TW201923177A - Sheet-shaped material - Google Patents

Abstract

The purpose of the present invention is to provide a sheet-shaped material having a natural leather-like texture, showing good deep black color-developing performance, and having an excellent frictional property. The present invention provides a sheet-like material, which has a fiber structure including ultrafine fibers with an average single filament diameter of 1-10 [mu]m, wherein the ultrafine fibers are sheath-core conjugate fibers having a sheath-core structure, and the core component of the sheath-core conjugate fibers includes a polyester containing 0.1-3 mass% of a pigment and the sheath component includes a polyester not containing any pigment.

Description

   Flakes   

The present invention relates to a sheet-like material, which is a fiber structure that has the touch of natural leather, is rich in dark hair color, and has excellent friction characteristics.

The artificial leather containing suede composed of ultra-fine fibers composed of polyester and polymer elastomer has excellent properties not found in natural leather in terms of durability, uniformity, and color development. Therefore, the aforementioned artificial leather is used for a wide range of applications such as furniture and automotive interior materials.

Compared with acetate fiber, acrylic fiber, rayon, and nylon, polyester fiber has a high refractive index and poor color development. Therefore, low refractive index substances such as silicone, silicon dioxide, fluorine, and polyurethane are attached to the surface of the polyester fiber, and micropores are formed on the surface of the fiber to reduce the reflection of light. Color development.

However, with regard to polyester fibers, since the color development is not easy to improve, it is necessary to increase the dye concentration. However, this method may cause deterioration of the color fastness to rubbing or increase of cost. In contrast to the foregoing, a method of blending carbon black into polyester fibers to reduce the dye concentration is known. As an actual product, there is a problem that the rubbing color fastness or the rubbing characteristics are deteriorated, and the eluted carbon black adheres to a processing machine and is contaminated, and the desired performance is not achieved.

In contrast to the problems described above, there is a method using a core-sheath structure fiber using a carbon black-added polyester as a core component and using a resin not containing a pigment as a sheath component. The core-sheath structure fiber was formed into a sheet, and the sheath component was removed by dissolution with a flow dyeing machine. A method for suppressing the problem of contamination generated during processing by such a method is proposed (refer to Patent Document 1).

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Laid-Open No. 10-077523

However, using the sheet material of the core-sheath structure fiber described in Patent Document 1, the black stock solution-colored fiber added with carbon black after the sheath component is dissolved has exposed the surface, so there is a problem of friction characteristics such as rubbing fastness and abrasion loss. As mentioned above, the conventional artificial leather does not have the texture of suede, deep black hair color, and abrasion resistance.

Therefore, in view of the above-mentioned state of the art, an object of the present invention is to provide a sheet-like article that has the touch of natural leather, and also has deep black hair color and excellent friction characteristics.

The sheet | seat object of this invention has the following structures.

(1) A sheet-like material, which is a sheet-like structure of a fiber structure including ultrafine fibers having an average single fiber diameter of 1 to 10 μm, the ultrafine fibers are core-sheath composite fibers having a core-sheath structure, and the core-sheath composite The core component of the fiber is a polyester containing 0.1 to 3% by mass of a pigment, and the sheath component is a polyester containing no pigment contained in the core component.

As a preferable aspect, there are the following flakes.

(2) The sheet according to (1), wherein the sheath component is a polyester containing no pigment of any kind.

(3) The sheet according to (1), wherein the core component of the core-sheath composite fiber does not contain titanium oxide, and the sheath component contains only titanium oxide as a pigment component, and the content of titanium oxide relative to the polyester of the sheath component and The sum of titanium oxide is more than 0% by mass and 0.01% by mass or less.

(4) The sheet according to any one of the preceding claims, wherein the sheet includes a nonwoven fabric composed of the ultrafine fibers and a polymer elastomer, and at least one side of the sheet is fleece.

(5) The flake according to any one of the preceding claims, wherein the pigment is a black pigment and contains 0.1 to 3% by mass based on the core component.

(6) The sheet-like material as described above, wherein the black pigment is carbon black and contains 0.1 to 3% by mass based on the core component.

(7) The sheet according to any of the foregoing, which satisfies each of the following conditions (A) to (C); (A) the color fastness to friction when wet is grade 4 or higher; (B) Martin generation The abrasion loss is 9.0 mg or less; (C) The reflectance of the surface with fluff is measured, and the L value calculated by the color difference formula of Lab is 19 or less.

Then, as a method for producing a sheet-like article as described above, the following aspects are available.

