WO2020003866A1

WO2020003866A1 - Sheet-shaped item and manufacturing method therefor

Info

Publication number: WO2020003866A1
Application number: PCT/JP2019/021238
Authority: WO
Inventors: 邦典吉水; 勝上野; 田辺　昭大; 西村　誠
Original assignee: 東レ株式会社
Priority date: 2018-06-29
Filing date: 2019-05-29
Publication date: 2020-01-02
Also published as: KR20210022551A; CN112218982A; EP3816340A1; JPWO2020003866A1; EP3816340A4; TW202016386A

Abstract

A sheet-shaped item including ultrafine fiber bundles that are obtained by gathering a plurality of ultrafine fibers comprising a thermoplastic resin, said sheet-shaped item comprising a base material layer and a nap layer, wherein the base material layer is a fiber entanglement comprising ultrafine fiber bundles, the nap layer has a nap consisting of ultrafine fibers on at least one surface of the sheet-shaped item, and the sheet-shaped item satisfies all of the following conditions (1)-(3). (1) The average single-fiber diameter of the ultrafine fibers is 0.1μm to 10μm. (2) Among the ultrafine fibers, the average fiber length of the ultrafine fibers in the nap layer is 250μm to 500μm. (3) The surface coverage of the ultrafine fibers in the nap layer is 60% to 100%. A sheet-shaped item with a fine surface and superior glossiness is thus provided.

Description

Sheet-like material and method for producing the same

The present invention relates to a sheet-like material and a method for producing the same.

The sheet-like material mainly composed of a nonwoven fabric made of microfibers and a polymer elastic material has excellent characteristics such as high durability and uniformity that are not found in natural leather. It has been used for various purposes such as materials, interior materials, shoes and clothing. Above all, in the napped sheet-like material in which the surface of the sheet-like material is polished and the fine fibers on the surface are raised, for example, depending on its use, a material having a uniform and smooth surface is used. Proposals have been made even to those having irregularities, such as a sheet-like material having a tactile sensation close to the moist and slimy feel of nubuck as disclosed in Document 1.

Among these, as those having a uniform and smooth surface, for example, as disclosed in Patent Documents 2 and 3, having a nap surface in which microfibers at the nanofiber level are densely arranged, suitable for polishing applications A sheet is disclosed.

International Publication No. WO 2016/051711 JP 2016-47560 A JP 2015-209594 A

By the way, unlike a non-uniform sheet having unevenness as exemplified in Patent Document 1, a suede-like sheet having a smooth surface and uniform as exemplified in Patent Documents 2 and 3 is used. In order to be used for interior materials, shoes, and clothing, it has been required that the sheet-shaped material has a more glossy appearance and an elegant and excellent appearance. However, the conventional sheet-like material having a smooth and uniform surface is suitable for polishing, and therefore, the properties such as light fastness and gloss required for interior materials, shoes, and clothing are not sufficient. There was a need for excellent abrasion resistance that was not easily broken during actual use.

Accordingly, it is an object of the present invention to provide a sheet-like article having an excellent appearance, that is, the fineness and glossiness of ultrafine fibers on the surface of the sheet-like article, and the abrasion resistance are remarkably improved.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, the conventional sheet-like material for polishing purposes hit the sheet-like material because the average fiber length of the ultrafine fibers in the nap layer was short. It has been found that light is irregularly reflected, so that a sufficient glossiness cannot be obtained, and that sufficient abrasion resistance cannot be obtained because of a small amount of a polymer elastic body as a binder. In other words, in order to achieve a fine touch and excellent glossiness on the suede-like artificial leather surface, it is important that the surface coverage and the fiber length of the ultrafine fibers in the nap layer be in a specific range. In addition, they have found that it is important to set the amount of the elastic polymer in a specific range in order to achieve the wear resistance, and have reached the present invention.

The present invention is to solve the above problems.

The sheet-like article of the present invention is a sheet-like article containing an ultrafine fiber bundle formed by combining a plurality of ultrafine fibers made of a thermoplastic resin, wherein the sheet-like article comprises a base layer and a nap layer, and The material layer is a fiber entangled body made of the ultrafine fiber bundle, and the nap layer has nap made of only the ultrafine fiber on at least one surface of the sheet-like material, and has the following conditions (1) to ( Satisfies all of 3).
(1) The average single yarn diameter of the ultrafine fibers is 0.1 μm or more and 10 μm or less.
(2) Among the ultrafine fibers, the average fiber length of the ultrafine fibers in the nap layer is 250 μm or more and 500 μm or less.
(3) The surface coverage of the ultrafine fibers in the nap layer is 60% or more and 100% or less.

According to a preferred aspect of the sheet-like material of the present invention, the sheet-like material is composed of the ultrafine fiber bundle and a polymer elastic body, and the polymer elastic body is provided inside the fiber entangled body. It is contained.

According to a preferred embodiment of the sheet-like material of the present invention, the ultrafine fiber bundle is composed of at least 10 fibers / bundle and at most 400 fibers / bundle.

According to a preferred embodiment of the sheet material of the present invention, the CV value (coefficient of variation) of the average fiber length of the ultrafine fibers in the nap layer is 30% or less.

According to a preferred embodiment of the sheet material of the present invention, the amount of the polymer elastic body applied to the ultrafine fibers is more than 0% by mass and 60% by mass or less.

The method for producing a sheet-like material of the present invention is a method for producing the above-mentioned sheet-like material, wherein the silicone-based lubricant is applied in an amount of 0.01% by mass or more and 3.0% by mass or less based on the mass of the sheet-like material. After that, a buffing process is performed on the product surface in a state where the sheet material is dried.

According to a preferred embodiment of the method for producing a sheet-like material of the present invention, the amount of grinding when buffing the product surface is 20 g / m ² or more and 250 g / m ² or less.

According to a preferred embodiment of the method for producing a sheet-like material of the present invention, the number of times of the buffing treatment of the product surface is performed in multiple stages of at least two or more, and the number of sandpaper is gradually reduced or the same. To

According to a preferred embodiment of the method for producing a sheet-like material of the present invention, among the ASTM D4158-08 (2016) "Standard \ Guide \ for \ Abrasion \ Resistance \ of \ Textile \ Fabrics \ (Uniform \ Abrasion)" (paper abrasion resistance evaluation method) The number of tears of sifter abrasion measured with a count of 180 and a load of 2 pounds is 20 times or more per 0.10 mm thickness of the sheet.

According to the present invention, by setting the surface coverage and the fiber length of the ultrafine fibers in the napped layer within the above ranges, an elegant appearance suitable for applications such as interior materials, shoes, and clothing, that is, the surface of a sheet-like material The density and glossiness of the ultrafine fibers can be remarkably improved, and a sheet having excellent abrasion resistance in actual use can be obtained.

FIG. 1 is a conceptual diagram illustrating a method for measuring the average fiber length of ultrafine fibers in a nap layer of a sheet-like material according to the present invention.

こと By doing so, the appearance quality of the sheet-like material can be made excellent in the denseness and glossiness of the above-described ultrafine fibers. Hereinafter, the configuration of the sheet-like material according to the present invention will be described in detail.

(Thermoplastic resin)
In the sheet-like material of the present invention, ultrafine fibers made of a thermoplastic resin constituting the sheet-like material are, for example, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyester such as polytrimethylene terephthalate and polylactic acid, and polyamides. 6, polyamide 66, polyamide 12, and the like; polyolefins such as acrylic, polyethylene, and polypropylene; and melt-spinnable resins such as polyphenylene sulfide (PPS) and thermoplastic cellulose. Among them, polyester is preferably used from the viewpoint of strength, dimensional stability and light resistance. From the viewpoint of environmental consideration, fibers obtained from recycled materials or plant-derived materials can also be used. Polycondensation polymers represented by polyesters and polyamides constituting fibers are often used because of their high melting points and excellent heat resistance to heat. Furthermore, it is also allowed that ultrafine fibers of different materials are mixed.

According to the desired physical properties of the sheet, inorganic particles such as titanium oxide particles, a lubricant, a pigment, a heat stabilizer, an ultraviolet absorber, a conductive agent, a heat storage agent, an antibacterial agent, etc. are added to the thermoplastic resin. Is also a preferred embodiment.

(Microfiber)
In the present invention, it is important that the average single yarn diameter of the ultrafine fibers is 0.1 μm or more and 10 μm or less. By setting the average single yarn diameter to 10 μm or less, preferably 8.0 μm or less, and more preferably 7.0 μm or less, a sheet-like material having a dense and soft touch with excellent surface quality can be obtained. Further, the number of naps per unit area of the surface on which the nap layer is formed is increased, and a smoother surface can be obtained.

Further, by setting the average single yarn diameter of the ultrafine fibers to 0.1 μm or more, preferably 1.0 μm or more, the sheet becomes a sheet having high single fiber strength and rigidity. It has excellent effects on fiber dispersibility during napping treatment such as grinding, and ease of handling.

