JP5088293B2 - Leather-like sheet material, interior material, clothing material and industrial material using the same, and method for producing leather-like sheet material - Google Patents

Description

  The present invention relates to a leather-like sheet-like material having a high-grade appearance, excellent physical properties, soft and supple texture, and excellent wear resistance, and interior materials, clothing materials and industrial materials using the same. It is.

  A leather-like sheet mainly composed of ultrafine fibers and polyurethane has excellent characteristics and is widely used in various applications. In particular, a leather-like sheet using a polyester-based ultrafine fiber is excellent in light resistance, and its use has spread year by year for use in clothing, chair upholstery, automobile interior materials, and the like.

  In the field of leather-like sheets, high quality is required, and there are demands on the sensibility aspects such as appearance (suede feeling, pilling), texture (soft touch), color development (color clarity, density). There is a demand for high quality products that satisfy all of them at a high level, and various proposals have been made to solve this.

  For example, in order to obtain a leather-like sheet-like material with a high-grade appearance and a flexible and supple texture, a method of making the fibers constituting the leather-like sheet material extremely fine is generally used. As it becomes thinner, it can only be dyed in a duller whitish color as it becomes thinner, so it has the disadvantage of being inferior in terms of color development, no matter how good the appearance and texture are.

  With respect to the improvement of the color developability of such leather-like sheet-like material, Patent Document 1 proposes dyeing by adding a readily dyeable resin to the napped surface of the suede-like artificial leather. There has also been proposed a dyeing method in which dyeing is performed with a dye that is reduced in the presence of water to become water-soluble and then oxidized to fix the dye. However, the method for improving color developability as described in the above-mentioned patent documents can improve the color developability itself, but reduces the appearance, touch and texture.

  In order to improve this color development and texture, various studies have been conducted using polytrimethylene terephthalate obtained by polycondensation of propylene terephthalate with a lower alkyl ester of terephthalic acid represented by terephthalic acid or dimethyl terephthalate. Yes. Polytrimethylene terephthalate has attracted attention for its features such as low elastic modulus, soft texture and easy dyeability, and its demand has been greatly expanded in recent years. However, only a polytrimethylene terephthalate yarn yields a fabric with low strength, and there is a drawback that when weaving and knitting, tension is applied to the yarn and the yarn is easily cut. In addition, it is generally known that a high draw ratio may be used to obtain a high-strength yarn. However, at a high draw ratio, the elongation decreases and the color developability deteriorates.

  Thus, with polytrimethylene terephthalate alone, a product having good color developability, softness and high strength could not be obtained. Therefore, in order to compensate for the shortcomings of single polytrimethylene terephthalate yarn, development of a core-sheath type composite fiber of polyethylene terephthalate and polytrimethylene terephthalate has been underway. For example, Patent Document 3 discloses reinforcement of strength and elastic modulus by disposing polyethylene terephthalate in the core and polytrimethylene terephthalate in the sheath. However, this reinforces the strength, but the elastic modulus becomes polyethylene terephthalate-like, so the color developability and softness are equivalent to polyethylene terephthalate, and both the color developability and softness unique to polytrimethylene terephthalate are achieved. However, the strength (toughness) could not be increased to an area favorable for post-processing. Furthermore, the core-sheath type composite fiber as described above has been developed as a yarn, but there are significant problems in properties such as spinnability and wearability when applied to ultrafine fibers. However, it was not possible to study leather-like sheets such as artificial leather.

As described above, a leather-like sheet-like material having a high-grade appearance, excellent physical properties, soft and supple texture, and excellent wear resistance has not been provided so far.
JP 50-135331 A JP-A-7-173778 JP-A-11-93021 (Claims)

  The present invention relates to a leather-like sheet-like material having a high-grade appearance, excellent physical properties, soft and supple texture, and excellent wear resistance, and interior materials, clothing materials and industrial materials using the same. It is.

  The leather-like sheet-like material of the present invention is “a leather-like sheet-like material comprising a non-woven fabric comprising an ultrafine fiber having an average single fiber diameter of 0.3 to 7 μm and an elastic polymer, and the ultrafine fiber is a core-sheath type composite. It is a leather-like sheet-like product characterized in that it is a core-sheath type composite fiber that is a fiber, the core component is made of polytrimethylene terephthalate, and the core ratio is 30% or more and less than 80%.

  ADVANTAGE OF THE INVENTION According to this invention, the leather-like sheet-like material excellent in the external appearance, texture, and abrasion resistance, and the interior material, clothing material, and industrial material which use it can be obtained.

The leather-like sheet of the present invention has an ultrafine fiber having an average single fiber diameter of 0.3 to 7 μm (average fineness of 0.001 to 0.5 dtex when converted to a polytrimethylene terephthalate density of 1.4 g / cm ³ ). It is a leather-like sheet-like material containing an elastic polymer in a non-woven fabric.