(8) A method for manufacturing a sheet, comprising: twisting a non-woven fiber composed of a core-sheath structure with a cross-section structure and a superfine fiber-phenotype fiber with a sea component surrounding the core-sheath structure to obtain a fiber twisted body A step of immersing the fiber twisted body in a solvent, and analysing the sea component, so that the ultrafine fiber phenotype fibers become core-sheath composite ultrafine fibers; and imparting a polymer elastomer to the fiber structure containing the obtained core-sheath composite fibers A step of performing a raising treatment on one or both sides of the fibrous structure containing the obtained polymer elastomer.

According to the present invention, a sheet is obtained, which has the touch of natural leather, and also has deep black hair color and excellent friction characteristics.

A form for implementing the invention

The sheet of the present invention is a fiber structure including ultrafine fibers having an average single fiber diameter of 1 to 10 μm. The ultrafine fibers are core-sheath composite fibers having a core-sheath structure, and the core of the core-sheath composite fibers. The component is a polyester containing 0.1 to 3% by mass of a pigment, and the sheath component is a polyester containing no pigment contained in a core component.

In addition, the core-sheath structure mentioned here is a structure in which two or more kinds selected from a polymer and a polymer composition are arranged almost concentrically in a cross-sectional view of the fiber, and the inner side is defined As the core, a round outer side covering the core was used as a sheath. The shape can also be slightly oval.

In the present invention, the average single fiber diameter of the ultrafine fibers is 1 to 10 μm. If the average single fiber diameter becomes larger, the sheet will have a rough feel, become a touch different from artificial leather, and become a sheet that lacks flexibility. Therefore, the average single fiber diameter is preferably 7 μm or less, more preferably It is 5 μm or less.

On the other hand, the average single fiber diameter is preferably 3 μm or more, and more preferably 5 μm or more, from the viewpoint of the dispersibility of the fibers and the ease of dismantling during the fluff treatment using abrasive paper or the like.

The average single fiber diameter of the ultrafine fibers is a scanning electron microscope photograph of a sheet-shaped cross section. 100 core-sheath composite fibers were randomly selected, the fiber diameter was measured, and the average value was calculated to calculate.

The core component polymer constituting the ultrafine fibers of the sheet of the present invention is a polyester containing a pigment. The proportion of the pigment contained in the aforementioned polymer composition of the core component is in the range of 0.1 to 3% by mass, preferably in the range of 0.5 to 2.5% by mass, and more preferably 1 relative to the sum of the polyester and the pigment. ~ 2% by mass. When the proportion of the pigment is small, the color development property tends to be poor. In addition, when the proportion of the pigment is large, physical properties such as strength and elongation tend to be impaired.

Examples of the pigment used in the present invention include carbon black, metal compounds, and metal oxide particles. Since a sheet having deep black hair color is formed, the pigment is preferably a black pigment. From the viewpoint of fiber forming properties, carbon black is more preferred as the black pigment. When a black pigment is used as the pigment, the black pigment is preferably 0.1 to 3% by mass relative to the sum of the polyester and the pigment. When carbon black is used as the black pigment, the carbon black is preferably 0.1 to 3% by mass based on the sum of the polyester and the pigment.

In addition, the sheath component polymer constituting the ultrafine fibers of the sheet of the present invention is a polyester that does not include a pigment of a type contained in the core component. More preferred is a polyester which does not contain a pigment.

However, in order to improve the black color of the obtained core-sheath composite fiber, it is also a preferable aspect to add a little titanium oxide to the polyester of the sheath component polymer. The titanium oxide is preferably contained in a content of more than 0% by mass and 0.01% by mass or less based on the sum of the polyester of the sheath component and the titanium oxide. More preferably, it is 0.001 to 0.01% by mass.

When the sheath component polymer contains a pigment such as carbon black, since pigment particles such as carbon black are easily exposed on the surface of the core-sheath composite fiber, the color fastness to rubbing tends to be impaired. In addition, when the content of titanium oxide is more than 0.01% by mass, it becomes difficult to see the core component polymer from the surface of the fiber, and black hair color is impaired. Therefore, in the present invention, titanium oxide is not allowed to be added without a sheath component.

Examples of the fibrous structure constituting the sheet of the present invention include artificial leather obtained by filling a nonwoven fabric or a fibrous structure thereof with a polymer elastomer. Depending on the cost and characteristics required for each use or purpose, it can be used separately as appropriate.