In the present invention, the average single yarn diameter of the ultrafine fibers adopts a value measured as follows.
(A) A scanning electron microscope (SEM) photograph of the surface of the sheet is taken.
(B) 100 ultrafine fibers are randomly selected and the diameter of 100 single yarns is measured.
(C) The arithmetic mean value of the 100 measured values is calculated, rounded to the second decimal place, and used as the average single yarn diameter.

However, when the ultrafine fiber has an irregular cross section as described later, the average single yarn diameter of the fiber is calculated by calculating the diameter and area of a circumscribed circle of the fiber cross section, and calculating the actual area of the fiber cross section with respect to the area of the circumscribed circle. The equivalent diameter calculated from the ratio is adopted.

In addition, the cross-sectional shape of the ultrafine fibers in the present invention may be, in addition to a round cross-section, an elliptical shape, a flat shape, a triangular shape such as a polygon, a fan shape, or a cross shape such as a cross shape in accordance with the characteristics of a desired sheet-like material. it can.

In the present invention, the ultrafine fibers constituting the fiber entangled body take the form of an ultrafine fiber bundle formed by combining a plurality of ultrafine fibers. The form of the ultrafine fiber bundle in which a plurality of the ultrafine fibers are combined refers to a so-called bundle-like state in which a plurality of the ultrafine fibers are present in contact at least in part. The particles may be bonded to each other by fusing, or may be aggregated.

では In the present invention, the number of fibers in the ultrafine fiber bundle is preferably from 10 / bundle to 400 / bundle, more preferably from 15 / bundle to 200 / bundle. When the number of fibers is less than 10 fibers / bundle, the fineness of the ultrafine fibers is poor, and for example, mechanical properties such as abrasion tend to decrease. When the number of fibers is more than 400 fibers / bundle, the spreadability at the time of raising the hair is reduced, and the fiber distribution on the raised hair tends to be uneven.

(Sheet-like material)
The sheet material of the present invention comprises a base material layer and a napped layer. The substrate layer is a fiber entangled body made of the ultrafine fiber bundle. The nap layer has nap made of only the ultrafine fibers on at least one surface of the sheet-like material.

において In the present invention, it is important that the average fiber length of the ultrafine fibers in the nap layer is 250 μm or more and 500 μm or less. Here, in order to quantitatively evaluate the index of the glossiness, the present inventors focused on the average fiber length constituting the nap layer. To be glossy means to have a surface with a high mirror reflectance of light, and to mean that the napped layer surface is smooth. Therefore, if the fiber length is long, the glossiness tends to be excellent. On the other hand, if the average fiber length of the ultrafine fibers constituting the nap layer is 500 μm or more, the ultrafine fibers are too long, and undesirably deteriorates the quality. When the thickness is 250 μm or less, the smoothness of the napped layer surface is poor, and light is irregularly reflected on the napped layer surface. When the average fiber length of the ultrafine fibers constituting the nap layer is 250 μm or more and 500 μm or less, preferably 300 μm or more and 400 μm or less, a sheet-like material excellent in glossiness can be obtained.

The average fiber length (μm) of the ultrafine fibers in the nap layer is a value measured as follows, as shown in the conceptual diagram of FIG.
(A) Using a lint brush, align the nap fibers with the barbs.
(B) A cross-sectional SEM image of the sheet is taken at a magnification of 40 ×.
(C) In the SEM image, a line L is drawn at the root of the ultrafine fibers in the non-woven fabric, and when the fiber bundle is formed, the upper limit where the fiber bundle exists.
(D) Draw a line U at the upper limit where the fiber closest to the observation surface is napped.
(E) Draw a plurality of lines Pn (P1, P2, P3,... P15) parallel to the thickness direction at intervals of 200 μm.
(F) Measure the length of the line segment from L to U on each line Pn.
(G) The lengths of the line segments on each of the nine different lines Pn are obtained, and their arithmetic average values are obtained.
(H) This operation is performed at ten selected places of the sheet.
(I) Each arithmetic average value is further arithmetically averaged and rounded to the second decimal place to obtain the average fiber length (μm) of the ultrafine fibers in the nap layer.

Further, by setting the CV value of the average fiber length of the ultrafine fibers in the napped layer to 30% or less, more preferably 25% or less, the above-mentioned glossiness can be sufficiently exhibited. The CV value of the average fiber length of the ultrafine fibers referred to here is obtained by calculating the arithmetic average value and the standard deviation by measuring the above average fiber length, and expressing the value obtained by dividing the standard deviation by the average value as a percentage (%). This indicates that the smaller the value, the more uniform.

In the present invention, it is important that the surface coverage of the ultrafine fibers in the nap layer is 60% or more and 100% or less. By setting the surface coverage to 60% or more, preferably 65% or more, it is possible to obtain a sheet-like material having a dense nap, an elegant surface appearance, an extremely soft surface touch, and less likely to lose fibers. Can be. The surface coverage was determined by enlarging the nap surface to an observation magnification of 30 to 70 times so that the presence of the nap fiber could be confirmed by SEM, and using image analysis software to calculate the ratio of the total area of the nap portion to a total area of 4 mm ² Calculated and defined as nap coverage. The ratio of the total area can be calculated by performing a binarization process on the photographed SEM image using the image analysis software “ImageJ” and setting the napped portion and the non-napped portion to a threshold value of 100. In the calculation of the nap coverage, when a substance that was not nap was calculated as nap and greatly affected the nap coverage, the image was manually edited and the portion was calculated as a non-nap portion.

As the image analysis system, the above-mentioned image analysis software “ImageJ” is exemplified. However, if the image analysis system is composed of image processing software having a function of calculating a specified pixel area ratio, the image analysis software It is not limited to “ImageJ”. It should be noted that the image processing software “ImageJ” is a commonly used software and was developed by the National Institutes of Health. The image processing software “ImageJ” has a function of specifying a necessary area in a captured image and performing pixel analysis.

シート The sheet material of the present invention is preferably composed of the ultrafine fiber bundle and a polymer elastic body, and the polymer elastic body is preferably contained inside the fiber entangled body.

That is, it is preferable to contain more than 0% by mass and 60% by mass or less of a polymer elastic body based on the mass of the ultrafine fibers of the fiber entangled body. By containing more than 0% by mass, preferably 3% by mass or more of the polymer elastic body with respect to the mass of the ultrafine fibers, it becomes possible to impart appropriate compression characteristics to the sheet-like material. In addition, the mass of the polymer elastic body in consideration of excellent abrasion resistance should be more than 20% by mass, preferably 25% by mass or more based on the mass of the ultrafine fibers of the fiber entangled body. Thereby, it becomes possible to impart appropriate compression characteristics and wear resistance to the sheet-like material. When the mass of the polymer elastic body is more than 60% by mass, the fiber opening property in the napping step becomes poor, and the flexibility of the sheet-like material may decrease.

場合 Furthermore, when the sheet-like material is used after being dyed, there is a difference in the color tone between the fiber of the fiber entangled body after dyeing and the elastic polymer, so that it may be preferable that the amount of the elastic polymer is smaller. On the other hand, from the viewpoint of environmental consideration, it is not preferable to excessively contain the elastic polymer because the amount of the organic substance used in the production process increases, and the less the elastic polymer, the less the recycled material or the plant-derived material. When the obtained fiber is used, it is easy to recover and collect and to dispose.

The above polymer elastic body, if necessary, pigments such as carbon black, dyes, fungicides and antioxidants, ultraviolet absorbers, light stabilizers such as light stabilizers, flame retardants, penetrants and lubricants, Antiblocking agents such as silica and titanium oxide, water repellents, viscosity modifiers, surfactants such as antistatic agents, defoamers, fillers such as cellulose, and coagulation regulators, and inorganics such as silica and titanium oxide Particles and the like can be contained.

Examples of the elastic polymer used in the present invention include polyurethane elastomer, polyurea, polyacrylic acid, ethylene / vinyl acetate elastomer, acrylonitrile / butadiene elastomer and styrene / butadiene elastomer, polyvinyl alcohol, and polyethylene glycol. From the viewpoints of properties and compressive properties, polyurethane elastomers are preferably used. A plurality of polymer elastic bodies can be contained in the polymer elastic body.

ポリウレタン Polyurethane-based elastomers particularly preferably used in the present invention include polyurethane and polyurethane-polyurea elastomers.

In the sheet-like material of the present invention, the sandpaper has a count of 180 pounds in ASTM D4158-08 (2016) “Standard—Guide—For—Abrasion—Resistence—of—Textile—Fabrics” (Uniform—Abrasion), with a load of 180 pounds of sandpaper. It is important that the number of times of tearing of the seafar measured by the above is 20 or more per 0.10 mm thickness of the sheet. By setting the number of times of tearing abrasion per 0.10 mm of the sheet material to 20 times or more, preferably 25 times, and more preferably 35 times or more, a sheet material excellent in tear resistance is obtained.