  The leather-like sheet-like material in the present invention has an excellent surface appearance such as suede, nubuck, silver surface, etc. like natural leather, and preferably has a raised appearance such as suede or nubuck. With good touch and excellent lighting effects.

The average single fiber diameter of the ultrafine fibers constituting the nonwoven fabric is 7 μm (average fineness of 0.5 dtex when converted to a polytrimethylene terephthalate fiber density of 1.4 g / cm ³ ) or less, preferably 6 μm (average fineness is 0.35 dtex) or less. More preferably, when the thickness is 5 μm (average fineness is 0.25 dtex) or less, a sheet-like product having excellent flexibility and napped quality can be obtained. On the other hand, after dyeing, it is 0.3 μm (average fineness is 0.001 dtex) or more, preferably 0.7 μm (average fineness is 0.005 dtex) or more, more preferably 1 μm (average fineness is 0.01 dtex) or more. Excellent color dispersibility, dispersibility of bundled fibers during napping such as grinding with sandpaper, etc.

  The average single fiber diameter of the ultrafine fibers constituting the nonwoven fabric is a scanning electron microscope (SEM) photograph of the surface of the leather-like sheet (or nonwoven fabric) when the cross section of the ultrafine fibers is circular or oval Is taken at a magnification of 2000 times, 100 ultrafine fibers are randomly selected, the fiber diameter is measured, and the average value is calculated. On the other hand, when the ultrafine fiber constituting the nonwoven fabric has an irregular cross section, the outer circumference circular diameter of the irregular cross section is calculated as a single fiber diameter in the same manner. Furthermore, when the circular cross section and the irregular cross section are mixed, or when the single fiber diameters are largely different, etc., 100 are selected and calculated so that each has the same number. The average single fiber fineness is converted from the calculated average single fiber diameter and the specific gravity of the raw material polymer (1.4 in the case of polytrimethylene terephthalate).

  Regarding the uniformity of the single fiber diameter of the ultrafine fibers constituting the nonwoven fabric, the single fiber diameter CV in the fiber bundle is preferably 10% or less. Here, the single fiber diameter CV is a percentage (%) value obtained by dividing the single fiber diameter standard deviation of the fibers constituting the fiber bundle by the average single fiber diameter in the bundle, and the smaller the value, the more uniform. It shows that. By setting the single fiber diameter CV to 10% or less, the appearance of napping on the surface of the leather-like sheet of the present invention becomes graceful, and the dyeing can be made uniform and good. The single fiber diameter 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 diameter.

  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. The core sheath shape is not particularly limited, such as a concentric core sheath or an eccentric core sheath.

  The ultrafine fiber constituting the nonwoven fabric constituting the leather-like sheet of the present invention is a core-sheath type composite fiber, and the core component is polytrimethylene terephthalate having 90 mol% or more of propylene terephthalate repeating units. Polytrimethylene terephthalate is a polyester obtained using terephthalic acid as the main acid component and trimethylene glycol as the main glycol component. However, it may contain a copolymer component capable of forming another ester bond at a ratio of less than 10 mol%. Examples of copolymerizable compounds include dicarboxylic acids such as isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, and sebacic acid, while glycol components include, for example, ethylene glycol, diethylene glycol, butanediol, neopentyl glycol, and cyclohexanedimethanol. , Polyethylene glycol, polytrimethylene glycol and the like can be mentioned, but are not limited thereto. Further, titanium dioxide as a matting agent, silica or alumina fine particles as a lubricant, hindered phenol derivatives, coloring pigments and the like as antioxidants can be added as necessary.

  Examples of the component disposed in the sheath include polyesters such as polyethylene terephthalate, polybutylene terephthalate and polylactic acid, polyamides such as 6 nylon and 66 nylon, and the like, although not particularly limited, such as strength and light resistance. From a viewpoint, the polyethylene terephthalate which 90 mol% or more consists of a repeating unit of ethylene terephthalate is preferable. Polyethylene terephthalate is a polyester obtained using terephthalic acid as the main acid component and ethylene glycol as the main glycol component. However, it may contain a copolymer component capable of forming another ester bond at a ratio of less than 10 mol%. As copolymerizable compounds, for example, dicarboxylic acids such as isophthalic acid, cyclohexanedicarboxylic acid, adipic acid, dimer acid, sebacic acid, etc., while as glycol components, for example, ethylene glycol, diethylene glycol, trimethylene glycol, butanediol, neopentyl glycol , Cyclohexanedimethanol, polyethylene glycol, polypropylene glycol and the like, but are not limited thereto. Further, titanium dioxide as a matting agent, silica or alumina fine particles as a lubricant, hindered phenol derivatives, coloring pigments and the like as antioxidants can be added as necessary.

