JP5029217B2 - Manufacturing method of sheet-like material - Google Patents

Description

  The present invention relates to a method for producing a sheet material having an elegant appearance and good strength properties and having a soft texture.

  A sheet-like material obtained by impregnating or adhering polyurethane to a nonwoven fabric mainly composed of ultrafine fibers has excellent characteristics not found in natural leather, and is widely used in various applications. In particular, sheet-like materials using polyester-based ultra-fine fibers are excellent in light resistance, so their use has been expanding year by year for clothing, chair upholstery, automotive interior materials, etc. There is a strong demand for higher strength and higher durability.

  Among these required characteristics, the surface feeling and strength properties of the sheet-like material are mainly determined by the type of nonwoven fabric and the manufacturing method. For example, non-woven fabrics can be divided into long-fiber non-woven fabrics and short-fiber non-woven fabrics depending on the fiber length, but the surface feel of the sheet-like material tends to express the denseness of the fibers. It is advantageous to use a long-fiber nonwoven fabric in which fibers are continuously connected if importance is placed on strength properties. When considering both high-quality surface feel and strength properties, it is relatively easier to improve strength properties with short fiber nonwovens than to improve the denseness of fibers with long fiber nonwovens. A short fiber nonwoven fabric is often used for the sheet-like material.

  The staple fiber non-woven fabric manufacturing method is generally a needle punch method or a paper making method. In the needle punch method, several webs of short fibers having a fiber length of about 10 mm to 100 mm are stacked and pierced with a needle in the thickness direction. The papermaking method is a method in which a wet web is formed on a base fabric or a net using a suspension in which short fibers having a fiber length of 10 mm or less are dispersed, and then fiber entanglement is advanced by high-pressure water jet treatment. is there. Although there is no significant difference in strength properties between the short fiber nonwoven fabrics produced by either method, the short fiber length of the nonwoven fabric surface tends to be more advantageous as the fiber length is shorter. Investigation of the sheet-like material that has been in progress is underway.

  For example, in Patent Document 1, a sheet-like material is obtained by forming an ultrafine fiber having a fineness of 0.5 denier or less directly spun into an entangled nonwoven fabric by a papermaking method and applying an aqueous polyurethane emulsion. However, there is a limit to the fineness that can be technically spun by direct spinning. For example, direct spinning of 0.1 denier or less is difficult, and it is difficult to obtain a high-quality and high-quality.

That is, there is a demand for a sheet-like material having a high-grade and high-quality and high strength, but a sheet-like material that satisfies these requirements has not yet been obtained.
Japanese Patent No. 3047951

  In view of the background of such conventional technology, the present invention provides a method for producing a sheet-like product having an elegant appearance and good strength properties and having a soft texture.

That is, the method for producing a sheet-like product of the present invention is described as follows: “After forming a wet web on a base fabric using a suspension containing ultrafine fiber-generating fibers having a fiber length of 0.1 mm to 10 mm, or After laminating a sheet made in advance using a suspension on a base fabric, a wet web or a sheet made on the base fabric is subjected to a high-pressure water jet treatment to entangle the ultrafine fiber generating fiber with the base fabric to form a nonwoven fabric, Then, after providing a water-soluble polymer to the nonwoven fabric, a method for producing a sheet-like product , wherein ultrafine fibers are generated from the ultrafine fiber-generating fibers constituting the nonwoven fabric.

  According to the present invention, it is possible to obtain a method for producing a sheet material having an elegant appearance and good strength properties and having a soft texture.

  The sheet-like material referred to in the present invention is a wet web made of ultrafine fiber-generating fibers or a non-woven fabric obtained by interlacing a paper sheet and a base fabric, and is suede, nubuck, silver surface like natural leather. Etc., and preferably has a smooth touch and an excellent lighting effect in a raised appearance such as suede or nubuck.

  In the present invention, first, a wet web or papermaking sheet is produced using a suspension containing ultrafine fiber generating fibers.

  The fiber length of the ultrafine fiber generating fiber contained in the suspension used in the present invention is 0.1 mm or more and 10 mm or less. If the fiber length is too long, it cannot be stably obtained as a suspension, and the fabric weight and thickness of the nonwoven fabric tend to be uneven. On the other hand, if the fiber length is too short, fluffing from the nonwoven fabric tends to occur. The fiber length of the ultrafine fiber generating fiber is preferably 1 mm or more and 7 mm or less.

  As the ultrafine fiber generation type fiber used in the present invention, two or more kinds of thermoplastic polymer components are used as sea components and island components, and sea island type composite fibers that use island components as ultrafine fibers by dissolving and removing the sea components, A two-component thermoplastic polymer component can be employed, such as a peelable composite fiber in which the fiber cross-sections are alternately arranged in a radial or multi-layer fashion, and each component is split and divided into ultrafine fibers. Above all, the sea-island type composite fiber can provide an appropriate gap between the island components, that is, between the ultrafine fibers inside the fiber bundle by removing the sea component, so from the viewpoint of the surface quality, flexibility, and texture of the nonwoven fabric. Is also preferable. In addition, the present invention generates (fines) ultrafine fibers by high-pressure water jet treatment after entanglement. However, in the case of a sea-island type composite fiber, the island components that should be ultrafine fibers are surrounded by sea components. It has the merit that the island component is not damaged by the high-pressure water jet treatment, and this is considered to be a factor for obtaining good strength properties.