The number of breaks of seafar abrasion (times / 0.10 mm) was determined using a seafarer abrasion test under the condition of a friction surface (φ50 mm) on the napped layer side of the sheet-like material and a sandpaper of 180 grit with a load of 2 pounds. Abrasion test is performed using a machine, the number of times until the sheet-like material tears limit is activated, and the abrasion tester stops, is divided by the thickness of the sheet-like material, and the number of seafar wear tears per 0.10 mm thickness (Times / 0.10 mm).

(Production method of sheet material)
The method for producing the sheet-like material will be described in more detail below.

(A) Step of forming fiber entangled body composed of ultrafine fiber-generating fibers In the method for producing a sheet-like material of the present invention, it is preferable to first form a fiber entangled body composed of ultrafine fiber-generating fibers. By doing so, it is possible to easily form a fiber entangled body in which the ultrafine fiber bundle is entangled, as compared with the case where the fiber entangled body is directly formed from the ultrafine fibers.

海 As the ultrafine fiber-generating fibers, sea-island fibers are particularly preferable. The sea-island type composite fiber is a sea-island type composite fiber in which two components, a sea component and an island component, are mutually arranged and spun using a sea-island type composite mouthpiece, or a mixed spinning in which the two components of a sea component and an island component are mixed and spun. There are fibers and the like. Among these sea-island fibers, a highly controlled ultrafine fiber is obtained, and a sufficiently long ultrafine fiber is obtained, which also contributes to the strength of a nonwoven fabric and a sheet-like material having the nonwoven fabric. Therefore, sea-island type composite fibers are preferably used.

In the sea-island composite fiber, the ratio of the sea component and the island component is preferably such that the mass ratio of the island fiber to the sea-island composite fiber is 0.2 to 0.9, and 0.2 to 0.8. Is a more preferred embodiment. By setting the mass ratio to 0.2 or more, the removal rate of sea components is reduced, and the productivity is improved. Further, it is preferable that the mass ratio be 0.9 or less, since the openability of the island fibers can be improved and the merging of the island components can be prevented.

島 In the sea-island composite fiber, the island component that becomes an ultrafine fiber in the process described later is as described for the thermoplastic resin. On the other hand, as the sea component, polyethylene, polypropylene, polystyrene, copolymerized polystyrene, copolymerized polyester obtained by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, and the like, polylactic acid, and the like can be used. It is preferable to use polystyrene or copolymerized polystyrene as a sea component in order to express high shrinkage in the densification shrinkage treatment described later.

In order to form a fiber entangled body composed of the above-mentioned ultrafine fiber-generating fibers, it is preferable to form a nonwoven fabric of the ultrafine fiber-generating fibers. By doing so, the surface quality of the sheet material can be improved when the raising process, which is a subsequent step, is performed.

As the nonwoven fabric, a nonwoven fabric obtained by a papermaking method, a short fiber obtained by applying a needle punch or a water jet punch after forming a laminated web using a card and a cross wrapper with short fibers, and a spun bonding method It can be appropriately selected from long-fiber nonwoven fabrics obtained by melt blowing or the like in accordance with desired characteristics, but short-fiber nonwoven fabrics are preferably used in terms of texture and quality.

繊維 In the short-fiber nonwoven fabric, the fiber length of the ultrafine fiber generating fiber is preferably 8 mm or more and 90 mm or less. By setting the fiber length to 8 mm or more, a sheet-like material having excellent wear resistance due to entanglement can be obtained. Further, by setting the fiber length to 90 mm or less, a sheet-like material having excellent compression characteristics and surface quality can be obtained. The fiber length is more preferably 25 mm or more and 90 mm or less. Note that fibers having a fiber length of less than 8 mm are less likely to be entangled, and fibers fall off during the manufacturing process of the sheet. Further, fibers longer than 90 mm are excellent in entanglement, but tend to have poor abrasion resistance and poor surface quality when a nap layer is formed.

ニードル In the needle used for the needle punching process, the number of needle barbs (cutting) is preferably one or more and nine or less. By using one or more needle barbs, efficient intertwining of fibers becomes possible. On the other hand, fiber damage can be suppressed by setting the number of needle barbs to nine or less.

The number of punches is preferably not less than 1000 pieces / cm ^{2 and not} more than 6000 pieces / cm ² . By setting the number of punching pieces to 1000 pieces / cm ² or more, denseness can be obtained, and high-precision finishing can be obtained. On the other hand, by setting the number of punches to 6000 / cm ² or less, it is possible to prevent deterioration in workability, fiber damage and strength reduction.

場合 In addition, when performing the water jet punching treatment, it is preferable to perform the water in a columnar flow state. Specifically, in a preferred embodiment, water is ejected from a nozzle having a diameter of 0.05 mm to 1.0 mm at a pressure of 2 MPa to 60 MPa.

Apparent density of the constructed nonwoven microfine fiber-forming fibers after needle punching or water jet punching is preferably 0.15 g / cm ³ or more 0.45 g / cm ³ or less. By setting the apparent density to 0.15 g / cm ³ or more, a nonwoven fabric having excellent morphological stability and dimensional stability can be obtained, and the occurrence of processing unevenness and scratch defects due to elongation of the polishing cloth during polishing can be suppressed. . On the other hand, by setting the apparent density to 0.45 g / cm ³ or less, a sufficient space for providing the elastic polymer can be maintained between the fibers.

不織布 From the viewpoint of densification, the nonwoven fabric composed of the ultrafine fiber-generating fibers obtained as described above can be shrunk by dry heat or wet heat or both to further increase the density. Further, it can be compressed in the thickness direction by calendering or the like.

(B) Step of Laminating and Integrating Fiber Entangled Body and Reinforcing Layer The sheet-like material of the present invention can include a reinforcing layer in the inner layer portion or the surface thereof for the purpose of improving the strength, etc. Thereafter, a step of laminating and integrating this reinforcing layer may be performed. As the reinforcing layer, a woven fabric, a knitted fabric, a nonwoven fabric (including paper), and a film-like material such as a plastic film or a metal thin film sheet can be used.

織物 In the case of a woven or knitted fabric in which the reinforcing layer is made of fibers, synthetic fibers made of polyester, polyamide, polyethylene, polypropylene, or a copolymer thereof are preferably used as the yarns. Among them, synthetic fibers composed of polyester, polyamide and their copolymers can be preferably used singly or in combination or in combination. Further, as a yarn constituting a woven or knitted fabric, a filament yarn, a spun yarn, a blended yarn of a filament and a short fiber, or the like can be used. In addition, the average single fiber diameter of the fibers constituting these yarns is preferably 0.1 μm or more and 20 μm or less from the viewpoint of the texture of the sheet.

ニードル When the needle punching step is applied as the lamination and integration step, the sheet-like material may be cut by a needle depending on the thread type of the woven or knitted material and the strength of the sheet-like material may be reduced. As means for suppressing this, it is preferable that the yarn type of the yarn constituting the woven or knitted fabric is a twisted yarn.

In the case where the yarn constituting the woven or knitted fabric is a twisted yarn, if the number of twists is 500 T / m or less, the single fibers constituting the yarn are insufficiently squeezed, so that the yarn is easily caught and damaged. . Further, if the number of twists is too large, the twisted yarn becomes too hard, and the feeling of the sheet-like material does not become flexible, which is not preferable. Therefore, the number of twists of the twisted yarn is preferably 500 T / m or more and 4500 T / m or less, more preferably 1000 T / m or more and 4000 T / m or less, and still more preferably 1500 T / m or more and 4000 T / m or less. Preferably it is 2000 T / m or more and 4000 T / m or less.

In addition, with regard to the fineness of the yarn constituting the woven or knitted fabric (total fineness in the case of a multifilament), if the fineness is 200 dtex or more, the basis weight of the woven or knitted fabric as the reinforcing layer and the basis weight of the sheet-like material are large. Become. As a result, the rigidity of the sheet is increased, and it is difficult to obtain sufficient flexibility as a sheet used for applications such as interior materials, shoes, and clothing. Therefore, it is preferably 30 dtex or more and 150 dtex or less, and more preferably 50 dtex or more and 130 dtex or less. In addition, the average single fiber fineness of the single fibers constituting the yarn constituting the woven or knitted fabric used in the present invention can be 1 dtex or more and 10 dtex or less, and ultrafine fibers having a single fiber fineness of 0.001 dtex or more and 1 dtex or less can be obtained. It can also be used.