  In the present invention, it is important to dispose polytrimethylene terephthalate in the core of the ultrafine fiber. By disposing polytrimethylene terephthalate in the core part, the poor wear resistance of polytrimethylene terephthalate can be covered with the sheath part, and a soft texture can be obtained.

  It is important that the polytrimethylene terephthalate core ratio of the ultrafine fibers constituting the nonwoven fabric is 30 wt% or more and less than 80 wt%. By setting the content to 30% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more, the characteristics of polytrimethylene terephthalate such as softness are exhibited. Moreover, the fiber strength reinforcement effect by a sheath part can be expressed by setting it as less than 80%.

  The tensile strength of the ultrafine fiber obtained in the present invention is preferably 2.0 cN / dtex or more, more preferably 2.2 cN / dtex or more, from the viewpoint of actual use of the sheet-like material. Similarly, the tensile strength of the sheet-like material made of ultrafine fibers is preferably 100 N / cm or more, and more preferably 120 N / cm or more.

  The intrinsic viscosity of the polymer disposed in the sheath is higher than the intrinsic viscosity of polytrimethylene terephthalate disposed in the core, and the difference is preferably 0.2 to 1.2. When the difference in intrinsic viscosity is less than the specified range, when the viscosity of polytrimethylene terephthalate is increased, it is generally necessary to set the spinning temperature to be high in accordance with the viscosity. At high spinning temperature, the thermal degradation of polytrimethylene terephthalate proceeds, Of course, not only spun yarn breakage occurs, but also low-strength yarns and, further, polytrimethylene terephthalate is deteriorated by heat deterioration, which is not preferable. Moreover, when the viscosity of polytrimethylene terephthalate is lowered, the characteristics of polytrimethylene terephthalate such as color developability and softness are not exhibited, which is not preferable. The lower limit of the difference in intrinsic viscosity is more preferably 0.3 or more. On the other hand, if the difference in intrinsic viscosity is not less than the specified range, if the viscosity of the sheath polymer is lowered, the effect of reinforcing the strength of the sheath polymer is lost, resulting in a low-strength yarn, and the viscosity of polytrimethylene terephthalate is not preferable. Is too high, it is not preferable because the yarn production itself becomes difficult. The upper limit of the difference in intrinsic viscosity is preferably 1.0 or less. Furthermore, in the core-sheath composite fiber of the present invention, in order not to impair the color developability and softness peculiar to polytrimethylene terephthalate, the intrinsic viscosity of the sheath polymer is 0.40 to 0.70, the limit of polytrimethylene terephthalate A viscosity of 0.80 to 1.70 is particularly preferred. In addition, intrinsic viscosity means the value measured by the method mentioned later.

  The nonwoven fabric constituting the leather-like sheet of the present invention may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric. However, when emphasis is placed on the texture and quality, a short fiber nonwoven fabric is preferred. Similarly, when emphasis is placed on the texture and quality, the fiber length of the short fibers is preferably 25 mm or more and 90 mm or less in consideration of wear resistance due to entanglement.

  The nonwoven fabric may be configured by mixing ultrafine fibers of different materials, and a woven fabric or a knitted fabric may be inserted into the nonwoven fabric for the purpose of improving the strength (hereinafter, the inserted woven fabric / Knitting is sometimes called scrim). As the types of woven fabrics or knitted fabrics, warp knitting represented by warp knitting, tricot knitting, lace knitting, and various knittings based on these knitting methods, or plain weaving, twill weaving, satin weaving and weaving these Any of various woven fabrics can be employed, and is not particularly limited.

  Depending on the yarn type, when the needle punch is integrated with the nonwoven fabric, the woven fabric or the knitted fabric may be easily cut. As a means for preventing this, it is preferable that these yarn types are strongly twisted yarns. In the present invention, it is preferable to use a strong twisted yarn having a twist number of 500 T / m or more and 4500 T / m or less as the yarn constituting the woven fabric or the knitted fabric. If it is less than 500 T / m, the single yarns that make up the yarn are not tightly constricted so that they can be caught and damaged by the needle, and even if the number of twists is too large, the fibers become too hard and the texture and flexibility of the product. From the point of view, it is not preferable, so 4500 T / m or less is preferable. The woven fabric or the knitted fabric preferably uses at least a part of the above-mentioned strong twisted yarn, and particularly preferable are all those using a strong twisted yarn. In this case, high strength can be exhibited. Further, these strongly twisted yarns may be provided with a polyvinyl alcohol-based or acrylic paste. It is preferable to use polyesters, polyamides, polyethylene, polypropylene, and copolymers thereof as the fibers constituting the woven or knitted fabric.