  For the sea-island type composite fiber, a sea-island type composite base is used, and a polymer inter-array system in which the two components of the sea and the island are mutually arranged and spun, and the mixed spinning in which the two components of the sea and the island are mixed and spun. Although a system etc. can be used, the sea island type composite fiber by a polymer array system is more preferable at the point from which the ultrafine fiber of uniform fineness is obtained.

  As sea components of the sea-island type composite fiber, olefins such as polystyrene, polyethylene, and polypropylene, polyethylene terephthalate, polyester such as polybutylene terephthalate, sodium 5-sulfoisophthalate, polyethylene glycol, sodium dodecylbenzenesulfonate, bisphenol A compound, Copolyesters obtained by copolymerizing 5 to 12 mol% of isophthalic acid, adipic acid, dodecadioic acid, cyclohexyl carboxylic acid, or the like, polylactic acid, or the like can be used. In particular, from the viewpoint of heat resistance and the environmental response of the solvent at the time of elution of sea components, it is preferable to use a polyethylene terephthalate copolymer obtained by copolymerizing 5 to 12 mol% of sodium 5-sulfoisophthalate that can be dissolved in a weak alkaline aqueous solution. These copolymers may be not only binary but also ternary or higher multi-component copolymers.

  On the other hand, the island component of the sea-island type composite fiber (the ultrafine fiber constituting the sheet-like material obtained in the present invention) is polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate. Polyesters such as rate, polyamides such as 6-nylon and 66-nylon, and various synthetic fibers such as acrylic, polyethylene, and polypropylene can be used alone or in combination. Of these, polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate are preferably used from the viewpoints of strength, dimensional stability, light resistance, and dyeability.

  The suspension used in the present invention contains ultrafine fiber generating fibers, but may contain a dispersant such as a surfactant or a water-soluble polymer for the purpose of improving the dispersibility of the ultrafine fiber generating fibers. .

  The dispersion medium for the suspension can be water, an organic solvent such as isopropyl alcohol, or a mixture thereof, and is preferably water from the viewpoint of environmental considerations.

  The dispersion method of the ultrafine fiber generating fiber in the dispersion medium is not particularly limited. For example, the ultrafine fiber generating fiber cut into short fibers is dispersed with a dispersion medium using a rotary device such as a pulper, and dispersed as necessary. The agents can be mixed together to perform disaggregation and uniform dispersion.

  By making paper using a suspension containing such ultrafine fiber-generating fibers, a wet web is formed on a base fabric or a sheet is obtained. However, the paper making method is not particularly limited. For example, a desired wet web or sheet can be efficiently obtained by using a general wet paper machine. Examples of papermaking nets used to obtain papermaking sheets include circular nets, short nets, and long nets. These papermaking nets can be used alone to form a single layer or a combination of papermaking nets. It is also possible to make a sheet of paper. From the viewpoint of obtaining a homogeneous paper sheet without formation unevenness, it is preferable to make a plurality of layers, and it is particularly preferable to make a two-layer paper by a short net-circular paper machine.

  The desired wet web or paper sheet can be obtained by drying after paper making. If necessary, hot pressing or the like can be further performed.

  The wet web in the present invention refers to a sheet-like structure of ultrafine fiber-generating fibers formed on the base fabric after flowing a suspension containing the ultrafine fiber-generating fibers on the base fabric. The sheet refers to a sheet-like material obtained by paper-making using a suspension containing ultrafine fiber-generating fibers in a normal paper-making apparatus and drying.

  The base fabric used in the present invention is preferably one that can be firmly gripped and fixed to the ultrafine fiber-generating fibers that are shrunk by heat treatment and entangled with the base fabric, and specifically, a woven fabric or a knitted fabric is preferable. The material for the base fabric is not particularly limited, and may be polyester fiber, polyamide fiber, acrylic fiber, polyolefin fiber, cellulose acetate fiber, polyurethane fiber, or the like, but woven fabric or knitted fabric made of polyester fiber is more preferable. The presence of the base fabric can impart good strength properties even if the ultrafine fibers are short fibers.

  The average single fiber fineness of the fibers constituting the base fabric is not particularly limited, and may be 0.001 dtex or more and 1 dtex or less.

  The support net for the base fabric when forming a wet web on the base fabric using a suspension containing ultrafine fiber-generating fibers is not particularly limited, but has good drainage properties In order to reduce the net mark, a metal net or plastic net having a smooth surface of 20 to 200 mesh, preferably 50 to 120 mesh can be used.

The preferred basis weight of the wet web formed on the base fabric or the paper sheet made in advance is 10 g / m ² or more and 200 g / m ² or less. When forming a wet web on the base fabric, after forming the wet web by multistage suction dewatering treatment or after the subsequent high pressure water jetting treatment, further multistage suction dewatering on the wet web or high pressure water jetting treatment sheet-like material. It is good also as forming such a wet basis weight by forming a wet web. Moreover, when using the papermaking sheet | seat produced in advance, it is good also as stacking a plurality of papermaking sheets, or making a papermaking sheet | seat further laminated | stacked on a high pressure water-jet-processed sheet-like thing, and this preferable basis weight.