Further, the woven or knitted fabric used in the present invention is a conjugate fiber in which two or more types of polymers are conjugated in a side-by-side type or an eccentric core-sheath type (hereinafter sometimes referred to as a “side-by-side or other conjugate fiber”). Can also be used. For example, in a composite fiber such as a side-by-side type composed of two or more polymers having a difference in intrinsic viscosity (IV), different internal strains occur between the two components due to stress concentration on the high viscosity side during stretching. Due to this internal strain, the high-viscosity side largely shrinks due to the difference in elastic recovery rate after stretching and the difference in heat shrinkage in the heat treatment step, and strain is generated in the single fiber, so that a three-dimensional coil-type crimp can be developed. .

織物 Further, examples of the woven fabric used in the present invention include plain woven, twill woven, satin woven and various woven fabrics based on their woven structures. Further, as the knitted fabric, any of a knitted fabric represented by warp knitting and tricot knitting, a lace knitted fabric, and various knitted fabrics based on these knitting structures can be adopted. Among them, a woven fabric is preferred from the viewpoint of processability, and a plain woven fabric is particularly preferably used in terms of cost.

(C) Step of Applying Water-Soluble Resin When obtaining a sheet-like material in which a polymer elastic body is contained inside the fiber entangled body, in order to obtain denseness and uniformity of fiber distribution on the surface of the sheet-like material. In a non-woven fabric (fiber entangled body) formed by entanglement of a fiber bundle of microfibers, the polymer elastic body is preferably not substantially present inside the fiber bundle of microfibers. When the polymer elastic body is present even inside the fiber bundle, the polymer elastic body is bonded to each of the ultrafine fibers, so that the surface fibers are easily torn off during the buffing process, and the nap is formed. hard.

As a method for obtaining a form in which the polymer elastic body is not substantially present inside the fiber bundle of the ultrafine fibers, for example, a polymer elastic body is applied to a nonwoven fabric composed of sea-island composite fibers of a microfine fiber generation type. It is preferable to provide a step of applying a water-soluble resin before the formation. By providing the step of applying this water-soluble resin, the surface of the fibers constituting the fiber bundle of the ultrafine fibers and the woven or knitted fabric is protected by the water-soluble resin, and the surface of the fibers constituting the fiber bundle of the ultrafine fibers or the woven or knitted fabric is In addition, the portion directly joined to the elastic polymer is not continuous but intermittent, and the bonding area can be appropriately suppressed. The timing at which the water-soluble resin is applied may be before or after the process of expressing the ultrafine fibers described below, as long as it is before the application of the elastic polymer.

ポリビニル As such a water-soluble resin, polyvinyl alcohol, polyethylene glycol, saccharides, starch and the like can be used. Among them, polyvinyl alcohol having a saponification degree of 80% or more is preferably used.

After imparting polyvinyl alcohol and protecting most of the periphery of the fiber, the sea component of the sea-island composite fiber is dissolved and removed with a solvent in which polyvinyl alcohol does not dissolve, and then impregnated with a solution of a polymer elastic material, and then water or A method of removing polyvinyl alcohol after coagulation in an organic solvent aqueous solution is preferably used.

The amount of the polyvinyl alcohol is preferably 0.1% by mass or more and 70% by mass or less based on the mass of the fibers contained in the nonwoven fabric.

(D) Ultrafine fiber developing step When the sea-island composite fiber is used as the ultrafine fiber-expressing fiber, the sea component is dissolved and removed from the sea-island composite fiber to express the ultrafine fiber from the ultrafine fiber generating fiber. The step is performed before or after the step of applying the polymer elastic body and the silicone-based lubricant described later, or at the timing before or after the raising processing step described later.

溶剤 As a solvent for dissolving the above sea component, an organic solvent such as toluene or trichloroethylene is used if the sea component is a polyolefin such as polyethylene or polystyrene. If the sea component is polylactic acid or a copolyester, an aqueous alkali solution such as sodium hydroxide can be used.

工程 This step can be performed by immersing the fiber entangled body made of the ultrafine fiber-generating fibers in the above-mentioned solvent and squeezing the solution.

装置 Further, in this step, devices such as a continuous dyeing machine, a vibro washer type deseamer, a liquid jet dyeing machine, a Wins dyeing machine and a Jigger dyeing machine can be used.

(E) Step of containing polymer elastic body Further, the polymer elastic body can be contained inside the above-mentioned fiber entangled body or inside the fiber entangled body laminated and integrated with the reinforcing layer.

ポリウレタン As the polyurethane elastomer used in the present invention, a polyurethane elastomer dissolved in a solvent or a water-dispersed polyurethane elastomer can be used. For example, a solvent-type polyurethane resin (“Chrisbon” (registered trademark) MP-812NB, manufactured by DIC Corporation) or a water-dispersed polyurethane resin (“Hydran” (registered trademark) WLI-602, manufactured by DIC Corporation) may be used. it can.

(4) When the polyurethane elastomer is of a solvent type, wet coagulation in which the polyurethane elastomer is immersed in water for coagulation is preferable, and when the polyurethane elastomer is a water-dispersed polyurethane, wet heat coagulation is preferably used. When the polyurethane-based elastomer is of a water-dispersed type, those exhibiting heat-sensitive coagulation properties are preferably used. In the case of the water-dispersed polyurethane elastomer, when the thermosetting property is not exhibited, the polyurethane elastomer liquid undergoes a migration phenomenon that concentrates on the surface layer of the fiber entangled body during dry coagulation, and the sheet material containing the polyurethane elastomer is , Tend to harden.

熱 Here, the thermosetting property refers to a property that when the polyurethane elastomer liquid is heated, when a certain temperature (thermal coagulation temperature) is reached, the fluidity of the polyurethane elastomer liquid decreases and solidifies.

(4) The heat-sensitive coagulation temperature of the water-dispersed polyurethane-based elastomer is preferably 40 ° C. or more and 90 ° C. or less. By setting the heat-sensitive coagulation temperature to 40 ° C. or higher, the stability of the polyurethane elastomer liquid during storage is improved, and adhesion of the polyurethane elastomer to the machine during operation can be suppressed. Further, by setting the heat-sensitive coagulation temperature to 90 ° C. or less, the migration phenomenon of the polyurethane elastomer in the fiber entangled body can be suppressed, and the polyurethane elastomer can be unevenly distributed.

(4) In order to set the heat-sensitive coagulation temperature as described above, a heat-sensitive coagulant can be appropriately added. Examples of the heat-sensitive coagulant include inorganic salts such as sodium sulfate, magnesium sulfate, calcium sulfate and calcium chloride, and radical reactions such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile and benzoyl peroxide. Initiators.

The wet coagulation temperature is not particularly limited in the case of a solvent-based polyurethane elastomer. In the case of a water-dispersed polyurethane elastomer, the temperature may be at least the thermosensitive coagulation temperature of the polyurethane elastomer, for example, preferably from 40 ° C to 100 ° C. By setting the temperature of wet coagulation in hot water to 40 ° C. or higher, more preferably 80 ° C. or higher, the time until solidification of the polyurethane elastomer can be shortened, and the migration phenomenon can be further suppressed.

(4) The temperature of the wet heat coagulation may be at least the heat-sensitive coagulation temperature of the water-dispersed polyurethane elastomer, and is preferably, for example, 40 ° C or more and 200 ° C or less. By setting the temperature of the wet heat coagulation at 40 ° C. or higher, more preferably at 80 ° C. or higher, the time until the coagulation of the polyurethane elastomer is shortened and the migration phenomenon can be further suppressed. On the other hand, by setting the temperature of the wet heat coagulation to 200 ° C. or lower, more preferably 160 ° C. or lower, the thermal deterioration of the polyurethane elastomer can be prevented.

ポリウレタン As the polyurethane elastomer used in the present invention, a polyurethane elastomer obtained by reacting a polymer diol, an organic diisocyanate, and a chain extender is preferably used.

ポリカーボネート As the above polymer diol, for example, a polycarbonate diol, a polyester diol, a polyether diol, a silicone diol, and a fluorine diol can be adopted, and a copolymer obtained by combining these can also be used. Above all, it is preferable to use a polycarbonate diol and a polyether diol from the viewpoint of hydrolysis resistance, and a more preferable embodiment is a polycarbonate diol from the viewpoint of abrasion resistance.

The above polycarbonate diol can be produced by a transesterification reaction between an alkylene glycol and a carbonate, or a reaction between phosgene or chloroformate and an alkylene glycol.

Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol. Linear alkylene glycols and branched alkylene glycols such as neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and 2-methyl-1,8-octanediol And alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol. In the present invention, either a polycarbonate diol obtained from a single alkylene glycol or a copolymerized polycarbonate diol obtained from two or more alkylene glycols can be used.

ポリエステル Examples of the polyester diol include polyester diols obtained by condensing various low-molecular-weight polyols with polybasic acids.

Examples of the low molecular weight polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,2-dimethyl-1,3-propane. Diols, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, and One or more selected from cyclohexane-1,4-dimethanol can be used.