The average single fiber diameter of the fibers constituting the woven fabric or knitted fabric is not particularly limited, and is 0.3 to 9.5 μm (average fineness of 0.001 to 0.001 in terms of density of polytrimethylene terephthalate fiber 1.4 g / cm ^3. 1 dtex) fiber.

  Elastic polymers contained in the nonwoven fabric include polyurethane, synthetic rubber, acrylate polymer or copolymer, resins elasticized by the use of plasticizers, such as elastic polymers such as polyvinyl chloride and polyamide, and the like. Although a polymer mainly composed of at least one selected elastic polymer can be selected, polyurethane is preferable because of its good elasticity recovery property, sponge formation property and the like.

  The polyurethane is, for example, at least one polymer diol selected from polyester diols having an average molecular weight of 500 to 3000, such as polyester diol, polyether diol, polycarbonate diol, or polyester polyether diol, and 4,4′-diphenylmethane diisocyanate. At least one diisocyanate selected from the group consisting of aromatics, cycloaliphatics such as isophorone diisocyanate, and aliphatic diisocyanates such as hexamethylene diisocyanate, ethylene glycol, butanediol, ethylenediamine, 4,4′-diamino Examples include polyurethanes obtained by reacting at least one low molecular weight compound having two or more active hydrogen atoms such as diphenylmethane at a predetermined molar ratio, and modified products thereof. It is.

  The resin may be dissolved in an organic solvent or dispersed in water.

  Elastic polymers include pigments such as carbon black, dyes, fungicides, antioxidants, UV absorbers, light stabilizers such as light stabilizers, flame retardants, penetrants and lubricants, silica and titanium oxide as necessary. It may contain a surfactant such as an antiblocking agent, an antistatic agent, an antifoaming agent such as silicone, a filler such as cellulose, a coagulation modifier, and the like.

  The sheet-like material of the present invention preferably has a tensile strength of 100 N / cm or more for each of length and width. If it is less than 100 cN / cm, the strength is too low to be practically usable, and more preferably 120 cN / cm or more.

  Next, the manufacturing method of the leather-like sheet material of this invention is demonstrated.

The method for producing a leather-like sheet according to the present invention includes the steps (1) to (3).
(1) A step of creating a sheet from a nonwoven fabric of sea-core core-sheath composite ultrafine fiber generating fiber using polytrimethylene terephthalate as an island core component.
(2) A step of treating the sheet with a solubilizing agent or a decomposing agent to develop ultrafine fibers.
(3) A step of applying an elastic polymer to the sheet and solidifying it.
By carrying out (1) to (3), a leather-like sheet can be obtained.

  As for the order, (1) should be the first, and any of the order of (1), (2), and (3) and (1), (3), and (2) is possible, and the order is particularly limited. is not.

First, the step (1) will be described.
As a means for obtaining ultrafine fibers constituting the nonwoven fabric, ultrafine fiber generating fibers are used. A nonwoven fabric in which ultrafine fibers are entangled can be obtained by performing ultrafine fiber after entanglement of ultrafine fiber generating fibers in advance. The ultra-fine fiber-generating fiber uses a sea-island type compound base, and is a polymer that spins by arranging the three components of sea, island sheath (island component sheath component), and island core (island component core component). It is preferable to use an array type sea-island core-sheath composite fiber in that ultrafine fibers having a uniform single fiber diameter can be obtained.

  The ultrafine fiber generation type fiber makes the island component an ultrafine fiber by dissolving and removing the sea component using a dissolving agent or a decomposing agent.

  The component dissolved or decomposed and removed in the ultrafine fiber-generating fiber is a polymer having a different solubility or decomposability with respect to the ultrafine fiber component and solvent or decomposing agent, and having a low compatibility with the ultrafine fiber component, and spinning. From the viewpoint of safety, for example, it is at least one polymer selected from polymers such as polyethylene, polystyrene, polystyrene copolymer, polyethylene propylene copolymer, polyethylene terephthalate copolymer and polylactic acid. Polyethylene terephthalate copolymers include polyethylene terephthalate, polybutylene terephthalate, and other polyesters, sodium 5-sulfoisophthalate, polyethylene glycol, sodium dodecylbenzenesulfonate, bisphenol A compounds, isophthalic acid, adipic acid, dodecadioic acid, cyclohexyl. Copolyesters obtained by copolymerizing 5 to 12 mol% of carboxylic acid, polylactic acid, or the like can be used. In particular, it is preferable to use a polyethylene terephthalate copolymer obtained by copolymerizing 5 to 12 mol% of sodium 5-sulfoisophthalate in view of heat resistance and solubility in a weak alkaline aqueous solution. These copolymers may be not only binary but also ternary or higher multi-component copolymers.

