order to further improve the surface quality. In the present invention, unevenness tends to be easily formed as the fiber basis weight increases, but conversely, the fabric tends to be exposed. Therefore, in order to give priority to the quality of the surface over the back surface, the above balance is preferable.

  The material of the non-woven fabric (C) is not particularly limited, but the same material as the non-woven fabric (A) or the woven or knitted fabric (B) is used, and it is dyed that the fibers constituting the leather-like sheet are a single material. From the viewpoint of recyclability and recyclability. Here, the single material refers to a range of materials that can be dyed with the same dye at a level that does not cause a problem in practice. For example, in the case of a single polyester material, in addition to polyethylene terephthalate, polybutylene terephthalate can be dyed with disperse dyes. , Polytrimethylene terephthalate, and the like, and copolymers thereof, but not nylon 6 which causes problems in fastness. Conversely, if it is a single polyamide material, it means nylon 6, nylon 66, nylon 12, etc. that can be dyed with an acid dye, and copolymers thereof.

  The non-woven fabric (C) is preferably a wet non-woven fabric such as a melt blown non-woven fabric or a non-woven fabric, and more preferably a non-woven fabric, in that a uniform low-weight non-woven fabric can be easily produced.

  For the purpose of improving the wear resistance, the leather-like sheet of the present invention may contain a polymer elastic body. Examples of the polymer elastic body include polyurethane resin, polyvinylidene chloride resin, polyvinyl chloride resin, polyamino acid resin, polyvinyl acetate resin, ethylene-vinyl ester copolymer resin, and polyacrylic acid copolymer. Resin, polyacrylate resin, SBR, NBR and copolymers thereof. Of these, ethylene-vinyl ester copolymer resins and polyurethane resins are particularly preferable in terms of the balance between wear resistance improvement effect and flexibility, and ethylene-vinyl ester copolymer resins are preferable in terms of wear resistance improvement effects. More preferred is a polyurethane-based resin in terms of flexibility. It is preferable to combine fine particles with an ethylene-vinyl ester copolymer resin or polyurethane resin since the effect of improving wear resistance is further improved.

  Here, the ethylene-vinyl ester copolymer resin is a resin made of a copolymer containing ethylene units and vinyl ester units. Examples of the vinyl ester unit include alkyl acid vinyl esters such as vinyl isononanoate, vinyl acetate, vinyl pivalate, vinyl propionate, vinyl laurate, and vinyl butyrate. As a vinyl ester unit, you may consist of two or more types of vinyl ester units. In particular, an ethylene-vinyl acetate copolymer is preferable from the viewpoint of water resistance, alkali resistance, weather resistance, and compatibility with nonpolar materials such as synthetic fibers.

  When an ethylene-vinyl ester copolymer resin or a polyurethane resin is included, the content is preferably 0.01% by weight or more, and 0.2% by weight or more based on the total fiber weight of the leather-like sheet. It is more preferable that Further, it is preferably 10% by weight or less, more preferably 5% by weight or less, and further preferably 3% by weight or less. When the content is 0.01% by weight or more, high wear resistance can be obtained. However, when the content exceeds 10% by weight, the texture tends to become hard, which is not preferable.

  Further, it is preferable that an ethylene-vinyl ester copolymer-based resin or a polyurethane-based resin is included and fine particles are included in that higher wear resistance can be obtained. Further, by including fine particles, it is possible to obtain an effect of giving a feel such as a dry feeling or a squeaky feeling. The material of the fine particles is not particularly limited as long as it is insoluble in water, and examples thereof include inorganic substances such as silica, colloidal silica, titanium oxide, aluminum and mica, and organic substances such as melamine resin.

  The average particle diameter of the fine particles is preferably 0.001 μm or more, more preferably 0.01 μm or more, and further preferably 0.05 μm or more. Moreover, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. When the average particle diameter of the fine particles is less than 0.001 μm, it is difficult to obtain the expected effect. On the other hand, if the average particle diameter of the fine particles exceeds 30 μm, the washing durability tends to be lowered due to the dropping of the fine particles. The average particle diameter of the fine particles can be measured using a measurement method suitable for each material and size, for example, a BET method, a laser method, a dynamic scattering method, a Coulter method, or the like. In the present invention, the volume (mass) average particle diameter determined using the BET method is particularly preferable.

  The amount of these fine particles can be appropriately adjusted within a range where the effects of the present invention can be exhibited. The content of the fine particles is preferably 0.01% by weight or more of the leather-like sheet, more preferably 0.02% by weight or more, and further preferably 0.05% by weight or more. Further, it is preferably 5% by weight or less of the leather-like sheet, more preferably 3% by weight or less, and further preferably 1% by weight or less. If the content is 0.01% by weight or more, the effect of improving the wear resistance can be remarkably exhibited, and the effect tends to increase as the amount is increased. However, when the content exceeds 5% by weight, the texture of the leather-like sheet becomes hard, which is not preferable.

  Moreover, in order to obtain a soft texture and a smooth surface touch, the leather-like sheet of the present invention preferably contains a softening agent. As the softening agent, it is preferable to select one generally used for artificial leather or woven or knitted fabric according to the fiber type.

The basis weight of the leather-like sheet is preferably 130 g / m ² or more, more preferably 150 g / m ² or more, and further preferably 170 g / m ² or more. Moreover, Preferably it is 550 g / m < ² > or less, More preferably, it is 500 g / m < ² > or less, More preferably, it is 450 g / m < ² > or less. If the basis weight of the leather-like sheet is less than 130 g / m ^2, it is difficult to obtain a good rebound feeling, which is not preferable. Moreover, when the fabric weight of a leather-like sheet | seat exceeds 550 g / m < ² >, since there exists a tendency for the workability to various uses to fall, it is unpreferable. The apparent fiber density of the leather-like sheet is preferably 0.25 g / cm ³ or more, more preferably 0.29 g / cm ³ or more, and further preferably 0.30 g / cm ³ or more. Also, preferably at 0.70 g / cm ³ or less, more preferably 0.60 g / cm ³ or less, further preferably 0.45 g / cm ³ or less. If the apparent fiber density is less than 0.25 g / cm ³ , the abrasion resistance is particularly lowered, which is not preferable. On the other hand, if the apparent fiber density exceeds 0.70 g / cm ³ , the processability for various uses is lowered, which is not preferable.