  In the present invention, a wet web or papermaking sheet on a base fabric and a base fabric are laminated, and then subjected to a high-pressure water jet treatment to entangle the ultrafine fiber generating fibers with the base fabric to obtain a nonwoven fabric. By the high-pressure water jet treatment, ultrafine fiber generating fibers can be entangled with the base fabric to form a nonwoven fabric having a three-dimensional solid entangled structure.

  As the high-pressure water jet process, it is preferable to perform a water jet punch process using a water stream in terms of the working environment. At this time, it is preferable to perform the water in a columnar flow state. In order to obtain a columnar flow, it is usually obtained by ejecting from a nozzle having a diameter of 0.06 to 1.0 mm at a pressure of 1 to 60 MPa. In order to obtain efficient entanglement and good surface quality, this treatment preferably has a nozzle diameter of 0.06 to 0.15 mm and an interval of 5 mm or less, and a diameter of 0.06 to 0.12 mm. The interval is more preferably 1 mm or less. These nozzle specifications do not need to be all the same when processing multiple times. For example, a nozzle having a large hole diameter and a small hole diameter can be used in combination, but the nozzle having the above configuration is used at least once. It is preferable. In particular, when the diameter exceeds 0.15 mm, the entanglement property between the ultrafine fibers decreases, the surface becomes easy to peach, and the surface smoothness also decreases. Accordingly, a smaller nozzle hole diameter is preferable. However, if the nozzle hole diameter is less than 0.06 mm, nozzle clogging is likely to occur. Further, for the purpose of achieving uniform entanglement in the thickness direction and / or improving the smoothness of the nonwoven fabric surface, the treatment is preferably repeated a number of times. Further, the water flow pressure is appropriately selected according to the basis weight of the nonwoven fabric to be treated, and the higher the basis weight, the higher the pressure. Further, for the purpose of highly entanglement of the ultrafine fiber generating fibers, it is preferable to treat at least once with a pressure of 10 MPa or more, and more preferably 15 MPa or more. Further, the upper limit is not particularly limited, but the cost increases as the pressure increases, and if the basis weight is low, the nonwoven fabric may be non-uniform or fluff may be generated by cutting the fiber. Yes, more preferably 30 MPa or less. By doing so, surface properties such as wear resistance can be improved. In addition, in order to improve the quality of the surface, the nozzle head and the non-woven fabric can be moved relative to each other, or a method such as inserting a wire net between the non-woven fabric and the nozzle after the entanglement can be performed.

  In the present invention, before generating ultrafine fibers from the ultrafine fiber generating fibers constituting the nonwoven fabric, the ultrafine fiber generating fibers may be firmly fixed to the base fabric by shrinking the base fabric in the nonwoven fabric by heat treatment. Good. The heat treatment is not particularly limited as long as the base fabric in the non-woven fabric contracts. For example, immersion in hot water, steam treatment, or dry heat treatment can be used.

  In the present invention, the nonwoven fabric may be pressed in the thickness direction in order to improve the density. Preferably, the press timing may be performed after shrinkage due to heat treatment. As a pressing method, a normal method such as a calendar roll can be adopted.

  You may give a polymeric elastic body to the nonwoven fabric of this invention. The polymer elastic body may be applied to a non-woven fabric composed of ultrafine fiber generating fibers, or may be applied to a sheet-like material in which ultrafine fibers are generated from ultrafine fiber generating fibers.

  The polymer elastic body is not particularly limited, and for example, polyurethane, acrylic, silicone, and the like may be used in combination. Among them, in the present invention, polyurethane is particularly preferable from the viewpoint of durability of the sheet-like material and expression of hand feeling like natural leather.

  Polyurethane may be carbonate-based, ether-based, ester-based or a combination thereof as a kind of polyol, but from the viewpoint of durability such as hydrolysis resistance, light resistance, heat resistance, etc. preferable.

  The polyurethane may be a solvent system in which polyurethane is dissolved in an organic solvent or a water emulsion system in which the polyurethane is dispersed in water. From the viewpoint of environmental addition, the polyurethane may be a water emulsion polyurethane. More preferred.

  The amount of the polymeric elastic body is not particularly limited, but if the amount is too large, the texture of the sheet-like material becomes hard, so that the weight of the nonwoven fabric in which the ultrafine fibers constituting the sheet-like material are generated is 100% by weight. % Or less is preferable, and 80% by weight or less is more preferable. The amount is particularly preferably 60% by weight or less.

  In addition, the polymer elastic body is an interface of pigments such as carbon black, dyes, antifungal agents, antioxidants, ultraviolet absorbers, light stabilizers such as light stabilizers, flame retardants, penetrants, lubricants, antistatic agents, etc. An activator, an antifoaming agent such as silicone, a filler such as cellulose, a coagulation adjusting agent, a heat-sensitive gelling agent and the like may be contained.