  The sea-island core-sheath conjugate fiber of the present invention can be produced by any known method, but the melt spinning method is most excellent in view of the stability and productivity of the composite structure. When melt-spinning the composite fiber, for example, polyester is preferably melted at 260 to 300 ° C. as a polymer serving as an island sheath component. In the melting, a pressure melter method and an extruder method can be mentioned, and melting by an extruder is preferable from the viewpoint of uniform melting and retention prevention.

  The polytrimethylene terephthalate serving as the island core component is preferably melted at 240 to 280 ° C. using a pressure melter or an extruder. Separately melted polymers pass through separate pipes, weigh and then flow into the base pack. Under the present circumstances, it is preferable that piping passage time is 5 to 30 minutes from a viewpoint of suppressing thermal deterioration. The polymer that has flowed into the pack is merged by the die, is combined into a concentric core-sheath shape by a known technique, and is discharged from the die. The polymer temperature at this time is suitably 263 to 280 ° C. If it is this range, the fall of productivity and the coloring property by a heat degradation and the fall of a soft feeling can be prevented.

  The obtained ultrafine fiber-generating fiber is preferably crimped and cut into a predetermined length to obtain a nonwoven raw cotton. A usual method can be used for crimping and cutting. The obtained raw cotton is made into a web using a cross wrapper or the like, and then the ultrafine fiber generating fiber is entangled to make a nonwoven fabric.

  As a method for obtaining a nonwoven fabric by entanglement of ultrafine fiber-generating fibers, usual methods such as needle punching and water jet punching can be used. The obtained non-woven fabric may be subjected to shrinkage treatment by warm water or steam treatment in order to improve the fineness of the fibers.

  In addition, the nonwoven fabric may be obtained by being cut in half (divided into two sheets) or divided into several sheets in the thickness direction of the nonwoven fabric before applying the elastic polymer.

Next, the process (2) will be described.
In the leather-like sheet-like material of the present invention, a sheet made of ultrafine fiber-generating fibers is treated with a solubilizer or a decomposing agent to develop ultrafine fibers.

  In the ultrafine fiber generating type fiber, the sea component constituent polymer of the fiber constituent polymer is treated with a solubilizing agent or a decomposing agent, or the ultrafine fiber is expressed by a mechanical or chemical treatment. The expression treatment of the ultrafine fiber generating fiber may be performed before or after the elastic polymer is applied. When the modification treatment is performed before applying the elastic polymer, a temporary filler that can be dissolved and removed, such as polyvinyl alcohol, is applied to the nonwoven fabric so that the ultrafine fibers and the elastic polymer do not adhere in order to soften the texture of the sheet. After that, it is preferable to give elastic polymerization and then remove the temporary filler.

  As the solubilizer or decomposer, trichlorethylene or toluene is used in the case of a solvent system. In the case of an aqueous dispersion, an alkaline aqueous solution or hot water is used.

The process (3) will be described.
The leather-like sheet material of the present invention imparts an elastic polymer to a non-woven fabric and solidifies it. The method for applying the elastic polymer to the nonwoven fabric is not particularly limited, and examples include a method of immersing and niping in an elastic polymer solution, and a method of applying an elastic polymer solution on the nonwoven fabric and sliding it with a roll that rotates at high speed. It is done.

  After the elastic polymer is applied to the nonwoven fabric, the elastic polymer is solidified. As the solidification method, a method of wet coagulation by dipping in a liquid containing a non-solvent of the elastic polymer, a dry type that is gelled and dried by heating. Examples include coagulation methods. As described above, the ultrafine fiber generating fiber may be expressed after the elastic polymer is applied. That is, the order of the step (2) and the step (3) is not limited.

  In the leather-like sheet-like material of the present invention, the content of the elastic polymer with respect to the total weight of the nonwoven fabric composed of ultrafine fibers is preferably 20% by weight or more and 200% by weight or less. By making it 20% by weight or more, it is possible to obtain sheet strength and prevent the fibers from dropping off, and by making it 200% by weight or less, it is possible to prevent the texture from becoming harder than necessary, and to achieve a desired good Napping quality can be obtained. More preferably, it is 30 wt% or more and 180 wt% or less.

  When applying the elastic polymer, additives such as a colorant, an antioxidant, an antistatic agent, a dispersant, a softening agent, and a coagulation adjusting agent can be blended in the elastic polymer as necessary.

  The leather-like sheet-like material of the present invention may be a nap-like leather-like sheet-like material having napped fibers of at least one surface. The raising process for forming napping on the surface of the leather-like sheet 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 grinding powder generated from the leather-like sheet by grinding tends to be difficult to deposit on the sandpaper.

  The leather-like sheet-like product may be obtained by dividing into half or several sheets in the sheet thickness direction before the raising treatment.