  Thus, the nap-like sheet | seat of this invention obtained in this way WHEREIN: It is preferable that an external appearance is a 3rd grade or more, and a weight loss is 20 mg or less in abrasion resistance evaluation.

  The abrasion resistance evaluation referred to in the present invention is 3,000 times and 20000 times in an abrasion resistance test measured according to JIS L 1096 (1999) 8.17.5 E method (Martindale method) furniture load (12 kPa). The appearance of the test cloth after the number of times of wear was determined according to the judgment standard table of JIS L 1076 (1999) Table 2, and all are preferably grades 3 to 5. Grades 4 to 5 are more preferred for both 3000 and 20000 times. If it is less than the third grade, sufficient quality cannot be maintained, and the fifth grade is the most preferable state for evaluation. Judgment is made using the standard table of JIS L 1076 (1999) Table 2 for the judgment, and the appearance after 20000 is evaluated as the appearance after long-term use and 3000 times is evaluated as the appearance after short-term use. The reason for the evaluation at two points is that the appearance does not change greatly after 20000 times is the most important to show the stability of the form, but even if it shows an equivalent grade value at that time, it is a low grade for short-term use This is because a value may be indicated. Furthermore, in the abrasion resistance test measured according to JIS L 1096 (1999) 8.17.5 E method (Martindale method) furniture load (12 kPa), the weight loss after 20,000 cycles is preferably 20 mg or less. The following is more preferable, and 5 mg or less is more preferable. When wear loss exceeds 20 mg, fluff tends to adhere to clothes and the like in actual use, which is not preferable. On the other hand, the lower limit is not particularly limited, and a leather-like sheet of the present invention can be obtained with little wear loss.

  In addition, the leather-like sheet of the present invention is not limited to the above-described effects, but includes dyes, softeners, texture modifiers, anti-pilling agents, antibacterial agents, deodorants, water repellents, and light resistance. Functional agents such as agents and anti-mold agents may be included.

  Among leather-like sheets, what is generally called synthetic leather or artificial leather is composed of a polymer elastic body such as polyurethane and a fiber material. However, the leather-like sheet of the present invention is preferably substantially made of a fiber material in order to solve the various problems described above, such as recyclability, color development, light resistance, yellowing resistance and the like. Here, being substantially made of a fiber material means a material that does not substantially contain a polymer elastic body. The phrase “substantially free of a polymer elastic body” permits the inclusion of a polymer elastic body in a range that does not impair the effects of the present invention. Specifically, the polymer elastic body contained in the leather-like sheet is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 1% by weight or less, and quite high. Most preferably, no molecular elastic body is contained.

  Next, an example of the manufacturing method of the leather-like sheet | seat of this invention is described.

  The manufacturing method of the fiber which comprises a nonwoven fabric (A) is not specifically limited, You may spin directly, The fiber which is a fiber of a normal fineness, and can generate | occur | produce the ultrafine fiber of this invention range (ultrafine fiber generation type) Fiber) may be spun and then ultrafine fibers may be generated. Examples of the method using the ultrafine fiber generating fiber include means such as a method of removing sea components after spinning sea-island fibers and a method of spinning after splitting-type fibers. Among these, in the present invention, ultrafine fibers can be obtained easily and stably, and the structure of the leather-like sheet of the present invention can be easily achieved. It is preferable to do. Furthermore, it is more preferable to manufacture using sea-island type fibers in that ultrafine fibers made of the same material can be easily obtained. For example, it is preferable that the ultrafine fibers are made of only polyester or only polyamide.

  The sea-island type fiber here refers to a fiber in which two or more components are combined or mixed to form a sea-island state. As a method for obtaining the sea-island fiber, for example, (1) a method in which two or more polymers are blended and spun in a chip state, and (2) a method in which two or more polymers are kneaded in advance to form a chip and then spun (3) A method of mixing two or more polymers in a melted state in a spinning machine pack using a static kneader or the like, (4) Japanese Patent Publication No. 44-18369, Japanese Patent Publication No. 54-116417, etc. Examples include a method in which two or more polymers in a molten state are merged in the die using the described die. In the present invention, any method can be used for satisfactory production, but the method (4) is preferably used because the selection of the polymer is easy.

  In the method (4), the cross-sectional shape of the island fiber obtained by removing the sea-island fiber and the sea component is not particularly limited, and examples thereof include a circle, polygon, Y, H, X, W, C, and π type. Can be mentioned. Further, the number of polymer species to be used is not particularly limited. However, considering the spinning stability and dyeability, 2 to 3 components are preferable, and it is particularly composed of 2 components of sea 1 component and island 1 component. preferable. The component ratio at this time is preferably 0.3 to 0.99, more preferably 0.4 to 0.97, and more preferably 0.5 to 0.8 in terms of the weight ratio of the island component to the entire sea-island fiber. Is more preferable. When the weight ratio of the island component is less than 0.3, the removal rate of the sea component increases, which is not preferable in terms of cost. On the other hand, when the weight ratio of the island components exceeds 0.99, the island components tend to merge with each other, which is not preferable in terms of spinning stability.

  When ultrafine fibers are obtained from sea-island type fibers, the island components become the intended ultrafine fibers. The polymer used as the island component is not particularly limited, and those that can be made into fibers can be appropriately selected and used. However, the polyesters and polyamides described above are preferably used in the present invention. The polymer used as the sea component is preferably incompatible with the island component and has chemical properties that are more soluble or degradable with respect to the solvent or drug used than the sea component polymer. Depending on the selection of the polymer constituting the island component, for example, polyolefins such as polyethylene and polystyrene, 5-sodium sulfoisophthalic acid, polyethylene glycol, sodium dodecylbenzenesulfonate, bisphenol A compound, isophthalic acid, adipic acid, dodecadioic acid, A copolymerized polyester obtained by copolymerizing cyclohexylcarboxylic acid or the like can be preferably used. Polystyrene is preferable from the viewpoint of spinning stability, but a copolymer polyester having a sulfone group is preferable from the viewpoint that it can be easily removed without using an organic solvent. The copolymerization ratio of the copolymerization component in the copolymerized polyester is preferably 5 mol% or more from the viewpoint of processing speed and stability, and preferably 20 mol% or less from the viewpoint of ease of polymerization, spinning and stretching. In the present invention, a preferable combination is a combination using polyester or polyamide for the island component, or both, and a copolymer polyester having polystyrene or sulfone group for the sea component. To these polymers, inorganic particles such as titanium oxide particles may be added to the polymer in order to improve the concealing property. In addition, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storages, etc. Materials, antibacterial agents, etc. can be added according to various purposes.