  The nonwoven fabric of the present invention may be provided with a water-soluble polymer before applying the polymer elastic body. By applying a water-soluble polymer, the nonwoven fabric structure can be fixed before the polymer elastic body is applied, and the sheet shape obtained by suppressing the change in the nonwoven fabric structure in the process of applying the polymer elastic body The surface quality of the object can be improved. The water-soluble polymer applied before applying the polymer elastic body may be removed by washing or the like after applying the polymer elastic body.

  The amount of the water-soluble polymer applied is not particularly limited, but if the amount applied is too large, the polymer elastic body cannot be applied, so the weight of the nonwoven fabric in which the ultrafine fibers constituting the sheet-like material are generated is reduced. On the other hand, it is preferably 70% by weight or less, and more preferably 50% by weight or less.

  As the water-soluble polymer, polyvinyl alcohol and a copolymer thereof, starch, polyvinyl pyrrolidone, or the like may be used.

  In the present invention, it is important to generate ultrafine fibers from the ultrafine fiber generating fibers after the ultrafine fiber generating fibers are entangled with a base fabric to form a nonwoven fabric. From the nonwoven fabric, that is, by generating ultrafine fibers after entanglement of the ultrafine fiber-generating fibers with the base fabric, a sheet-like product in which the ultrafine fiber bundles are intertwined can be obtained. High strength physical properties can be expressed while expressing a soft texture. When ultrafine fibers are generated from ultrafine fiber generation type fibers and then entangled with the base fabric, the ultrafine fibers are entangled with each other instead of the fiber bundle, and the texture of the sheet-like material is It becomes hard and the tearing strength is significantly reduced in terms of strength properties.

  The method for generating ultrafine fibers from the ultrafine fiber-generating fibers is not particularly limited. For example, in the case of a sea-island type composite fiber, it is treated with an organic solvent, hot water, alkaline aqueous solution, or the like that can dissolve or remove sea components Thus, an ultrafine fiber can be generated, and if it is a peelable composite fiber, the ultrafine fiber can be generated by physical force such as water flow or stagnation, swelling of the fiber by an organic solvent, or the like.

  Examples of the organic solvent capable of eluting and removing sea components of the sea-island type composite fiber include toluene, trichlorethylene and the like.

  The average single fiber fineness of the generated ultrafine fibers is preferably 0.001 dtex or more and 0.5 dtex or less from the viewpoint of flexibility and napped quality of the sheet-like material. Preferably it is 0.3 dtex or less, More preferably, it is 0.2 dtex or less. On the other hand, it is preferably 0.005 dtex or more from the viewpoints of color developability after dyeing, dispersibility of fibers during raising treatment such as grinding with sandpaper, and ease of spreading.

  In addition, the average single fiber fineness of the ultrafine fibers constituting the sheet-like material is a scanning electron microscope (SEM) photograph of the surface of the sheet-like material (or non-woven fabric) when the cross-section of the ultrafine fibers is circular or an elliptical shape close to a circle. Is taken at a magnification of 2000 times, 100 ultrafine fibers are selected at random, the fiber diameter is measured, the specific gravity of the material polymer is converted into the fineness, and the average value of the 100 is calculated.

  On the other hand, in the case where the ultrafine fibers constituting the sheet-like material have an irregular cross section, the outer peripheral circular diameter of the irregular cross section is calculated as the fiber diameter in the same manner. Furthermore, when a circular cross section and an irregular cross section are mixed, or when those having greatly different finenesses are mixed, 100 are selected and calculated so that each has the same number.

  Regarding the uniformity of the fineness of the ultrafine fibers constituting the sheet-like material, the fineness CV in the fiber bundle is preferably 10% or less. Here, the fineness CV is a percentage (%) value obtained by dividing the fineness standard deviation of the fibers constituting the fiber bundle by the average fineness within the bundle, and indicates that the smaller the value, the more uniform. . By setting the fineness CV to 10% or less, the appearance of napping on the surface of the sheet-like material of the present invention becomes graceful, and the dyeing can be made uniform and good. The fineness CV when the cross section of the ultrafine fiber is not a circle or an ellipse close to a circle is obtained by the same method as the calculation of the average single fiber fineness.

  The cross-sectional shape of the ultrafine fiber may be a round cross-section, but may be a polygonal shape such as an ellipse, a flat shape, or a triangle, or an irregular cross-section such as a sector shape or a cross shape.

  In the present invention, in order to make the sheet-like material a sheet-like material having naps of ultrafine fibers on at least one surface, raising treatment may be performed. The raising treatment for forming napping on the surface of the sheet-like material can be performed by a grinding method using a sandpaper or a roll sander. A lubricant such as a silicone emulsion may be applied before the raising treatment.

  In addition, it is preferable to apply an antistatic agent before the raising treatment, because the grinding powder generated from the sheet-like material by grinding tends to be difficult to deposit on the sandpaper.

  Further, the sheet-like material may be divided into half or several sheets in the sheet thickness direction before the raising treatment.

  In the present invention, it is preferable to dye the sheet-like material. The dyeing method is not particularly limited, and the dyeing machine may be any one of a liquid dyeing machine, a thermosol dyeing machine, a high-pressure jigger dyeing machine, etc. Therefore, it is preferable to use a liquid dyeing machine. As the liquid dyeing machine, a normal liquid dyeing machine can be used.