付加 Also, adducts obtained by adding various alkylene oxides to bisphenol A can be used.

Examples of polybasic acids include, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydroacid One type or two or more types selected from isophthalic acid can be mentioned.

ポリ Examples of the polyether diol used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a copolymerized diol obtained by combining them.

数 The number average molecular weight of the polymer diol is preferably in the range of 500 or more and 4000 or less when the molecular weight of the polyurethane-based elastomer is constant. By setting the number average molecular weight to preferably 500 or more, more preferably 1500 or more, it is possible to prevent the sheet from becoming hard. Further, by setting the number average molecular weight to 4000 or less, more preferably 3000 or less, the strength as a polyurethane elastomer can be maintained.

Examples of the organic diisocyanate used in the present invention include an aliphatic diisocyanate such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and an aromatic diisocyanate such as diphenylmethane diisocyanate and tolylene diisocyanate. And these can be used in combination.

As the chain extender, amine chain extenders such as ethylenediamine and methylenebisaniline and diol chain extenders such as ethylene glycol can be preferably used. Further, a polyamine obtained by reacting a polyisocyanate with water can be used as a chain extender.

ポリウレタン The polyurethane used in the present invention may be used in combination with a crosslinking agent for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like. The cross-linking agent may be an external cross-linking agent added as a third component to the polyurethane-based elastomer, or an internal cross-linking agent that introduces a reaction point to be a cross-linked structure in the polyurethane molecular structure in advance. It is preferable to use an internal cross-linking agent from the viewpoint that a cross-linking point can be formed more uniformly in the polyurethane molecular structure and a decrease in flexibility can be reduced.

化合物 As the crosslinking agent, a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group, or the like can be used.

(F) Step of Applying Silicone-Based Lubricant In the step (b) of applying a water-soluble resin, that is, in the case of obtaining a sheet-like material in which a polymer elastic body is contained inside the fiber entangled body, fibers The sheet after impregnating and solidifying the entangled body with the elastic polymer is preferably provided with a silicone-based lubricant in an amount of 0.01% by mass or more and 3.0% by mass or less based on the mass of the sheet. By giving 0.01% by mass or more, the surface of the coagulated polymer elastic body is covered with a silicone-based lubricant, thereby improving the releasability of the polymer elastic body and the microfiber during the step of forming the raised layer described below. The fine fibers are dispersed, and a uniform nap layer is easily formed. On the other hand, when the content exceeds 3.0% by mass, it is difficult to form nap due to the sliding effect of silicone. A more preferable range of the silicone-based lubricant is 0.1% by mass or more and 2.0% by mass or less based on the mass of the sheet material. As the silicone-based lubricant, for example, “SM7036EX” manufactured by Toray Cortex Co., Ltd. can be used.

As a method of applying the silicone-based lubricant, there is a method of impregnating the sheet with a silicone oil liquid or a method of spraying and applying by spraying. For more uniform application, the sheet is impregnated with the silicone oil liquid and applied. The method is preferred.

It is preferable to apply the silicone oil immediately after the solidification of the elastic polymer. For example, when polyurethane is coagulated in water, it is preferable to apply silicone oil before heating to dry the water.

(G) Half-cutting step After the ultrafine fiber developing step, when a polymer elastic body and / or a silicone-based lubricant is applied to the fiber entangled body, the sheet is cut in half in the thickness direction after the step. Or, it can be divided into several pieces. This is preferable because a sheet-like material can be obtained more efficiently.

(H) Step of Forming a Napped Layer The sheet-like material of the present invention includes the base layer and the napped layer as described above, and the napped layer has the napped only of the ultrafine fibers on at least one surface of the sheet-shaped material. Things.

立 The nap is generally obtained by buffing treatment, but the buffing treatment is preferably performed by a method of grinding the sheet surface of the ultrafine fiber nonwoven fabric using a sandpaper or a roll sander. In particular, by raising the sheet surface using sandpaper, a uniform and dense nap can be formed.

とおり As described above, by applying a silicone-based lubricant to the sheet-like material before the raising treatment, the releasability of the elastic polymer and the microfiber is improved, and a long glossy nap is developed. In addition, the surface of the ultrafine fiber is protected, the effect of suppressing fusion is exhibited, and the fiber opening property is improved by the lubricating effect. In addition, applying an antistatic agent before the raising treatment of the sheet-like material is a preferable embodiment in that grinding powder generated from the sheet-like material by grinding is less likely to be deposited on sandpaper.

There is a method in which the surface of the fiber entangled body such as a nonwoven fabric or the entire fiber entangled body is treated in a wet state with water or a chemical in order to make the nap surface more uniform and dense nap in a state of high nap coverage. In a preferred embodiment, the sheet is in a dry state during the raising process. When the sheet is in a wet state, the sandpaper is also in a wet state, and the paper life is shortened, such as breakage during continuous processing. Further, since it is necessary to remove water by drying after the raising process, the production efficiency is inferior and this is an unfavorable aspect.

研削 In order to form a uniform nap on the sheet surface, it is preferable to reduce the grinding load. In order to reduce the grinding load, the number of times of buffing is at least two times, preferably three or more times, and the number of sandpapers used in each step is further reduced stepwise or at least the same. By doing so, the nap can be finished uniformly. In addition, the count of the sandpaper is a preferred embodiment in which the particle size P specified in JIS R6252: 2006 “Abrasive paper” is in the range of 120 to 600.

In order to make the average fiber length CV value of the ultrafine fibers in the napped layer on the sheet surface 30% or less, the grinding amount at the time of buffing treatment is 20 g / m ² or more and 250 g / m ² or less, preferably 30 g / m ^2. In a preferred embodiment, the concentration is at least 100 g / m ² . When the grinding amount is less than 20 g / m ² , the fiber length constituting the nap layer has large variation, the rate of irregular reflection of light applied to the nap surface increases, and the glossiness becomes insufficient. Further, disadvantages such as exposure of the polyurethane to the surface occur.

(I) Dyeing step The sheet can be dyed according to the application. As a method for dyeing the sheet-like material, it is preferable to use a liquid jet dyeing machine since the sheet-like material can be softened by imparting a kneading effect at the same time as dyeing the sheet-like material. If the dyeing temperature of the sheet-like material is too high, the polymer elastic body may be deteriorated. On the other hand, if the temperature is too low, the dyeing to the fiber becomes insufficient. Generally, the dyeing temperature is preferably from 80 ° C to 150 ° C, more preferably from 110 ° C to 130 ° C.

The dye can be selected according to the type of fiber constituting the sheet. For example, a disperse dye is used for polyester fibers, and an acid dye or a gold-containing dye is used for polyamide fibers, and a combination thereof can be used.

好ましい It is also a preferred embodiment to use a dyeing aid at the time of dyeing the sheet. By using the dyeing aid, the uniformity and reproducibility of the dyeing can be improved. Further, a finishing agent treatment using a softening agent such as silicone, an antistatic agent, a water repellent, a flame retardant, a light resistant agent, an antibacterial agent, or the like can be performed in the same bath or after the dyeing.

In a preferred embodiment, the sheet-like material of the present invention does not have a partially crimped portion or a resin-coated portion on the raised surface. Here, the partial pressure bonding includes processing by hot embossing and the like. Although it is possible to impart irregularities to the surface of the sheet-like material by partial pressure bonding or resin coating, there are portions with no nap on the surface where such treatment is performed. In a part without piloerection, a dense feeling and a glossy feeling as the object of the present invention may not be obtained. However, in applications where it is sufficient to have a partially good tactile sensation, these treatments may be performed as necessary.

Apparent density of the sheet of the present invention, it is preferably, more preferably 0.200 g / cm ³ or more 0.700 g / cm ³ or less or less 0.100 g / cm ³ or more 0.900 g / cm ³ . When the apparent density is 0.100 g / cm ³ or more, the denseness and mechanical properties of the sheet material are good, and when the apparent density is 0.900 g / cm ³ or less, it is possible to prevent the texture from becoming hard.

In addition, in this invention, the apparent density of a sheet-shaped thing points out the value measured as follows.
(A) The basis weight of the sheet is measured by a method according to JIS L 1096: 2010 “Test method for fabrics and knitted fabrics” 8.3.2. That is, two test pieces of 20 cm × 20 cm were sampled, their mass (g) was weighed, and the arithmetic average value was expressed as mass per 1 m ² (g / m ² ).
(B) As a thickness of a sheet-like material, five points are measured at equal intervals in the sheet width direction under a load of 10 kPa using a thickness gauge (disc diameter of 9 mm or more) with a scale of 0.01 mm, and the arithmetic average value is obtained.
(C) The apparent density is calculated by the following formula using the basis weight and thickness of the sheet obtained in (A) and (B), and the value is rounded to four decimal places.
Apparent density (g / cm ³ ) = weight (g / m ² ) thickness (mm) ÷ 1000
The thickness of the sheet is preferably 0.1 mm or more and 7 mm or less. By setting the thickness to 0.1 mm or more, preferably 0.3 mm or more, the sheet-like material is excellent in morphological stability and dimensional stability. On the other hand, by setting the thickness to 7 mm or less, more preferably 5 mm or less, the formability of the sheet is excellent.