  The sea-island fiber spun in this way can be drawn and crystallized. For example, after drawing an unstretched yarn, it can be stretched 1-3 stages by wet heat stretching or dry heat stretching, or both. In addition, when using split type | mold fiber, it can mainly carry out according to the manufacturing method of the above-mentioned sea-island type | mold fiber, compounding 2 or more components within a nozzle | cap | die.

  Next, the obtained ultrafine fiber generating fiber is made into a nonwoven fabric. As the method, a spunbond method can be used for long fibers, and a dry method using a card, a cross wrapper, a random web or the like, or a wet method such as a papermaking method can be used for short fibers. In the present invention, it is preferable to use a long-fiber non-woven fabric in terms of production cost, but in terms of easily achieving the structure of the leather-like sheet of the present invention, two types of entanglement methods, a needle punch method and a high-speed fluid treatment, are used. A dry method using combined short fibers is preferred. The basis weight of the leather-like sheet can be appropriately adjusted according to the amount of the fiber used for making the nonwoven fabric and the basis weight of the woven or knitted fabric to be laminated.

  In order to make the sea-island type composite fiber into a long-fiber nonwoven fabric, specifically, for example, the aforementioned polymer is discharged from the die shown in the method (4) above, and 3000 to 9000 m by an air jet method or a roller method. After stretching at a speed of / min, it can be obtained by collecting on a collection surface such as a web conveyor. At this time, if the stretching and collection are continuously performed by the air jet method, it is not necessary to open the fiber after winding up, which is preferable in terms of productivity. Here, the air jet method is a method of drawing and spinning a spun yarn with air using an ejector or air soccer.

  In addition, when using split type composite fiber, it can mainly carry out according to the manufacturing method of the above-mentioned sea-island type composite fiber by compounding two or more components in the die.

  Although the long fiber web thus obtained can be fixed by heat fusion or the like, it is preferable to perform entanglement by needle punching as will be described later.

  In addition, in the case of a short fiber nonwoven fabric, a web can be obtained from ultrafine fiber generating short fibers using a card, a cross wrapper, etc., and then entangled by performing a needle punch process described later.

The long fiber or short fiber web composed of the ultrafine fiber-generating fibers obtained as described above has a fiber apparent density of preferably 0.12 g / cm ³ or more, more preferably 0.15 g / cm, by needle punching. ³ or more, 0.30 g / cm ³ or less, more preferably 0.25 g / cm ³ or less. When the apparent fiber density is less than 0.12 g / cm ³ , fiber entanglement is insufficient, and it is difficult to obtain desired values for physical properties such as tensile strength, tear strength, and abrasion resistance of the nonwoven fabric. The upper limit of the apparent fiber density is not particularly limited, but if it exceeds 0.30 g / cm ³ , problems such as breakage of the needle needle and remaining of the needle hole are not preferable.

  Moreover, when performing needle punching, it is preferable that the average single fiber fineness of an ultrafine fiber generation type | mold fiber is 1-10 decitex, 2-8 decitex is more preferable, and 2-6 decitex is further more preferable. When the average single fiber fineness is less than 1 dtex or exceeds 10 dtex, the entanglement by the needle punch becomes insufficient, and it becomes difficult to obtain an ultrafine fiber nonwoven fabric with good physical properties.

The needle punch in the present invention is not a role as temporary fixing for obtaining simple process passability, and it is preferable to sufficiently entangle the fibers. Therefore, the driving density is preferably 100 / cm ² or more, more preferably 500 / cm ² or more, and still more preferably 1000 / cm ² or more. Moreover, it is preferable to use a 1 barb type in terms of excellent surface quality.

  The nonwoven fabric thus obtained is preferably shrunk by dry heat treatment or wet heat treatment, or both, and further densified.

  Next, ultrafine fibers are expressed from the ultrafine fiber-generating fibers by ultrafine treatment to obtain a long fiber or short fiber web (A2) made of ultrafine fibers. The long fiber or short fiber web (A2) referred to in the present invention is a precursor of the long fiber or short fiber nonwoven fabric (A), and is in a state before being sufficiently entangled to achieve the object and effect of the present invention. Say. This long fiber or short fiber web (A2) is preferably entangled between ultrafine fibers by high-speed fluid treatment to obtain a long fiber or short fiber nonwoven fabric (A). The high-speed fluid treatment may be performed after the ultrafine processing, or the high-speed fluid treatment may be performed simultaneously with the ultrafine processing. Further, high-speed fluid processing may be performed simultaneously with the ultrafine processing, and then further high-speed fluid processing may be performed. When the high-speed fluid treatment is performed at the same time as the ultrafine treatment, it is preferable to perform the high-speed fluid treatment at least after the ultrafine treatment is mostly completed in order to further promote the entanglement between the ultrafine fibers. It is more preferable to perform high-speed fluid processing after performing ultrafine processing. As will be described later, it is preferable that the long fiber or the short fiber web (A2) is made into the long fiber or the short fiber nonwoven fabric (A) and simultaneously laminated and integrated with the woven or knitted fabric because the peel strength is improved.