  If the dyeing temperature is too high, there is a limit to dyes that can develop color. Conversely, if the dyeing temperature is too low, the dyeing to the fiber becomes insufficient, so it may be changed depending on the type of fiber, and generally 80 ° C or higher and 150 ° C or lower is preferable. 110 ° C. or higher and 130 ° C. or lower is more preferable.

  The dye is not particularly limited and may be selected according to the ultrafine fiber constituting the sheet-like material. For example, a polyester-based ultrafine fiber is a disperse dye, and a polyamide-based ultrafine fiber is a dye such as an acid dye or a metal-containing dye, And dyes combining them can be used.

  When dyed with disperse dyes, reduction washing may be performed after dyeing.

  Moreover, it is preferable to use a dyeing assistant during dyeing for the purpose of improving the uniformity and reproducibility of dyeing. Furthermore, finishing agents such as silicone softeners, antistatic agents, water repellents, flame retardants, light proofing agents, anti-pilling agents, antibacterial agents, deodorants, and fragrances may be applied. However, the same bath as dyeing may be used.

  The sheet-like material produced according to the present invention preferably has a tensile strength in the vertical and horizontal directions of 30 N / cm or more. More preferably, it is 40 N / cm or more. If the tensile strength in either the vertical or horizontal direction is less than 30 N / cm, depending on the application to which the sheet is applied, problems such as poor workability and easy breakage are likely to occur. Although an upper limit is not specifically limited, Usually, it will be 200 N / cm or less. Tensile strength was measured according to JISL 1096-8.12.1 (2005 edition) by taking a sample with a width of 5 cm and a length of 20 cm, and using a constant-speed extension type tensile tester with a gripping interval of 10 cm and a tensile speed of 10 cm / min. And stretched. From the obtained value, the load per 1 cm width was defined as tensile strength (unit: N / cm).

In addition, the above-mentioned tensile strength can be obtained by the basis weight of 100 to 550 g / m ² , preferably 120 to 450 g / m ² , more preferably 140 to 350 g / m ² in the sheet-like material obtained by the production method of the present invention. it can. If it is less than 100 g / m ² , the tensile strength is lowered, and the appearance of the base fabric inside the nonwoven fabric is easily visible on the surface of the sheet-like material, which is not preferable because the quality is lowered. On the other hand, if it exceeds 550 g / m ² , the wear resistance tends to decrease, which is not preferable.

  The sheet-like material produced according to the present invention preferably has a tear strength in the vertical and horizontal directions of 3 to 50N. More preferably, it is 5-30N. If the tearing strength in either the vertical or horizontal direction is less than 3N, the process passability is lowered and stable production becomes difficult. On the other hand, if the tearing strength in either the vertical or horizontal direction exceeds 50 N, it generally tends to be too soft and it is difficult to balance the texture. The tear strength was measured based on JISL 1096-8.15.5 (2005 version) Method D (Pendulum Method).

In addition, the range of the above-mentioned tear strength is obtained by the basis weight of 100 to 550 g / m ² , preferably 120 to 450 g / m ² , more preferably 140 to 350 g / m ² in the sheet-like material obtained by the production method of the present invention. be able to. If it is less than 100 g / m ² , the tearing strength is lowered, and the appearance of the base fabric inside the nonwoven fabric becomes easier to see on the surface of the sheet-like material, which is not preferable. On the other hand, if it exceeds 550 g / m ² , the wear resistance tends to decrease, which is not preferable.

  The sheet-like material produced by the present invention is an interior material, shirt having a very elegant appearance as a skin material for furniture, chairs, wall materials, seats, ceilings, interiors, etc. in vehicles such as automobiles, trains, and airplanes. , Jackets, casual shoes, sports shoes, men's shoes, women's shoes, uppers and trims for shoes, bags, belts, wallets, etc., and clothing materials, wiping cloths, polishing cloths, CD curtains used for some of them It can use suitably as industrial materials, such as.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely using an Example, this invention is not limited only to a following example.

[Evaluation methods]
(1) Average single fiber fineness A scanning electron microscope (SEM) photograph of the surface of a non-woven fabric or sheet-like material was taken at a magnification of 2000 times, and 100 fibers having a circular shape or a nearly elliptic shape were randomly selected, and the fiber diameter was selected. It measured and converted into the fineness from the specific gravity of the raw material polymer of fiber, and also calculated by calculating the average value of 100 pieces.

(2) Fineness CV
The cross section inside the non-woven fabric or sheet-like material is observed with a scanning electron microscope (SEM) at a magnification of 2000 times, and from the photograph, the fiber diameter of the ultrafine fibers constituting one bundle of bundle fibers is measured. The value obtained by converting the fiber diameter to the fineness of each single fiber and dividing the fineness standard deviation of the fibers constituting the fiber bundle by the average fineness in the bundle was expressed as a percentage (%). The same measurement was performed on the five bundle fibers, and the average value was defined as the fineness CV.

(3) Weight per unit area Measured by the method of JIS L 1096-8.4.2 (2005 edition).

(4) Tensile strength According to JIS L 1096-8.12.1 (2005 version), a sample having a width of 5 cm and a length of 20 cm is taken, and a tensile rate of 10 cm is obtained with a constant-speed extension type tensile tester at a gripping interval of 10 cm. Elongated at / min. The obtained value was converted to the tensile strength per 1 cm width.