Since the sheet-like material of the present invention has an elegant appearance and a very smooth touch, and also has abrasion resistance, it can be used for uppers of shoes such as shirts, jackets, casual shoes, sports shoes, men's shoes and women's shoes, It can be suitably used for clothing such as trims, bags, belts, wallets, and accessories for clothing such as buttons and pockets.

Next, the sheet-like material of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Next, the evaluation method used in the examples and the measurement conditions will be described. However, in the measurement of each physical property, unless otherwise specified, the measurement was performed based on the method described above.

<Evaluation method>
(1) Average Single Yarn Diameter In the measurement of the average single yarn diameter, VE-7800 manufactured by KEYENCE CORPORATION was used as a scanning electron microscope.

(2) Intrinsic viscosity of polymer (IV)
0.8 g of a sample polymer is dissolved in 10 mL of orthochlorophenol (hereinafter sometimes abbreviated as OCP), and the relative viscosity η _r is determined by the following equation using an Ostwald viscometer at a temperature of 25 ° C., and the intrinsic viscosity ( IV) was calculated.
Η _r = η / η ₀ = (t × d) / (t ₀ × d ₀ )
-Intrinsic viscosity (IV) = 0.0242 η _r + 0.2634
(Where η is the viscosity of the polymer solution, η ₀ is the viscosity of the OCP, t is the falling time of the solution (seconds), d is the density of the solution (g / cm ³ ), and t ₀ is the falling time of the OCP (seconds) , _{d 0} is the density of OCP a (g / cm ^3), representing respectively.).

(3) Polymer melt flow rate (MFR)
ISO 1133: 2005 "Plastics-Determination of the melt mass-flow rate (MFR) and the melt volume-flow rate (MVR)" (G) was measured. The same measurement was repeated three times, and the arithmetic average value was defined as MFR (g / 10 minutes).

(4) Average fiber length of microfibers in the nap layer (μm), CV value of average fiber length of microfibers (%)
In the measurement of the average fiber length (μm) of the ultrafine fibers and the CV value (%) of the average fiber length, VE-7800 manufactured by KEYENCE CORPORATION was used as a scanning electron microscope.

(5) Surface coverage of microfibers in the nap layer (%)
In the measurement of the surface coverage, VE-7800 manufactured by KEYENCE CORPORATION was used as a scanning electron microscope, and "ImageJ" was used as image analysis software.

(6) Appearance Grade A total of 20 healthy adult men and 10 adult females were evaluated by visual and sensory evaluations as shown below in A, B, and C, and the most evaluated was the appearance. And dignity. A good level in the present invention is "A".
A: The dispersion state of the fibers is good, and the fibers have a high density and glossiness.
B: The dispersion state of the fibers is good, but slightly inferior in denseness and gloss.
C: The dispersion state of the fibers is very poor as a whole, and the fineness and glossiness are poor.

<Notation of chemical substances>
-PU: polyurethane-DMF: N, N-dimethylformamide-PET: polyethylene terephthalate-PVA: polyvinyl alcohol

[Example 1]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 minutes is used as a sea component, and a sea-island type composite mouthpiece having 36 islands is used. After melt-spinning at an island / sea mass ratio of 55/45, the fiber was drawn and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet.

After shrinking this sheet with hot water at 96 ° C., the sheet is impregnated with a 10% aqueous PVA solution and dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 30% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 2.1 μm.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 12%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion adjusted to a concentration of 1% by mass, and the silicone-based lubricant applied amount was reduced to 0.5% by mass with respect to the total mass of the fiber mass and the polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 30% by mass relative to the island component mass of the sheet (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 100 g / m ² with endless sandpaper of 180, 180 and 240 sandpaper counts to form a raised surface.

The sheet thus obtained was dyed with a jet dyeing machine at 110 ° C., and then dried with a drier to obtain a sheet having a thickness of 0.5 mm and an apparent density of 0.360 g / cm ³ . A product was obtained.

The obtained sheet-like material had an average fiber length of the ultrafine fibers in the nap layer of 370 μm, a CV value of the average fiber length of 15%, a surface coverage of the ultrafine fibers in the nap layer of 80%, and a seafar wear breakage of 65%. Times / 0.10 mm, and the appearance quality was A.

[Example 2]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 minutes is used as a sea component, and a sea-island type composite mouthpiece having 36 islands is used. After melt-spinning at an island / sea mass ratio of 55/45, the fiber was drawn and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

After shrinking the sheet with hot water at 96 ° C., the sheet is impregnated with a 10% aqueous PVA solution and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 25% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 2.1 μm.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 10%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water, and a silicone oil emulsion adjusted to a concentration of 1% by mass was impregnated, so that the amount of the silicone-based lubricant applied was 0.2% by mass based on the total mass of the fiber mass and the polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air of 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 25% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 60 g / m ² with endless sandpaper of 180th, 180th, and 240th counts of sandpaper to form a raised surface.

The obtained sheet-like material had an average fiber length of the microfibers in the nap layer of 260 μm, a CV value of the average fiber length of 20%, a surface coverage of the microfiber in the nap layer of 73%, and a number of seafar wear tears of 40. Times / 0.10 mm, and the appearance quality was A.

[Example 3]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 minutes is used as a sea component, and a sea-island type composite mouthpiece having 36 islands is used. After melt-spinning at an island / sea mass ratio of 55/45, the fiber was drawn and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

After shrinking the sheet with hot water at 96 ° C., the sheet is impregnated with a 15% aqueous PVA solution and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 40% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 2.1 μm.

(4) The desealed sheet made of this ultrafine fiber was impregnated with a DMF solution of a polycarbonate / polyester polyurethane adjusted to a solid content of 9.5%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, the PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion adjusted to a concentration of 1% by mass, and the silicone-based lubricant applied amount was reduced to 0.6% by mass based on the total mass of the fiber mass and the polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air of 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 23% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric) of the sheet.

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 70 g / m ² with endless sandpaper of 180 count, 180 count, and 240 count of sandpaper to form a napped surface.

The obtained sheet-like material has an average fiber length of 400 µm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 10%, a surface coverage of the ultrafine fibers in the nap layer of 90%, and a number of sifter wear tears of 45. Times / 0.10 mm, and the appearance quality was A.

[Example 4]
Nylon 6 having an MFR of 58.3 g / 10 min was used as an island component, and polystyrene (Co-PSt) obtained by copolymerizing 22 mol% of 2-ethylhexyl acrylate having a MFR of 300 g / 10 min as a sea component was used. Using a sea-island composite mouthpiece with 36 islands, melt-spun at an island / sea mass ratio of 30/70, stretched and crimped, then cut to 51 mm, and a single fiber fineness of 24 μm is used. Fiber raw cotton was obtained.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking this sheet with 85 ° C. hot water, the sheet is impregnated with a 15% PVA aqueous solution and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 50% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. The cross section of the desealed sheet was SEM, and the average single yarn diameter was 1.0 μm.

脱 The desealed sheet made of the ultrafine fibers was impregnated with a polyether / polyester polyurethane DMF solution adjusted to a solid content of 9%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion solution adjusted to a concentration of 0.5% by mass, and the silicone-based lubricant applied amount was 0.1% by mass based on the total mass of the fiber mass and polyurethane mass. %. Subsequently, the sheet was dried with hot air at 100 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 20% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric) of the sheet.

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 30 g / m ² with endless sandpaper of 150-, 180-, and 180-th sandpaper to form a napped surface.

The sheet thus obtained was dyed with a jet dyeing machine at 85 ° C., and then dried with a drier to obtain a sheet having a thickness of 0.5 mm and an apparent density of 0.300 g / cm ³ . A product was obtained.

The obtained sheet-like material has an average fiber length of the ultrafine fibers in the nap layer of 280 μm, a CV value of the average fiber length of 28%, a surface coverage of the ultrafine fibers in the nap layer of 62%, and a number of sifter abrasion breakage of 20. Times / 0.10 mm, and the appearance quality was A.

[Example 5]
Nylon 6 having an MFR of 58.3 g / 10 min was used as an island component, and polystyrene (Co-PSt) obtained by copolymerizing 22 mol% of 2-ethylhexyl acrylate having a MFR of 300 g / 10 min as a sea component was used. Using a sea-island-type composite die with 280 islands, melt-spun at an island / sea mass ratio of 30/70, stretched and crimped, then cut to 51 mm, and single-fiber fineness of 24 μm was used for the sea-island composite. Fiber raw cotton was obtained.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking the sheet with hot water at 85 ° C, the sheet is impregnated with a 12% PVA aqueous solution and dried with hot air at a temperature of 100 ° C for 10 minutes to obtain a sheet having a PVA weight of 40% by weight based on the sheet weight. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 1.0 μm.