  The ultrafine treatment method is not particularly limited, and examples thereof include a mechanical method and a chemical method. The mechanical method is a method of making ultrafine fiber generating fibers fine by applying a physical stimulus. Specifically, for example, in addition to the method of giving an impact such as the needle punch method or the water jet punch method, a method of pressurizing between rollers, a method of performing ultrasonic treatment, and the like can be mentioned. Moreover, as a chemical method, the method of giving a change of swelling, decomposition | disassembly, melt | dissolution, etc. with a chemical | medical agent with respect to at least 1 component which comprises a sea-island type fiber, for example is mentioned. In particular, a method for producing a long fiber or a short fiber nonwoven fabric (A) with an ultrafine fiber-generating fiber using an alkali-degradable polymer as a sea component, and then treating it with a neutral to alkaline aqueous solution to make it ultrafine is organic. This is one of the preferred embodiments of the present invention because it is preferable in the working environment without using a solvent. The neutral to alkaline aqueous solution here is an aqueous solution having a pH of 6 to 14. For example, an aqueous solution containing an organic or inorganic salt and exhibiting a pH in the above range can be preferably used. Examples of the organic or inorganic salts include alkali metal salts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate and sodium hydrogen carbonate, and alkaline earth metal salts such as calcium hydroxide and magnesium hydroxide. Further, if necessary, an amine such as triethanolamine, diethanolamine, monoethanolamine, a weight loss accelerator, a carrier and the like can be used in combination. Of these, sodium hydroxide is preferable in terms of price and ease of handling. Furthermore, after the above-mentioned neutral to alkaline aqueous solution treatment is applied to the long-fiber or short-fiber nonwoven fabric, it is preferably neutralized and washed as necessary to remove residual chemicals or decomposition products and then dried. .

  As the high-speed fluid treatment, a water jet punch treatment using a water flow is preferable from the viewpoint of the working environment. In the water jet punching process, water is preferably performed in a columnar flow state. The columnar flow is usually obtained by ejecting water from a nozzle having a diameter of 0.06 to 1.0 mm at a pressure of 1 to 60 MPa. In order to obtain a nonwoven fabric with efficient entanglement and good surface quality, the nozzle diameter is preferably 0.06 mm or more and 0.15 mm or less, and the interval is preferably 5 mm or less, and the diameter is 0.08 mm or more and 0.14 mm or less, The interval is more preferably 1 mm or less. The nozzle plates of these configurations do not need to be the same when processing multiple times, for example, using a nozzle plate including nozzles with a large hole diameter and a small hole diameter, using a nozzle plate with a different structure in combination, It is also possible to use a nozzle plate outside the above range. When the diameter of the nozzle exceeds 0.15 mm, the entanglement between the ultrafine fibers decreases, the surface becomes easy to peach, and the surface smoothness also decreases. Therefore, a smaller nozzle hole diameter is preferable, but if it is less than 0.06 mm, nozzle clogging is likely to occur, and this is not preferable because the cost is increased due to the necessity of highly filtering water. Further, if the nozzle interval exceeds 5 mm, the generated streaks tend to stand out, which is not preferable. In order to achieve uniform entanglement in the thickness direction and / or to improve the smoothness of the nonwoven fabric surface, it is preferable to repeat the high-speed fluid treatment a plurality of times.

  Note that at least one process means that the process is performed by one nozzle head (one injector) including a nozzle plate having a plurality of nozzle holes. When processing is continuously performed with a plurality of nozzle heads, the number of times of the plurality of nozzle heads is processed, and the number is not counted once.

  The pressure of the fluid is appropriately selected depending on the fiber basis weight of the nonwoven fabric to be treated, and the higher the basis weight, the higher the pressure. Furthermore, it is preferable to treat at least once with a pressure of 10 MPa or more in order to highly entangle the ultrafine fibers and obtain the desired physical properties such as tensile strength, tear strength, and abrasion resistance. The pressure is more preferably 15 MPa or more, and further preferably 20 MPa or more. The upper limit of the pressure is not particularly limited, but the cost increases as the pressure increases, and in the case of a low-weight nonwoven fabric, the nonwoven fabric is likely to be non-uniform, and fluff may be generated by cutting the fibers. Is 40 MPa or less, more preferably 35 MPa or less.

In addition, in order to obtain higher strength and wear resistance, the flow rate used in high-speed fluid processing is an important factor. In the present invention, it is preferable to treat at a flow rate of 15 to 800 L / m ² at least once for the purpose of highly intertwining ultrafine fibers. More preferably 20L / ^{m 2} or more, 25L / ^{m 2} or more is more preferable. 700 L / m ² or less is more preferable, and 600 L / m ² or less is more preferable. When the flow rate is 15 L / m ² or more, there is no generation of peaches in the dyeing process, and higher wear resistance can be obtained. Moreover, although it becomes the tendency for the unevenness | corrugation of a surface to be easy to be formed by the said process simultaneously, this is a preferable aspect at the point which can suppress this with the manufacturing method of this invention and can exhibit the effect of this invention more. However, if the flow rate exceeds 800 L / m ² , the cost increases, and tearing may occur during processing, which is not preferable.

  As means for obtaining such a flow rate, the hole diameter, the hole interval, the water pressure in the chamber, and the conveyance speed of the nonwoven fabric are adjusted. The flow rate is calculated according to the following formula 1 with the hole diameter as the fluid discharge diameter.

Q: Flow rate per time (L / m ² )
di: Hole diameter (mm)
Pg: Water pressure (MPa)
p: hole interval (mm)
s: Conveying speed (m / min)
In the case of ultrafine fibers obtained from ultrafine fiber generation type fibers, it is common that the ultrafine fibers are intertwined in a bundled fiber bundle, but by performing high-speed fluid treatment under the above conditions, An ultrafine fiber nonwoven fabric in which ultrafine fibers are entangled to such an extent that entanglement due to the state of the fiber bundle is hardly observed can be obtained. Thereby, the leather-like sheet | seat which consists of a fiber material substantially can be manufactured, and surface characteristics, such as abrasion resistance, can also be improved. In addition, you may perform a water immersion process before performing a high-speed fluid process. Furthermore, in order to improve the quality of the nonwoven fabric surface, a method of relatively moving the nozzle head and the nonwoven fabric, or a method of inserting a wire mesh between the nonwoven fabric and the nozzle and performing a watering treatment can be performed.