(5) Tear strength Measured based on JIS L 1096-8.15.5 (2005 edition) D method (penjuram method).

(6) Appearance quality The surface quality of the sheet was evaluated by visual inspection and sensory evaluation as follows.
○: A lighting effect can be clearly confirmed by the presence of sufficient napped length and the napped orientation.
X: Although there is napping, the lighting effect cannot be confirmed because it is not oriented.

(7) Texture Based on A method (45 ° cantilever method) described in JIS L1096-8.19.1 (2005 version), 5 test pieces each having a size of 2 × 15 cm are prepared in the vertical direction and the horizontal direction at 45 ° C. The test piece was slid, the scale when the center point of one end of the test piece was in contact with the slope was read, and the average value of five pieces was obtained.

[Notation of chemical substances]
The meanings of the abbreviations of chemical substances used in each example and comparative example are as follows.
PET: Polyethylene terephthalate Ny: 6-nylon co-PET: Copolyester PST comprising terephthalic acid and ethylene glycol as main components and containing 8 mol% of sodium 5-sulfoisophthalate with respect to the total acid components: Polystyrene WJP: Water jet punch PTMG: Polytetramethylene glycol PHC: Polyhexamethylene carbonate diol MDI: Diphenylmethane diisocyanate H12MDI: Dicyclohexylmethane diisocyanate HDA: Hexamethylenediamine DMF: N, N-dimethylformamide.

[ Reference Example 1]
Using terephthalic acid and ethylene glycol as the main constituents as sea components and a copolymer polyester containing 8 mol% sodium 5-sulfoisophthalate with respect to the total acid components, polyethylene terephthalate as the island components, and 16 islands Using the sea-island type composite base of the island, the sea-island type composite fiber was spun at a composite ratio of 45% by weight of the sea component and 55% by weight of the island component, and then drawn, cut, cut into a fiber length of 5 mm, and submerged in water. Dispersed to form a suspension. This suspension was made into a paper sheet having a basis weight of 150 g / m ² and a basis weight of 100 g / m ² . The papermaking sheet was laminated on both sides of a plain woven fabric having a weight per unit area of 50 g / m ^{2 made} of 84 dtex / 72 filament PET fibers, and three-dimensionally entangled and integrated by jetting a high-speed water stream with a water jet punch. The high-speed water flow was injected at a pressure of 12 MPa from a straight flow injection nozzle having a hole diameter of 0.1 mm.

The laminated sheet was placed on an 80-mesh metal mesh having a suction device on the lower surface, and a high-pressure water stream was collided at a position 30 mm from the nozzle. This operation was performed from both the front and back sides of the laminated sheet to produce a nonwoven fabric having a basis weight of 300 g / m ² and a thickness of 1.15 mm.

  A self-emulsification type of ether-carbonate copolymer composed of PTMG and PHC as a polyol in a weight ratio of 3: 7, H12MDI as an isocyanate, HDA as a chain extender, and a diamine having polyethylene glycol as an internal emulsifier in the side chain. After impregnating with a polyurethane water emulsion (concentration = 10% by weight) and adjusting the amount of polyurethane water emulsion adhered with a squeeze roll, it was treated in a steam atmosphere at 100 ° C. for 5 minutes and dried at 120 ° C. for 10 minutes. A sheet-like material having a polyurethane application amount of 30% by weight with respect to the weight of the nonwoven fabric in which the fibers were generated was obtained.

  Thereafter, the copolyester, which is a sea component, is decomposed and removed in an aqueous sodium hydroxide solution having a concentration of 10 g / L, and dried to obtain an ultrafine fiber having a basis weight of 390 g / m2, an average single fiber fineness of 0.14 dtex, and a fineness CV of 7.2%. A sheet-like material consisting of

  One side of this sheet-like material was buffed using 150 mesh and then 240 mesh sandpaper, and dyed with disperse dye to obtain a sheet-like material.

  The obtained sheet-like material had good tensile strength and tear strength, and the texture was flexible, and the appearance quality was napped and the lighting effect with a high-class feeling could be confirmed.

[Example 2]
Sea-island composite fibers were spun at a composite ratio of 45% by weight sea component and 55% by weight island component using polystyrene as the sea component and polyethylene terephthalate as the island component and using a sea-island type composite base having 16 islands. Then, it was stretched, cut, cut to a fiber length of 5 mm, and dispersed in water to obtain a suspension. This suspension was made into a paper sheet having a basis weight of 100 g / m ² . The papermaking sheet was laminated on both sides of a plain woven fabric having a weight per unit area of 50 g / m ^{2 made} of 84 dtex / 72 filament PET fibers, and three-dimensionally entangled and integrated by jetting a high-speed water stream with a water jet punch. The high-speed water flow was injected at a pressure of 3 MPa from a straight flow injection nozzle having a hole diameter of 0.1 mm.

The laminated sheet was placed on an 80-mesh metal mesh having a suction device on the lower surface, and a high-pressure water stream was collided at a position 30 mm from the nozzle. This operation was performed from both the front and back sides of the laminated sheet to produce a nonwoven fabric having a basis weight of 250 g / m ² and a thickness of 0.95 mm.