(5) The desealed sheet made of the ultrafine fibers was impregnated with a polyether / polyester-based polyurethane DMF solution adjusted to a solid concentration of 10%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion adjusted to a concentration of 0.1% by mass, and the silicone-based lubricant applied amount was 0.01% by mass based on the total mass of the fiber mass and polyurethane mass. %. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 35% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric) of the sheet.

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 40 g / m ² with endless sandpaper of 150-, 180-, and 180-th sandpaper to form a napped surface.

In the obtained sheet-like material, the average fiber length of the microfibers in the nap layer was 260 μm, the CV value of the average fiber length was 10%, the surface coverage of the microfibers in the nap layer was 70%, and the number of sifter abrasion was 30. Times / 0.10 mm, and the appearance quality was A.

[Example 6]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 minutes is used as a sea component, and a sea-island type compound mouthpiece having 50 islands is used. After melt-spinning at an island / sea mass ratio of 80/20, it was stretched and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island composite fiber having a single fiber fineness of 3.1 dtex.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking the sheet with hot water of 96 ° C., the sheet is impregnated with a 5% PVA aqueous solution and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 30% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 7.0 μm.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 11%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion adjusted to a concentration of 5% by mass, so that the silicone-based lubricant applied amount became 2.0% by mass based on the total mass of the fiber mass and polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet in which the polyurethane content was 40% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 160 g / m ² with endless sandpaper of sand paper counts 120, 150, and 180 to form a raised surface.

The sheet thus obtained was dyed with a jet dyeing machine at 110 ° C., and then dried with a drier to obtain a sheet having a thickness of 1.0 mm and an apparent density of 0.400 g / cm ³ . A product was obtained.

The obtained sheet-like material had an average fiber length of the microfibers in the nap layer of 350 μm, a CV value of the average fiber length of 25%, a surface coverage of the microfiber in the nap layer of 65%, and a number of tears of 80 stiffener abrasion. Times / 0.10 mm, and the appearance quality was A.

[Example 7]
Nylon 6 having an MFR of 58.3 g / 10 min was used as an island component, and polystyrene (Co-PSt) obtained by copolymerizing 22 mol% of 2-ethylhexyl acrylate having a MFR of 300 g / 10 min as a sea component was used. Using a sea-island type composite die with 100 islands, melt-spun at an island / sea mass ratio of 30/70, stretched and crimped, then cut into 51 mm, and a single fiber fineness of 24 μm is used. Fiber raw cotton was obtained.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking the sheet with hot water at 85 ° C., the sheet is impregnated with a 20% aqueous PVA solution and dried with hot air at a temperature of 100 ° C. for 10 minutes to obtain a sheet having a PVA weight of 60% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 1.0 μm.

脱 The desealed sheet made of the ultrafine fibers was impregnated with a polyether / polyester polyurethane DMF solution adjusted to a solid content of 9%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion solution adjusted to a concentration of 3% by mass, and the silicone-based lubricant applied amount was reduced to 1.0% by mass based on the total mass of the fiber mass and the polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 5% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric) of the sheet.

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 50 g / m ² with endless sandpaper of 150th and 180th counts of sandpaper to form a raised surface.

The obtained sheet-like material has an average fiber length of 400 µm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 25%, a surface coverage of the ultrafine fibers of the nap layer of 99%, and a number of sifter abrasion breakage of 10%. Times / 0.10 mm, and the appearance quality was A.

Example 8
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 minutes is used as a sea component, and a sea-island type composite mouthpiece having 36 islands is used. After melt-spinning at an island / sea mass ratio of 55/45, the fiber was drawn and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

収縮 After the sheet was shrunk with hot water at 96 ° C, the sea component was dissolved and removed in trichlorethylene to obtain a desealed sheet in which ultrafine fibers and a woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 2.1 μm.

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 20 g / m ² with endless sandpaper of 180th, 180th and 240th counts of sandpaper to form a napped surface.

The obtained sheet-like material had an average fiber length of the fine fibers in the nap layer of 250 μm, a CV value of the average fiber length of 29%, a surface coverage of the ultra-fine fibers in the nap layer of 62%, and a number of sifter abrasion breakage of 7. Times / 0.10 mm, and the appearance quality was A.

[Example 9]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 minutes is used as a sea component, and a sea-island type composite mouthpiece having 16 islands is used. After melt-spinning at an island / sea mass ratio of 80/20, it was stretched and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island composite fiber having a single fiber fineness of 3.1 dtex.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. The web and plain weave (single yarn consisting of a single component having an intrinsic viscosity (IV) of 0.65, multifilaments (84 dtex, 72 filaments) having a twist number of 2500 T / m are used as warp and weft, and the weaving density is reduced. 97 pieces / 2.54 cm, 76 pieces / 2.54 cm) to obtain a sheet. After shrinking the sheet with hot water of 96 ° C., the sheet is impregnated with a 5% aqueous solution of PVA and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 20% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 4.4 μm.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 11%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water, and a silicone oil emulsion adjusted to a concentration of 1% by mass was impregnated, so that the amount of the silicone-based lubricant applied was 0.2% by mass based on the total mass of the fiber mass and the polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 27% by mass relative to the island component mass of the sheet (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 60 g / m ² with an endless sandpaper of sand paper counts 120, 150 and 180 to form a raised surface.

The obtained sheet-like material had an average fiber length of 450 µm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 20%, a surface coverage of the ultrafine fibers in the nap layer of 80%, and a number of 55 times of seafar abrasion. The number of times / 0.10 mm appearance quality was A.

[Example 10]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 minutes is used as a sea component, and a sea-island type composite mouthpiece having 16 islands is used. After melt-spinning at an island / sea mass ratio of 80/20, it was stretched and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island composite fiber having a single fiber fineness of 3.1 dtex.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 11%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion solution adjusted to a concentration of 1% by mass, and the silicone-based lubricant applied amount was reduced to 0.05% by mass with respect to the total mass of the fiber mass and the polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 27% by mass relative to the island component mass of the sheet (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, cut in half and the resulting sheet in the thickness direction, sandpaper count 120 fastest the half-cut surface, 120 fastest, the product surface at 150 fastest endless sandpaper 80 g / m ² by grinding to form a napped surface.

The obtained sheet-like material had an average fiber length of 300 µm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 28%, a surface coverage of the ultrafine fibers of the nap layer of 63%, and a number of seafar wear tears of 50%. Times / 0.10 mm, and the appearance quality was A.

[Comparative Example 1]
Nylon 6 having an MFR of 58.3 g / 10 min was used as an island component, and polystyrene (Co-PSt) obtained by copolymerizing 22 mol% of 2-ethylhexyl acrylate having a MFR of 300 g / 10 min as a sea component was used. Using a sea-island composite nozzle with 500 islands, melt-spun at an island / sea mass ratio of 30/70, stretched and crimped, then cut to 51 mm, and a single fiber fineness of 24 μm Fiber raw cotton was obtained.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking the sheet with hot water at 85 ° C., the sheet is impregnated with a 12% aqueous PVA solution and dried with hot air at a temperature of 100 ° C. for 10 minutes to obtain a sheet having a PVA weight of 45% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 0.5 μm.

脱 The desealed sheet made of the ultrafine fibers was impregnated with a polyether / polyester polyurethane DMF solution adjusted to a solid content of 9%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion solution adjusted to a concentration of 1.0% by mass, and the silicone-based lubricant applied amount was 0.2% by mass based on the total mass of the fiber mass and polyurethane mass. %. Subsequently, the sheet was dried with hot air of 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 25% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 15 g / m ² with endless sandpaper of 150th and 180th counts of sandpaper to form a raised surface.

The obtained sheet-like material had an average fiber length of 200 µm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 35%, a surface coverage of the ultrafine fibers in the nap layer of 70%, and a number of sifter abrasion breaks of 23. Times / 0.10 mm, and the appearance quality was B.

[Comparative Example 2]
Nylon 6 having an MFR of 58.3 g / 10 min was used as an island component, and polystyrene (Co-PSt) obtained by copolymerizing 22 mol% of 2-ethylhexyl acrylate having a MFR of 300 g / 10 min as a sea component was used. Using a sea-island-type composite die with 300 islands, melt-spun at an island / sea mass ratio of 30/70, stretched and crimped, then cut to 51 mm, and single-fiber fineness of 24 μm Fiber raw cotton was obtained.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking the sheet with hot water at 85 ° C, the sheet is impregnated with a 12% PVA aqueous solution and dried with hot air at a temperature of 100 ° C for 10 minutes to obtain a sheet having a PVA weight of 40% by weight based on the sheet weight. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. The average single yarn diameter was 1.0 μm by SEM of the cross section of the sea-removed sheet.