  In addition, as a method of performing ultrafine treatment and high-speed fluid treatment at the same time, for example, a method of using sea-island fibers using a water-soluble polymer as a sea component, and removing sea components and entanglement of ultrafine fibers by a water jet punch , Using sea-island fibers using an alkali-soluble polymer as a sea component, and after decomposing the sea component through an alkali treatment liquid, performing a final removal of the sea component and entanglement treatment of ultrafine fibers by a water jet punch, Etc.

  Next, a method for producing the woven or knitted fabric (B) will be described. The manufacturing method of the fiber used for the woven or knitted fabric (B) is not particularly limited, and a known manufacturing method can be applied. For example, two or more different polyester components are combined in a side-by-side type or an eccentric core-sheath type. The method described in Japanese Patent Publication No. 63-42021, Japanese Patent Application Laid-Open No. 4-308271, Japanese Patent Application Laid-Open No. 11-43835, and the like can be applied to the method for producing the fibers. Further, by using these fibers and using a knitting machine suitable for the required structure, a woven or knitted fabric such as a woven fabric or a knitted fabric can be obtained.

  The woven fabric or the knitted fabric is not particularly limited, and any may be used. However, the woven fabric is preferable in that wrinkles due to tension are few and can be stably produced by the production method of the present invention.

  In the case of producing a woven fabric, a loom such as a shuttleless loom such as a water jet loom or an air jet loom, a fly shuttle loom, a tappet loom, a dobby loom, or a jacquard loom is not particularly limited. The air permeability can be controlled by the cover factor. When the same fiber is used, the air permeability improves as the density decreases.

  The knitted fabric may be either a weft knitting or a warp knitting. The weft knitting is manufactured by, for example, a weft knitting machine, a circular knitting machine, etc. Can do.

  Next, it is preferable that the woven or knitted fabric is subjected to a relaxation treatment and contracted as necessary to perform an intermediate setting. For example, when two or more different kinds of polyesters preferably applied to the leather-like sheet of the present invention are woven or knitted fabrics composed of composite fibers combined in a side-by-side type or an eccentric core-sheath type, crimps are expressed by a relaxation treatment. Is preferred. Even a woven or knitted fabric manufactured from the same fiber is an important process because the stretchability and the like vary greatly depending on the conditions of the relaxation treatment and the intermediate set. As the shrinkage rate increases, the air permeability tends to decrease, and is adjusted as appropriate so as to be within the air permeability range of the woven or knitted fabric of the present invention.

  When performing the relaxation treatment, it is 80 to 140 ° C., preferably 90 to 130 ° C. with a continuous spreading relaxation treatment machine such as an open soaper, relaxer, or softer, or a batch type treatment machine such as a jigger, wins, or a liquid dyeing machine. More preferably, the treatment is performed at a temperature of 105 to 120 ° C. If it is less than 80 ° C., the stretchability tends to be insufficient, which is not preferable. On the other hand, when the temperature exceeds 140 ° C., the air permeability decreases as the density increases, and it tends to be difficult to obtain the air permeability range of the present invention, which is not preferable. In addition, the relaxation process using a liquid dyeing machine makes it easy to obtain good stretch properties, and is a particularly preferable method in the present invention. Prior to the relaxation treatment using the liquid dyeing machine, it is preferable to perform the pre-shrinkage with a continuous spreading-type continuous relaxation treatment machine from the viewpoint that uniform shrinkage treatment can be performed.

  In addition, the intermediate set is generally 100 to 190 ° C., and can be appropriately set in consideration of setting properties. In the present invention, a method in which a woven or knitted fabric is contracted by a relaxation process in advance and fixed in a form by an intermediate set, and then laminated with a nonwoven fabric is preferable in terms of imparting a moderate feeling of elongation and improving surface quality. Therefore, in order to suppress thermal shrinkage of the fibers constituting the woven or knitted fabric after lamination, the intermediate set is preferably 140 ° C. or higher, more preferably 165 ° C. or higher, and further preferably 175 ° C. or higher.

  In the intermediate set, overfeeding in the vertical direction is preferable in that the stretch property in the vertical direction can be easily imparted. The overfeed rate is preferably 1% or more, and more preferably 2% or more. Moreover, it is preferable that it is 15% or less, and 10% or less is more preferable.

  Further, as described above, the nonwoven fabric (C) can be produced by any method such as a melt blow method, a spun bond method, a needle punch method, a paper making method, etc. From the viewpoint of quality, uniformity, ease of weight reduction, etc. It is preferable to manufacture by a papermaking method. As an example of the paper making method, for example, after the fibers are disaggregated with a pulper, a beater, etc., a dispersing agent is added to adjust the dispersion liquid, and a paper making web (C2) is obtained by a paper machine such as a round net or a slanted short net. Entanglement.

  Here, the nonwoven fabric (C) can be laminated with the woven or knitted fabric (B) after the paper web (C2) is entangled to form a nonwoven fabric. In this respect, it is preferable that the woven or knitted fabric (B) is entangled after being overlapped at the stage of the papermaking web (C2). That is, in the method for producing a leather-like sheet of the present invention, a paper web (C2) and a woven / knitted fabric (B) are superposed to form a composite non-woven fabric (D), and then superposed on a long fiber or short fiber web (A2). It is preferable to obtain by entanglement by fluid treatment. In the high-speed fluid treatment, the conditions applied in the method for producing the above-described long fiber or short fiber nonwoven fabric (A) are employed. Thereby, a nonwoven fabric (C) and a long fiber or a short fiber nonwoven fabric (A) are finally formed.

  In order to obtain the composite nonwoven fabric (D), a paper web (C2) is once produced, and then the woven or knitted fabric (B) is superposed and integrated by high-speed fluid treatment. A method of forming a paper web (C2) at a stretch by a paper making method can also be employed. The former is preferable in terms of ease of production, and the latter is preferable in terms of cost. In addition, the high-speed fluid treatment employed in this case does not require the above-described condition treatment performed after the short fiber web (A) is finally stacked, and the fluid pressure is preferably 1 to 10 MPa from the viewpoint of provisional entanglement. .