  The nonwoven fabric composed of the sea-island type composite fibers was impregnated with a 10% aqueous solution of polyvinyl alcohol having a saponification degree of 87%, and then dried to give 20% by weight of polyvinyl alcohol to the weight of the nonwoven fabric in which the ultrafine fibers were generated. .

  Thereafter, polystyrene, which is a sea component, is extracted and removed in trichlorethylene, and then polyvinyl alcohol is removed in hot water, followed by drying to form a sheet of ultrafine fibers having an average single fiber fineness of 0.14 dtex and a fineness of CV of 7.3%. I got a thing.

This sheet was impregnated with a DMF solution (concentration = 10% by weight) of an ether-carbonate copolymer polyurethane composed of PTMG and PHC as a polyol in a weight ratio of 3: 7, MDI as an isocyanate, and HDA as a chain extender. After adjusting the amount of polyurethane solution attached with a squeeze roll, the polyurethane is wet-coagulated in an aqueous solution with a DMF concentration of 30% at 30 ° C. and dried at 100 ° C. for 10 minutes, so that the amount of polyurethane applied to the weight of the sheet-like material is increased. A sheet-like material having a basis weight of 275 g / m ² that was 10% by weight was obtained.

  One side of the sheet was buffed with 150 mesh and then 240 mesh sandpaper, and dyed with disperse dye to obtain a sheet.

  The obtained sheet-like material had good tensile strength and tear strength, and the texture was flexible, and the appearance quality was napped and the lighting effect with a high-class feeling could be confirmed.

[Example 3]
Sea-island composite fiber is spun at a composite ratio of 55% by weight of sea component and 45% by weight of island component, using polystyrene as the sea component, 6-nylon as the island component, and a sea-island type composite base having 16 islands. Then, it was stretched, cut, cut into a fiber length of 5 mm, and dispersed in water to obtain a suspension. This suspension was made into a paper sheet having a basis weight of 50 g / m ² . The papermaking sheet was laminated on both sides of a plain woven fabric having a weight per unit area of 50 g / m ^{2 made} of 84 dtex / 72 filament PET fibers, and three-dimensionally entangled and integrated by jetting a high-speed water stream with a water jet punch. The high-speed water flow was injected at a pressure of 3 MPa from a straight flow injection nozzle having a hole diameter of 0.1 mm.

The laminated sheet was placed on an 80-mesh metal mesh having a suction device on the lower surface, and a high-pressure water stream was collided at a position 30 mm from the nozzle. This operation was performed from both the front and back sides of the laminated sheet to produce a nonwoven fabric having a basis weight of 150 g / m ² and a thickness of 0.55 mm.

  This nonwoven fabric made of sea-island type composite fibers is impregnated with a 10% aqueous solution of polyvinyl alcohol having a saponification degree of 87%, and then dried to obtain 20% by weight of polyvinyl alcohol based on the weight of the sheet-like material on which the ultrafine fibers are generated. Granted.

  Thereafter, polystyrene as a sea component is extracted and removed from trichlorethylene, and then polyvinyl alcohol is removed in hot water, followed by drying to form a sheet made of ultrafine fibers having an average single fiber fineness of 0.12 dtex and a fineness of CV of 7.5%. I got a thing.

After impregnating this nonwoven fabric with a DMF solution (concentration = 10% by weight) of an ether polyurethane composed of PTMG as a polyol, MDI as an isocyanate, and HDA as a chain extender, and adjusting the amount of the polyurethane solution adhered with a squeeze roll the polyurethane allowed wet coagulation in an aqueous solution of 30 ° C. DMF concentration of 30%, sheet having a basis weight of 180 g / ^{m 2} polyurethane application amount for sheet weight is 20 wt% by drying 10 minutes at 100 ° C. Got.

  One side of the sheet was buffed with 150 mesh and then 240 mesh sandpaper, and dyed with a metal-containing dye to obtain a sheet.

  The obtained sheet-like material had good tensile strength and tear strength, and the texture was flexible, and the appearance quality was napped and the lighting effect with a high-class feeling could be confirmed.

[Example 4]
Sea-island composite fibers were spun at a composite ratio of 45% by weight sea component and 55% by weight island component using polystyrene as the sea component and polyethylene terephthalate as the island component and using a sea-island type composite base having 16 islands. Then, it was stretched, cut, cut to a fiber length of 5 mm, and dispersed in water to obtain a suspension. Using this suspension, a wet web is formed on one side of a plain woven fabric with a basis weight of 50 g / m ^{2 made} of 84 dtex / 72 filament PET fiber, and entangled and integrated three-dimensionally by jetting a high-speed water stream with a water jet punch. I let you. The high-speed water flow was injected at a pressure of 3 MPa from a straight flow injection nozzle having a hole diameter of 0.1 mm.

The laminated sheet was placed on an 80-mesh metal mesh having a suction device on the lower surface, and a high-pressure water stream was collided at a position 30 mm from the nozzle. This operation was performed from the surface of the laminated sheet to produce a nonwoven fabric having a basis weight of 100 g / m ² and a thickness of 0.35 mm.