  The leather-like sheet material of the present invention contains functional agents such as dyes, pigments, softeners, texture modifiers, anti-pilling agents, antibacterial agents, deodorants, water repellents, light proofing agents, weathering agents and the like. May be.

  The leather-like sheet of the present invention may be dyed. Dyeing is performed with a high-temperature and high-pressure dyeing machine using a disperse dye, a cationic dye or other reactive dye, and if necessary, using a dispersant, a pH adjuster, a sequestering agent, and the like. The dyeing temperature is preferably 80 to 150 ° C. By setting the temperature to 80 ° C. or higher, more preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and still more preferably 110 ° C. or higher, the disperse dye sufficiently diffuses in polytrimethylene terephthalate. By setting the temperature to 150 ° C. or lower, more preferably 140 ° C. or lower, there is a concern that the strength of the base material may be reduced due to the hydrolysis of the elastic polymer in the base material, or the fluff may fall off. Note that reduction cleaning 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. Further, a finishing agent treatment such as a softening agent such as silicone, an antistatic agent, a water repellent, a flame retardant, and a light resistance agent may be applied. The finishing treatment may be performed after dyeing or in the same bath as dyeing.

  The leather-like sheet-like material of the present invention can be used as a skin material of various materials, such as furniture, chairs, wall materials, interior materials such as seats, ceilings, interiors, etc., shirts and jackets in vehicle interiors such as automobiles, trains and aircraft. , Casual shoes, sports shoes, men's shoes, women's shoes, uppers, trims, bags, belts, wallets, etc., and industrial materials such as clothing materials, wiping cloths, abrasive cloths, etc. Can be suitably used.

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

[Evaluation method]
(1) Average single fiber diameter A scanning electron microscope (SEM) photograph of the surface of a non-woven fabric or leather-like sheet was taken at a magnification of 2000 times, and 100 randomly selected circular or near-elliptical fibers were selected. It was calculated by measuring the fiber diameter and calculating the average value.

(2) Average single fiber fineness A scanning electron microscope (SEM) photograph of the surface of a nonwoven fabric or leather-like sheet was taken at a magnification of 2000 times, and 100 fibers were selected at random from circular or nearly elliptical fibers. The diameter was measured and converted from the specific gravity of the fiber material polymer (polytrimethylene terephthalate has a specific gravity of 1.4) to fineness, and the average value of 100 was calculated.

(3) Single fiber diameter CV
The cross section inside the nonwoven fabric or leather-like sheet was observed with a scanning electron microscope (SEM) at a magnification of 2000 times, and from the photograph, the single fiber diameter of the ultrafine fibers constituting one bundle of bundle fibers And the value obtained by dividing the single fiber diameter standard deviation of the fibers constituting the fiber bundle by the average single fiber diameter 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 single fiber diameter CV.

(4) Intrinsic viscosity [η]
The intrinsic viscosity [η] is a value obtained based on the following definition formula.

  Ηr in the definition formula is a value obtained by dividing the viscosity at 25 ° C. of a diluted polymer solution dissolved in O-chlorophenol having a purity of 98% or more by the viscosity of the solvent itself measured at the same temperature, Is defined. C is the solute weight value in grams in 100 ml of the solution.

(5) Measurement of yarn strength According to JIS-L1013 (1999), the ultrafine fiber yarn strength (cN / dtex) after the sea component was dissolved was measured.

(6) Tensile strength measurement of sheet-like material Tensile strength (N / cm) was measured based on the measurement method of tensile strength and elongation of 8.12.1 of JIS-L1096 (1990).

(7) Appearance quality The surface quality of the sheet was evaluated by visual inspection and sensory evaluation as follows. A good level of the present invention was “◯”.
○: Napped length and fiber dispersion state are good.
Δ: Napped length is good, but fiber dispersion is poor.
X: Napped length and fiber dispersion state are poor.

(8) Pilling evaluation The pilling evaluation of leather-like sheets was conducted by James H. as a Martindale abrasion tester. Heal & Co. The model 406 made by using the company's ABRASIVE CLOTH SM25 as a standard friction cloth, a load equivalent to 12 kPa was applied, and the appearance of the sample after being rubbed under conditions of 20,000 wear times was visually observed and evaluated. . The evaluation criteria were grade 5 when the appearance of the sample was not changed from before friction, grade 1 when the appearance of many hairballs was graded, and the grade was divided by 0.5 grade. Moreover, the pass level in this invention was made into the 4th grade or more.

(9) Texture 10 healthy adult men and 10 adult women each, with a total of 20 evaluators, the following evaluations were made by tactile sensation. A good level of the present invention was “◯”.
○: Very flexible and moderate rebound.
(Triangle | delta): Although it is flexible, there is no rebound feeling. Or, there is a rebound, but it is hard.
X: Hard.