Here, when performing lamination by high-speed fluid treatment, the air permeability of the composite nonwoven fabric (D) greatly affects the surface quality of the leather-like sheet. In the present invention, the air permeability of the composite nonwoven fabric (D) is preferably 50 cc / cm ² / sec or more, more preferably 80 cc / cm ² / sec or more, and 100 cc / cm ² / sec or more. More preferably. When it is 50 cc / cm ² / sec or more, a problem such as poor processability due to stagnant water does not occur even under conditions preferably applied in the above-described production method of the present invention during high-speed fluid treatment, and processing is performed satisfactorily. And even better surface quality can be obtained. The upper limit is not particularly limited from the viewpoint of surface quality, but generally it should be set according to the material to be employed because it tends to decrease strength when air permeability is improved. Therefore, although it is preferable to set appropriately according to the purpose of use, it is usually 1000 cc / cm ² / sec or less.

  When obtaining a leather-like sheet having a suede-like or nubuck-like napping, it is preferable to raise the surface of the laminated sheet obtained by the above-described production method with sandpaper or a brush. Such brushing treatment is preferably performed before dyeing because the sandpaper or brush is colored when it is performed after the dyeing step described later.

  The leather-like sheet thus obtained is preferably dyed. The dyeing method is not particularly limited, and the dyeing machine to be used may be any of a liquid dyeing machine, a thermosol dyeing machine, a high-pressure jigger dyeing machine, etc., but the liquid dyeing is advantageous in that the texture of the obtained leather-like sheet is excellent. It is preferable to dye using a machine. The conditions of the dyeing process are not particularly limited, but it is preferable to perform the dyeing process at 100 to 140 ° C. for 1 to 60 minutes using a liquid dyeing machine in terms of excellent texture. The treatment time is more preferably 10 to 60 minutes. Further, from the viewpoint of keeping the surface appearance smooth and preventing smearing, the number of rotations of the dyeing machine is set as small as possible, and the nozzle used is preferably for the span rather than for the filament.

  Means for imparting a softener, resin, fine particles and the like to the leather-like sheet can be appropriately selected from a pad method, a method using a liquid dyeing machine and a jigger dyeing machine, and a spraying method. These are preferably applied after dyeing. If applied before dyeing, the effect may be reduced due to omission during dyeing or uneven dyeing may occur, which is not preferable.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.

(1) Mass per unit area, fiber apparent density The mass per unit area of webs, nonwoven fabrics, and leather-like sheets was measured by the method described in JIS L 1096 8.4.2 (1999). Further, the thickness of the web, nonwoven fabric, and leather-like sheet was measured with a dial thickness gauge (manufactured by Ozaki Mfg. Co., Ltd., trade name “Peacock H”), and the apparent fiber density was determined by dividing the basis weight value by the thickness value. . In addition, as a fiber fabric weight of a web or a nonwoven fabric, when polyvinyl alcohol was contained in addition to a fiber, the fabric weight was calculated | required from the weight of the fiber part except it.
(2) Average fiber length 100 fibers were each extracted from arbitrary three places, and fiber length was measured. The number average of 300 measured fiber lengths was determined.
(3) Average single fiber fineness After 100 cross sections were randomly selected with an optical microscope and the cross section was measured, the number average of 100 cross sections was determined. From the average value of the obtained fiber cross-sectional area and the specific gravity of the fiber, the fineness was obtained by calculation. The specific gravity of the fiber was measured based on JIS L 1015.

(4) Martindale Abrasion Test JIS L 1096 (1999) 8.17.5 After wearing 20,000 times in the abrasion resistance test measured according to E method (Martindale method) furniture load (12 kPa) In addition to evaluating the weight loss of the test cloth, the appearance after wearing 3000 times and 20000 times was graded according to the judgment standard table of JIS L 1076 Table 2.

(5) Surface quality The ratio of unevenness appearing on the leather-like sheet was visually evaluated and evaluated in three stages.

Uneven unevenness None: A, Slightly occurring: B, Mostly occurring: C
Reference example 1
A low viscosity component composed of 100% polyethylene terephthalate having an intrinsic viscosity of 0.50 and a high viscosity component composed of polyethylene terephthalate having an intrinsic viscosity of 0.75 are bonded to the side-by-side at a weight composite ratio of 50:50 and spun and stretched. A composite fiber of 56 dtex 12 filaments was obtained. This was additionally twisted at 1500 T / m, and then a plain woven fabric was woven at a woven density of 94 × 65 / 2.54 cm. Subsequently, it processed at 80-90 degreeC with the softener, and processed at 110 degreeC with the liquid dyeing machine, and obtained the textile fabric (B) of 122x87 piece / 2.54cm.
The fabric (B) obtained had a basis weight of 63.5 g / m ² and an air permeability of 367 cc / cm ² / sec.

Reference example 2
A low viscosity component composed of 100% polyethylene terephthalate having an intrinsic viscosity of 0.50 and a high viscosity component composed of polyethylene terephthalate having an intrinsic viscosity of 0.75 are bonded to the side-by-side at a weight composite ratio of 50:50 and spun and stretched. 110 dtex 24 filament composite fiber was obtained. After twisting this at 1300 T / m, a plain woven fabric was woven at a woven density of 179 × 86 pieces / 2.54 cm. Subsequently, it processed with the softener at 80-90 degreeC, and it processed at 110 degreeC with the liquid dyeing machine, and obtained the textile fabric of 256 * 109 piece /2.54cm.
The resulting fabric had a basis weight of 231 g / m ² and an air permeability of 33.2 cc / cm ² / sec.

Reference example 3
After twisting the conjugate fiber obtained in Reference Example 1 at 1500 T / m, a 2/2 twill fabric was woven at a weaving density of 118 × 110 pieces / 2.54 cm. Subsequently, it processed at 95 degreeC with the softener, and processed at 130 degreeC with the liquid dyeing machine, and obtained the textile fabric of 158 * 110 piece / 2.54cm.
The obtained fabric had a basis weight of 89.1 g / m ² and an air permeability of 157.0 cc / cm ² / sec.