  The nonwoven fabric composed of the sea-island type composite fibers was impregnated with a 10% aqueous solution of polyvinyl alcohol having a saponification degree of 87%, and then dried to give 20% by weight of polyvinyl alcohol to the weight of the nonwoven fabric in which the ultrafine fibers were generated. .

  Thereafter, polystyrene, which is a sea component, is extracted and removed in trichlorethylene, and then polyvinyl alcohol is removed in hot water, followed by drying to form a sheet of ultrafine fibers having an average single fiber fineness of 0.14 dtex and a fineness of CV of 7.3%. I got a thing.

This sheet was impregnated with a DMF solution (concentration = 10% by weight) of an ether-carbonate copolymer polyurethane composed of PTMG and PHC as a polyol in a weight ratio of 3: 7, MDI as an isocyanate, and HDA as a chain extender. After adjusting the amount of polyurethane solution attached with a squeeze roll, the polyurethane is wet-coagulated in an aqueous solution with a DMF concentration of 30% at 30 ° C. and dried at 100 ° C. for 10 minutes, so that the amount of polyurethane applied to the weight of the sheet-like material is increased. A sheet-like material having a basis weight of 110 g / m ² that was 10% by weight was obtained.

  One side of the sheet was buffed with 150 mesh and then 240 mesh sandpaper, and dyed with disperse dye to obtain a sheet.

  The obtained sheet-like material had good tensile strength and tear strength, and the texture was flexible, and the appearance quality was napped and the lighting effect with a high-class feeling could be confirmed.

[Comparative Example 1]
PET ultrafine fibers having a single fiber fineness of 0.1 dtex were produced by a direct spinning method, and short fibers cut to a fiber length of 5 mm were dispersed in water to obtain a suspension. This suspension was made into a paper sheet having a basis weight of 50 g / m ² . The papermaking sheet was laminated on both sides of a plain woven fabric having a weight per unit area of 50 g / m ^{2 made} of 84 dtex / 72 filament PET fibers, and three-dimensionally entangled and integrated by jetting a high-speed water stream with a water jet punch. The high-speed water flow was injected at a pressure of 3 MPa from a straight flow injection nozzle having a hole diameter of 0.1 mm.

The laminated sheet was placed on an 80-mesh metal mesh having a suction device on the lower surface, and a high-pressure water stream was collided at a position 30 mm from the nozzle. This operation was performed from both the front and back sides of the laminated sheet to produce an ultrafine fiber nonwoven fabric having a basis weight of 150 g / m ² , a thickness of 0.55 mm, and a fineness CV of 8.2%.

After impregnating this nonwoven fabric with a DMF solution (concentration = 10% by weight) of an ether polyurethane composed of PTMG as a polyol, MDI as an isocyanate, and HDA as a chain extender, and adjusting the amount of the polyurethane solution adhered with a squeeze roll The polyurethane is wet-coagulated in an aqueous solution with a DMF concentration of 30% at 30 ° C. and dried at 100 ° C. for 10 minutes to obtain a polyurethane-applied sheet having a weight per unit area of 165 g / m ^{2 with} a polyurethane application amount of 10% by weight relative to the weight of the nonwoven fabric. It was.

  One side of the polyurethane-applied sheet was buffed using 150 mesh and then 240 mesh sandpaper, and dyed with disperse dye to obtain a sheet.

  The obtained sheet-like product had good tensile strength and tear strength, and the texture was flexible, but the appearance quality was not napped, and a high-quality lighting effect could not be confirmed.

[Comparative Example 2]
A sheet-like material was obtained by the same method as in Example 2 except that the sea component of sea-island fibers was eluted and removed before the water jet punch.

  The obtained sheet was low in tensile strength and tear strength, and the texture was hard. In addition, the appearance quality did not have napped orientation, and a high-quality lighting effect could not be confirmed.

Claims (6)

After forming a wet web on a base fabric using a suspension containing ultrafine fiber-generating fibers having a fiber length of 0.1 mm or more and 10 mm or less, or using a sheet made in advance using the suspension as a base fabric After the lamination, the wet web or the paper sheet on the base fabric is subjected to a high-pressure water jet treatment to entangle the ultrafine fiber generating fiber with the base fabric, and then a water-soluble polymer is applied to the nonwoven fabric. A method for producing a sheet-like product, wherein ultrafine fibers are generated from ultrafine fiber-generating fibers constituting the nonwoven fabric. The method for producing a sheet-like material according to claim 1, wherein the ultrafine fiber generating fiber constituting the nonwoven fabric is a sea-island type composite fiber. The method for producing a sheet-like material according to claim 2, wherein the island component of the sea-island type composite fiber is a polymer mainly composed of polyester. The method for producing a sheet-like material according to claim 3, wherein the polyester is polyethylene terephthalate. The sea component of the sea-island composite fiber is mainly composed of terephthalic acid and ethylene glycol, and is composed of a copolyester containing 5 to 12 mol% sodium 5-sulfoisophthalate with respect to the total acid component. The manufacturing method of the sheet-like material in any one of Claims 2-4 characterized by the above-mentioned. The method for producing a sheet-like material according to claim 1 or 2 , wherein the polymer elastic body is applied after the ultrafine fibers are generated from the ultrafine fiber generating fibers constituting the nonwoven fabric.