[Notation of chemical substances]
The meanings of the abbreviations of chemical substances used in each example and comparative example are as follows.
PTT: polytrimethylene terephthalate PET: polyethylene terephthalate PHC: polyhexamethylene carbonate diol MDI: diphenylmethane diisocyanate H12MDI: dicyclohexylmethane diisocyanate 3MPC: poly (3-methylpentane carbonate) diol HDA: hexamethylenediamine.

[Polyurethane type]
The composition of the polyurethane used in the examples and comparative examples is as follows. The solid content concentration of each solution was 30% by weight.

(1) Solvent-based polyurethane (PU-1)
Polyisocyanate: MDI
Polyol: PHC
Internal emulsifier: None
Chain extender: Water (diamine obtained by reaction of isocyanate and water)
Internal crosslinking agent: None Contained organic solvent: 100% by weight (solvent N, N-dimethylformamide).

(2) Self-emulsifying polyurethane water dispersion (PU-2)
Polyisocyanate: H12MDI
Polyol: 3MPC
Chain extender: HDA
Internal emulsifier: Diol compound having polyethylene glycol in the side chain Internal cross-linking agent: γ- (2-aminoethyl) aminopropyltrimethoxysilane-containing organic solvent: 0.1% by weight.

[Example 1]
It is a form in which 36 islands are contained in one filament at a ratio of 30 parts copolymer polystyrene as sea component, 53 parts polytrimethylene terephthalate as island core component, and 17 parts polyethylene terephthalate as island sheath component. A web is formed through a card and a cross-wrapper using sea-island fiber staples (fiber length 51 mm) having an average fiber diameter of 16 μm (average single fiber fineness of 2.8 dtex), and a scrim of 2000 T / m of 84 dtex-72 filaments. A woven fabric using strong twisted yarn was laminated on the top and bottom of the web, and a nonwoven fabric was formed by needle punching.

  After the nonwoven fabric is subjected to hot water shrinkage, it is impregnated with an aqueous polyvinyl alcohol solution and dried with hot air at a drying temperature of 125 ° C. for 10 minutes, so that the polyvinyl alcohol weight is 45% by weight with respect to the island component weight of the nonwoven fabric. A given sheet was obtained. The sea component was dissolved and removed from this sheet in trichlorethylene to obtain a sea removal sheet in which ultrafine fibers were entangled.

  This seawater-removed sheet made of ultrafine fibers is impregnated with an organic solvent polyurethane liquid (PU-1) adjusted to a solid content concentration of 12%, and the polyurethane is coagulated in an aqueous solution with a DMF (N, N-dimethylformamide) concentration of 30%. I was damned. Thereafter, polyvinyl alcohol and DMF were removed with hot water and dried with hot air at 120 ° C. for 10 minutes to obtain a sheet provided with polyurethane so that the polyurethane weight relative to the island component weight of the nonwoven fabric was 30% by weight.

  Then, the sea removal sheet is cut in half in the thickness direction, and the surface opposite to the half-cut surface is brushed by grinding using a 240 mesh endless sandpaper, and then dyed with a disperse dye in a circular dyeing machine. An inventive leather-like sheet was obtained. The obtained leather-like sheet was good in appearance quality, abrasion resistance and texture.

[Examples 2 to 4]
Except for changing the intrinsic viscosity and the island-shell ratio of polytrimethylene terephthalate and polyethylene terephthalate, the same treatment as in Example 1 was performed to obtain a leather-like sheet material of the present invention. All of the obtained leather-like sheets had good appearance quality, wear resistance, and texture.

[Examples 5 and 6]
Except for changing the scrim conditions, the same treatment as in Example 1 was performed to obtain a leather-like sheet material of the present invention. All of the obtained leather-like sheets had good appearance quality, wear resistance, and texture.

[Example 7]
Polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate as a sea component, 30 parts as an island core component, 56 parts of polytrimethylene terephthalate as an island core component, and 14 parts of polyethylene terephthalate as an island sheath component in one filament The island is contained in 36 islands, and a sea island type fiber staple (fiber length 51 mm) having an average fiber diameter of 16 μm (average single fiber fineness of 2.8 dtex) is used to form a web through a card and a cross wrapper. A woven fabric using 84 Ttex-72 filament 2000 T / m strong twisted yarn as the scrim was laminated on the top and bottom of the web, and a nonwoven fabric was formed by needle punching.

  This non-woven fabric was shrunk by treating in hot water at 90 ° C. for 2 minutes and dried at 100 ° C. for 5 minutes. Next, it is impregnated with a self-emulsifying polyurethane aqueous dispersion (PU-1), treated for 5 minutes in a moist and hot atmosphere at 100 ° C., and then dried with hot air for 10 minutes at a drying temperature of 125 ° C. The sheet | seat which provided the polyurethane so that a weight might be 50 weight% was obtained.