Example 1
A web was prepared by passing sea island type composite short fibers having an average single fiber fineness of 3 dtex, 36 islands, and an average fiber length of 51 mm consisting of 45 parts of polystyrene as a sea component and 55 parts of polyethylene terephthalate as an island component through a card machine and a cross wrapper. . The obtained web was subjected to needle punching at a driving density of 2200 pieces / cm ² using a 1 barb type needle punching machine to obtain a composite short fiber nonwoven fabric having an apparent fiber density of 0.22 g / cm ³ . Next, it is immersed in an aqueous solution of 5% by weight of polyvinyl alcohol (PVA) having a polymerization degree of 500 and a saponification degree of 88% heated to 95 ° C. for 2 minutes, and 15% in terms of solid content with respect to the weight of the nonwoven fabric. The impregnation was carried out at the same time as the amount of adhesion was reduced. Thereafter, the nonwoven fabric was dried at 100 ° C. to remove moisture. Next, the composite short fiber nonwoven fabric was treated with tricrene at 30 ° C. until the polystyrene was completely removed, thereby expressing ultrafine fibers having an average single fiber fineness of 0.046 dtex from the composite short fibers. The ultra-thin short fiber nonwoven fabric thus obtained was split into two pieces perpendicular to the thickness direction using a standard splitting machine manufactured by Murota Manufacturing Co., Ltd., and the fiber basis weight was 112.9 g / m ² . A short fiber web (A2) was obtained.

On the other hand, the paper web (C2) made of polyethylene terephthalate having an average single fiber fineness of 0.33 dtex, a fiber length of 5 mm, and a fiber basis weight of 33 g / m ² and the woven fabric (B) prepared in Reference Example 1 were stacked, In a water jet punch machine having a nozzle head having a nozzle diameter of 0.1 mm and having a nozzle plate of 0.6 mm interval inserted, water jet punch processing is performed three times at a pressure of 9 MPa at a processing speed of 7 m / min. A composite nonwoven fabric (D) was obtained. The air permeability of the composite nonwoven fabric was 77.5 cc / cm ² / sec.

Next, the short fiber web (A2) and the composite non-woven fabric (D) are overlapped so that the woven fabric (B) is in the center, and the short fiber web (A2) is used for the 7m The treatment was performed 3 times at a pressure of 17 MPa at a treatment speed of 1 min / min, and then 3 times in the same manner from the back side (the composite fiber nonwoven fabric side). The flow rate per time at this time was 20.3 L / m ^{2 according} to Equation 1.
By these water jet punch processes, PVA is removed from the nonwoven fabric, and the ultrafine fibers of the short fiber web (A2) are entangled to form a short fiber nonwoven fabric (A). At the same time, the short fiber nonwoven fabric (A) and the composite nonwoven fabric ( D) was entangled.

  The short fiber nonwoven fabric (A) side of the laminated sheet thus obtained was subjected to raising treatment with sandpaper made of silicon carbide abrasive grains having a particle size of P500, using a wide belt sander manufactured by Kikukawa Iron Works. Furthermore, using a liquid dyeing machine, "Sumikaron Blue S-BBL200" (manufactured by Sumika Chemtex Co., Ltd.) was used and dyed with a liquid dyeing machine at 120 ° C for 45 minutes at a concentration of 20% owf. The obtained sheet was subsequently dip-niped with an ethylene-vinyl acetate copolymer water emulsion (trade name; Sumikaflex (registered trademark) 755, manufactured by Sumika Chemtex Co., Ltd.) at a wet pickup rate of 150%. It was dried to give a solid content of 1% by weight.

  The leather-like sheet thus obtained had no irregularities on the surface and was excellent in quality. The abrasion resistance of the leather-like sheet is shown in Table 1.

Example 2
The papermaking web (C2) was processed in the same manner as in Example 1 except that the average single fiber fineness was 0.66 dtex and the fiber length was 10 mm.

  The leather-like sheet thus obtained had no irregularities on the surface and was excellent in quality. Further, compared with Example 1, the quality on the back side was slightly inferior. The abrasion resistance of the leather-like sheet is shown in Table 1.

Example 3
The composite spinning device heated to 290 ° C comprises 50 parts of polyethylene terephthalate copolymerized with 8 mol% of 5-sodiumsulfoisophthalic acid as the sea component and 50 parts of polyethylene terephthalate as the island component so that the number of islands is 36 islands. It extruded from the nozzle | cap | die which arranged the flow path. The extruded yarn is cooled by a cooling device using normal temperature air, and then taken up at a speed of 5000 m / min by an ejector using normal temperature air placed at a position of 100 cm below the spinneret and moved. Filaments were stacked on a made-up deposition apparatus to produce a web. The single fiber fineness of the composite fiber obtained at this time was a circular sectional shape of 3 dtex. Next, needle punching was performed with a 1 barb-type needle at a driving density of 250 pieces / cm ^{2 on} both sides (total 500 pieces / cm ² ) to obtain a sea-island type composite long fiber nonwoven fabric with an apparent fiber density of 0.200 g / cm ^3. It was. Next, it was immersed in water heated to about 95 ° C., contracted for 2 minutes, and dried at 100 ° C. to remove moisture. The obtained sheet was immersed in an alkaline aqueous solution containing 100 g / L of sodium hydroxide and 15 g / L of a surfactant, impregnated with 112% by weight of the aqueous alkaline solution, and immediately filled with 90 ° C. steam. In the box, continuous weight loss treatment was performed with microwaves for 5 minutes, followed by washing with water and drying to obtain an ultrafine fiber web (A2) having a single fiber fineness of about 0.042 dtex.

  Next, the long-fiber web (A2) and the composite nonwoven fabric (D) obtained in the same manner as in Example 1 are stacked so that the woven fabric (B) is in the center, and then the same processing as in Example 1 is performed. As a result, a leather-like sheet was obtained. Although the quality of the obtained leather-like sheet was good, it was inferior to the leather-like sheet obtained in Examples 1 and 2.

Comparative Example 1
It processed like Example 1 except having used the composite nonwoven fabric (D-2) which made the average short fiber fineness of the papermaking web (C2) 0.11 dtex. The air permeability of the composite nonwoven fabric (D-2) at this time was 22.8 cc / cm ² / sec.
The leather-like sheet thus obtained had fine irregularities formed on the surface and was inferior to Example 1 in terms of quality. The abrasion resistance of the leather-like sheet is shown in Table 1.