脱 The desealed sheet made of the ultrafine fibers was impregnated with a polyether / polyester polyurethane DMF solution adjusted to a solid content of 9%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water, and dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 30% by mass relative to the island component mass (total mass of the ultrafine fibers and the woven or knitted fabric) of the sheet. Obtained.

Then, the obtained sheet is cut in half in the thickness direction, and the cut sheet is impregnated with water so that the mass of the sheet containing water becomes 200% of the dry mass, and then squeezed. The product surface was ground at 15 g / m ² with endless sandpaper of 150 count, 180 count, and 180 count of paper to form a napped surface.

In the obtained sheet-like material, the average fiber length of the microfibers in the nap layer was 150 μm, the CV value of the average fiber length was 40%, the surface coverage of the microfibers in the nap layer was 80%, and the number of tears of seafar abrasion was 25. Times / 0.10 mm, and the appearance quality was C.

[Comparative Example 3]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 min is used as a sea component, and a sea-island type compound mouthpiece having 25 islands is used. After melt-spinning at an island / sea mass ratio of 80/20, it was stretched and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island composite fiber having a single fiber fineness of 3.1 dtex.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking the sheet with hot water of 96 ° C., the sheet is impregnated with a 5% aqueous PVA solution and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 35% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 5.0 μm.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 10%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 15% by mass relative to the island component mass (the total mass of the ultrafine fibers and the woven or knitted fabric) of the sheet.

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was ground at 15 g / m ² with endless sandpaper having a sandpaper count of 120 to form a napped surface.

The sheet thus obtained was dyed with a jet dyeing machine at 110 ° C., and then dried with a drier to obtain a sheet having a thickness of 1.0 mm and an apparent density of 0.400 g / cm ³ . A product was obtained. Thereafter, the raised surface of the dyed fiber base material was embossed using an embossing roll having a pattern having shallow shrink wrinkles along the pores of natural leather. The width of the projections of the embossing roll was 220 μm, the engraving depth was 750 μm, and the area ratio of the projections was 13%. The conditions of the embossing treatment were performed at a surface temperature of the embossing roll of 140 ° C., a pressure of 0.3 MPa, and an embossing roll speed of 1.5 m / min to obtain a sheet.

The obtained sheet-like material has an average fiber length of 300 µm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 40%, a surface coverage of the ultrafine fibers in the nap layer of 50%, and a number of sifter abrasion breakage of 16. Times / 0.10 mm, and the appearance quality was C.

[Comparative Example 4]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 min is used as a sea component, and a sea-island type compound mouthpiece having 25 islands is used. After melt-spinning at an island / sea mass ratio of 55/45, the fiber was drawn and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking this sheet with hot water at 96 ° C., the sheet is impregnated with a 10% aqueous PVA solution and dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 30% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 2.0 μm.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 10%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion adjusted to a concentration of 10% by mass, so that the silicone-based lubricant applied amount was 6.0% by mass based on the total mass of the fiber mass and polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air at 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 20% by mass relative to the island component mass of the sheet (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, the obtained sheet was cut in half in the thickness direction, and the cut surface was sanded with sandpaper count 180 and endless sandpaper to grind the product surface by 20 g / m ² to form a raised surface.

The obtained sheet-like material had an average fiber length of 600 μm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 40%, a surface coverage of the ultrafine fibers of the nap layer of 45%, and a number of 28 times of tearing abrasions. Times / 0.10 mm, and the appearance quality was C.

[Comparative Example 5]
Polyethylene terephthalate (PET) having an intrinsic viscosity (IV) of 0.718 is used as an island component, polystyrene having an MFR of 18 g / 10 min is used as a sea component, and a sea-island type compound mouthpiece having 25 islands is used. After melt-spinning at an island / sea mass ratio of 55/45, the fiber was drawn and crimped, and then cut into 51 mm to obtain a raw cotton of sea-island type composite fiber having a single fiber fineness of 3.1 dtex.

Using the raw cotton of this sea-island type composite fiber, a laminated web is formed through a card and a cross wrapper process, needle punched at a punch count of 600 / cm ² , and then needle punched at a punch count of 2900 / cm ^2. To give a sheet. After shrinking this sheet with hot water of 96 ° C., the sheet is impregnated with a 3% aqueous solution of PVA, and dried with hot air at a temperature of 110 ° C. for 10 minutes to obtain a sheet having a PVA weight of 10% by weight based on the weight of the sheet. Was. The sea component was dissolved and removed from the sheet in trichlorethylene to obtain a desealed sheet in which the ultrafine fibers and the woven fabric were entangled. SEM observation of the cross section of the sea-removed sheet revealed that the average single yarn diameter was 2.0 μm.

(4) The desealed sheet made of the ultrafine fibers was impregnated with a DMF solution of a polycarbonate-based polyurethane adjusted to a solid concentration of 10%, and the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%. Thereafter, PVA and DMF were removed with hot water and impregnated with a silicone oil emulsion adjusted to a concentration of 5% by mass, so that the silicone-based lubricant applied amount became 2.0% by mass based on the total mass of the fiber mass and the polyurethane mass. It was given to be. Subsequently, the sheet was dried with hot air of 110 ° C. for 10 minutes to obtain a sheet having a polyurethane content of 65% by mass relative to the island component mass of the sheet (the total mass of the ultrafine fibers and the woven or knitted fabric).

Then, the obtained sheet is cut in half in the thickness direction, and the cut surface is ground at 20 g / m ² with endless sandpaper of 150-, 180-, 240-, 320-, and 600-th sandpaper. Surface formed.

The obtained sheet-like product had an average fiber length of 330 µm of the ultrafine fibers in the nap layer, a CV value of the average fiber length of 40%, a surface coverage of the ultrafine fibers in the nap layer of 45%, and a number of sifter abrasion breakage of 100. Times / 0.10 mm, and the appearance quality was C.

The sheet-shaped article of the present invention has high formability while having an elegant appearance and a very smooth touch, and is used for furniture, chairs and wall materials, and seats and ceilings in vehicle interiors such as automobiles, trains and aircraft. Interior materials with a very elegant appearance as skin materials for interiors, shirts, jackets, casual shoes, sports shoes, uppers for shoes such as men's shoes and women's shoes, trims, etc., bags, belts, wallets, etc. Can be suitably used as an industrial material such as a clothing material, a wiping cloth, a filter-related material, and a CD curtain used as a part of the material.

Claims

A sheet-like material including an ultrafine fiber bundle formed by combining a plurality of ultrafine fibers made of a thermoplastic resin, wherein the sheet-like material includes a base layer and a napped layer, and the base layer is formed from the ultrafine fiber bundle. A fiber entangled body, wherein the nap layer has nap made of only the ultrafine fibers on at least one surface of the sheet-like material, and satisfies all of the following conditions (1) to (3): Sheets.
(1) The average single yarn diameter of the ultrafine fibers is 0.1 μm or more and 10 μm or less.
(2) Among the ultrafine fibers, the average fiber length of the ultrafine fibers in the nap layer is 250 μm or more and 500 μm or less.
(3) The surface coverage of the ultrafine fibers in the nap layer is 60% or more and 100% or less.
The sheet according to claim 1, wherein the sheet comprises the ultrafine fiber bundle and a polymer elastic body, and the polymer elastic body is contained inside the fiber entangled body.
The sheet-like material according to claim 1 or 2, wherein the ultrafine fiber bundle is composed of 10 to 400 ultrafine fibers.
The sheet according to any one of claims 1 to 3, wherein the CV value of the average fiber length of the ultrafine fibers in the nap layer is 30% or less.
(5) The sheet according to any one of (2) to (4), wherein the amount of the elastic polymer added to the ultrafine fibers is more than 0% by mass and 60% by mass or less.
The method for producing a sheet according to any one of claims 1 to 5, wherein the silicone-based lubricant is applied in an amount of 0.01% by mass or more and 3.0% by mass or less based on the mass of the sheet, and then the sheet is produced. A method for producing a sheet-like material, wherein buffing treatment is performed on a product surface in a state where the material is dried.
Method for producing a grinding amount at the time of the product surface was buffed at 20 g / m 2 or more 250 g / m 2 or less, the sheet-like product according to claim 6.
8. The method for producing a sheet-like material according to claim 7, wherein the number of buffing treatments of the product surface is performed in multiple stages of at least two or more, and the count of the sandpaper is gradually reduced or equalized.
Of ASTM D4158-08 (2016) "Standard Guide for For Abrasion Resistance of Textile Fabrics (Uniform Abrasion)" (abrasion resistance evaluation method), the number of times of sandpaper was 180 and the load was 2 lbs. The sheet according to any one of claims 2 to 5, wherein the thickness of the sheet is at least 20 times per 0.10 mm of the sheet.