  Next, this sheet was immersed in an aqueous solution of sodium hydroxide having a concentration of 10 g / L heated to 90 ° C. and treated for 30 minutes to obtain a sea removal sheet from which sea components of sea-island fibers were removed.

Then, the sea removal sheet is cut in half in the thickness direction, and the surface opposite to the half-cut surface is brushed by grinding using a 240 mesh endless sandpaper, and then dyed with a disperse dye in a circular dyeing machine. An inventive sheet was obtained.
The obtained sheet-like product had good appearance quality, abrasion resistance, and texture.

[Example 8]
50 parts polyethylene terephthalate copolymerized with 8 mol% sodium 5-sulfoisophthalate as sea component, 40 parts polytrimethylene terephthalate as island core component, 10 parts polyethylene terephthalate as island sheath component in one filament The island component is contained in 36 islands, and a sea-island fiber staple (fiber length 51 mm) having an average fiber diameter of 20 μm (average single fiber fineness of 4.3 dtex) is used to form a web through a card and a cross wrapper. A woven fabric using 84 Ttex-72 filament 2000 T / m strong twisted yarn as the scrim was laminated on the top and bottom of the web, and a nonwoven fabric was formed by needle punching.
A sheet material of the present invention was obtained in the same manner as in Example 7 except that this nonwoven fabric was used.
The obtained sheet-like product had good appearance quality, abrasion resistance, and texture.

[Example 9]
Polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate as a sea component, 20 parts as an island core component, 64 parts of polytrimethylene terephthalate as an island core component, and 16 parts of polyethylene terephthalate as an island sheath component in one filament The island component is contained in 36 islands, and a sea island type fiber staple (fiber length 51 mm) having an average fiber diameter of 19 μm (average single fiber fineness of 3.9 dtex) is used to form a web through a card and a cross wrapper. A woven fabric using 84 Ttex-72 filament 2000 T / m strong twisted yarn as the scrim was laminated on the top and bottom of the web, and a nonwoven fabric was formed by needle punching.
A sheet material of the present invention was obtained in the same manner as in Example 7 except that this nonwoven fabric was used.
The obtained sheet-like product had good appearance quality, abrasion resistance, and texture.

[Comparative Examples 1-5]
A leather-like sheet was obtained in the same manner as in Example 1 except that the intrinsic viscosities, island sheath ratios, and scrims of polytrimethylene terephthalate and polyethylene terephthalate were changed. The obtained leather-like sheet was inferior in appearance quality, abrasion resistance and texture.

Claims (9)

A leather-like sheet-like material comprising a nonwoven fabric composed of ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm and an elastic polymer, wherein the ultrafine fibers are core-sheath type composite fibers, and the core component is polytrimethylene A leather-like sheet-like product comprising a core-sheath type composite fiber comprising terephthalate and having a core ratio of 30 wt% or more and less than 80 wt%. The sheath component of the core-sheath composite fiber is polyester, and the intrinsic viscosity of polytrimethylene terephthalate disposed in the core component is higher than that of the polyester disposed in the sheath component, and the difference is 0.2 or more. The leather-like sheet-like product according to claim 1, which is 2 or less. The leather-like sheet material according to claim 1 or 2, wherein the intrinsic viscosity of polytrimethylene terephthalate is 0.80 to 1.68. The leather-like sheet-like material according to any one of claims 1 to 3, wherein the leather-like sheet-like material has a structure in which a nonwoven fabric composed of ultrafine fibers and a woven fabric or a knitted fabric are intertwined. The leather-like sheet material according to claim 4, wherein the yarn constituting the woven fabric or the knitted fabric is a strong twisted yarn having a twist number of 500 T / m or more and 4500 T / m or less. An interior material comprising the leather-like sheet-like material according to any one of claims 1 to 5 as a skin material. A material for clothing comprising the leather-like sheet-like material according to any one of claims 1 to 5 as a skin material. An industrial material characterized in that the leather-like sheet material according to any one of claims 1 to 5 is used as a skin material. It is a manufacturing method of the leather-like sheet material in any one of Claims 1-5, Comprising: The manufacturing method of the leather-like sheet material which has the process of the following (1)-(3).
(1) A step of creating a sheet from a nonwoven fabric of sea-core core-sheath composite ultrafine fiber generating fiber using polytrimethylene terephthalate as an island core component.
(2) A step of treating the sheet with a solubilizing agent or a decomposing agent to develop ultrafine fibers.
(3) A step of applying an elastic polymer to the sheet and solidifying it.