Comparative Example 2
It processed like Example 1 except having used the composite nonwoven fabric (D-3) using the textile fabric obtained by the reference example 2. FIG. At this time, the air permeability of the composite nonwoven fabric (D-3) was 7.9 cc / cm ² / sec.

  The leather-like sheet thus obtained had fine irregularities formed on the surface and was inferior to Example 1 in terms of quality. The abrasion resistance of the leather-like sheet is shown in Table 1.

Comparative Example 3
The same treatment as in Example 1 was performed except that the composite nonwoven fabric (D-4) using the woven fabric obtained in Reference Example 3 was used. The air permeability of the composite nonwoven fabric (D-4) at this time was 42.6 cc / cm ² / sec.

  The leather-like sheet thus obtained had a good surface quality as compared with Comparative Example 2, but slightly formed unevenness and was inferior to Example 1 in terms of quality. there were. The abrasion resistance of the leather-like sheet is shown in Table 1.

Comparative Example 4
In Comparative Example 1, the short fiber web (A2) and the composite nonwoven fabric (D-2) are overlapped so that the woven fabric (B) is in the center, and the short fiber web (A2) is processed using a water jet punch machine. In this case, the treatment was performed three times at a pressure of 8 MPa at a treatment speed of 7 m / min, and then three times in the same manner from the back side (the composite fiber nonwoven fabric side). The flow rate per time at this time was 11 L / m ^{2 according} to Equation 1.

  The leather-like sheet thus obtained did not form fine irregularities on the surface, and there was no problem in terms of quality, but it was inferior in wear resistance. The abrasion resistance of the leather-like sheet is shown in Table 1.

  ADVANTAGE OF THE INVENTION According to this invention, although it is a leather-like sheet | seat which consists of a fiber material substantially, abrasion resistance is favorable and the leather-like sheet excellent in the resilience can be provided.

  The leather-like sheet of the present invention can be suitably used for apparel, furniture, car seats, etc. that particularly require repulsion and formability.

Claims (19)

On one surface of the woven or knitted fabric (B) having an air flow rate of 200 cc / cm ² / sec or more, the nonwoven fabric (A) composed of fibers having an average single fiber fineness of 0.0001 to 0.5 decitex constituting the surface is provided on the other side. The leather-like sheet | seat characterized by laminating | stacking the nonwoven fabric (C) of the average single fiber fineness of 0.2-1.0 dtex which comprises a back surface on the surface . The leather-like sheet according to claim 1, wherein the nonwoven fabric (A) is a short fiber nonwoven fabric having an average fiber length of 2 to 10 cm. The leather-like sheet according to claim 1 or 2, wherein the nonwoven fabric (C) is a short fiber nonwoven fabric having an average fiber length of 0.1 to 1.5 cm. The leather-like sheet according to any one of claims 1 to 3, wherein the nonwoven fabric (C) has an average single fiber fineness of 0.5 dtex or less and is larger than the average single fiber fineness of the nonwoven fabric (A). . The leather-like sheet according to any one of claims 1 to 4, wherein the fiber basis weight of the nonwoven fabric (A) is larger than that of the nonwoven fabric (C). The leather-like sheet according to any one of claims 1 to 5, which is substantially made of a fiber material. The leather-like sheet according to any one of claims 1 to 6, wherein the fibers constituting the nonwoven fabric (A), the woven / knitted fabric (B) and the nonwoven fabric (C) are a single material. The leather-like sheet according to any one of claims 1 to 7, wherein the woven or knitted fabric (B) is a woven fabric. Nonwoven (C) is leather-like sheet according to claim 1, wherein the fiber basis weight is papermaking nonwoven 10 to 50 g / ^{m 2.} The leather-like sheet according to any one of claims 1 to 9 fiber basis weight of the nonwoven fabric (A) is characterized in that it is a 30 to 150 g / ^{m 2.} The leather-like sheet according to any one of claims 1 to 10, wherein the fiber constituting the woven or knitted fabric is a composite fiber in which different kinds of polyester components are joined in a side-by-side type or an eccentric core-sheath type. The leather-like sheet according to any one of claims 1 to 11, wherein the woven or knitted fabric is composed of a twisted yarn of 600 to 3000 T / m. In the abrasion test in the Martindale method, on the surface of the nonwoven fabric (A), the weight loss when it is worn 20000 times is 20 mg or less, and the appearance when it is worn 3000 times and 20000 times is grade 3 or higher. The leather-like sheet according to any one of claims 1 to 12. The leather-like sheet according to any one of claims 1 to 13, comprising an ethylene-vinyl ester copolymer. The manufacturing method of the leather-like sheet | seat characterized by consisting of the process of the following (1)-(3).
(1) An ultrafine fiber that can generate ultrafine fibers having an average single fiber fineness of 0.0001 to 0.5 decitex, entangled with an ultrafine fiber generating short fiber having an average single fiber fineness of 1 to 10 decitex by needle punching, and then (2) A web (A2) is obtained by generating a web (2) A woven or knitted fabric (B) having an air flow rate of 200 cc / cm ² / sec or more and a 0.2 to 1.0 dtex paper web (C2) are laminated to form a composite Step (3) of obtaining the nonwoven fabric (D) The long fiber or short fiber web (A2) and the composite nonwoven fabric (D) are laminated by high-speed fluid treatment so that the woven / knitted fabric side of the composite nonwoven fabric (D) is in the middle, and A2 The process which makes the back surface layer which originates in the surface layer which originates in C2 and C2 The method for producing a leather-like sheet according to claim 15, wherein the web (A2) is a short fiber web having an average fiber length of 2 to 10 cm. The leather-like sheet according to claim 15 or 16, wherein the papermaking web (C2) is a short fiber nonwoven fabric having an average fiber length of 0.1 to 1.5 cm. The method for producing a leather-like sheet according to any one of claims 15 to 17 , wherein the air permeability of the composite nonwoven fabric (D) is 50 cc / cm ² / sec or more. In high-speed fluid treatment, a manufacturing method of the leather-like sheet according to any one of claims 15 to 18, wherein at least one treatment flow rate is 15~800L / ^{m 2.}