In the present invention, the fibrous structure preferably contains a nonwoven fabric. As the nonwoven fabric, general short-fiber nonwoven fabrics or long-fiber nonwoven fabrics, needle-punched nonwoven fabrics or hand-made nonwoven fabrics, spun-bonded nonwoven fabrics or meltblown nonwoven fabrics, electrospun nonwoven fabrics, and the like can be used, as well as all nonwoven fabrics exhibited in various categories. Here, from the viewpoint of the texture with a full texture or the quality due to the fine fluff, since the durability of the sheet or the abrasion resistance of the surface is excellent, it is preferable to fill the non-woven fabric with polymer elasticity. Experienced.

The sheet of the present invention is preferably one in which at least one side is fleece. With the fluff fibers exposed on the surface of the sheet, the surface feel closer to natural leather can be obtained.

The ultrafine fibers used in the present invention are core-sheath composite ultrafine fibers having a core-sheath structure.

As a method for obtaining the core-sheath composite ultrafine fiber used in the present invention, the following method can be exemplified.

A method of spinning using a core-sheath composite spinning nozzle and using two components of a core component and a sheath component.

A method of using a sea-island type composite spinning nozzle and spinning using a core component, a sheath component, and three components surrounding the sea component, and then removing the sea component. From the viewpoint of excellent productivity, the latter method using three components is preferred. Hereinafter, a fiber obtained by spinning the core component, the sheath component, and the three components that surround these sea components is referred to as an ultrafine fiber expression type fiber.

The sea component polymer constituting the ultrafine fiber phenotype fiber used in the present invention can be dissolved and removed by using only a sea component to obtain a core-sheath composite fiber.

As the solvent for dissolving the sea component, when the sea component is polyethylene, polypropylene, and polystyrene, an organic solvent such as toluene or trichloroethylene is used. When the sea component is a copolymerized polyester and polylactic acid, an alkali aqueous solution such as an aqueous sodium hydroxide solution or hot water is used.

The number of cores in one core-sheath composite fiber is usually one. In the cross-sectional structure of an ultrafine fiber phenotype fiber composed of a sea component and a core-sheath composite fiber, the number of core-sheath structures is preferably 5 to 400 islands / branch, and more preferably 7 to 100 islands / branch.

Each of the polymer constituting the core component and the polymer constituting the sheath component of the ultrafine fiber-phenotype fiber used in the present invention is a polyester. Examples thereof include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polylactic acid. Among these, polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate are preferred from the viewpoints of strength, dimensional stability, light resistance, and color development.

In addition, the ratio of the mass of the core component and the sheath component constituting the core-sheath composite fiber that becomes an ultrafine fiber is preferably a core component: sheath component = 95: 5 to 50:50, more preferably 90:10 to 70: 30 range. If it is this range, the processing machine will not be contaminated with pigments, such as carbon black, and a sheet-like thing excellent in black color property will be obtained.

The average single fiber diameter of the ultrafine fibers used in the present invention is in the range of 1 to 10 μm. In order to obtain the feel and softness of artificial leather, it is preferably 7 μm or less, and more preferably 5 μm or less.

In the method for producing a sheet-like article of the present invention, it is preferable to use a fiber twist composed of a network of ultrafine fiber expression fibers as an intermediate. By forming into a fiber twisted body, a uniform and beautiful appearance or texture can be obtained. As the form of the fiber twisted body, any short fiber twisted body or long fiber twisted body can be used, but in the present invention, the short fiber twisted body is preferred, and the length of the short fiber is preferably 25 to 90 mm. By forming the fiber length of the short fibers to 90 mm or less, good quality and texture are achieved, and by forming the fiber length to 25 mm or more, a sheet having good abrasion resistance can be formed. As a method for cutting ultrafine fiber expression fibers to form short fibers, a known method can be used. The short fibers (raw cotton) obtained by the cutting process are formed into a fiber web by a folder or the like. The basis weight of the net can be appropriately set in consideration of the final product form, dimensional changes in subsequent steps, and characteristics of the processing machine.

In the manufacturing method of the sheet-like object of this invention, it is preferable to twist the web which consists of superfine fiber expression type fiber. As this method, a method such as pin rolling or water jet punching can be used. From the viewpoint of product quality, among them, a preferable aspect is entanglement treatment by needle rolling.

From the standpoint of densification, a fiber twisted body composed of ultrafine fiber-phenotype fibers obtained by entanglement treatment is preferably applied to the polymer elastomer by dry heat or damp heat or Both of them shrink and further increase the density. The range of the area shrinkage of the fiber twisted body in the shrinking step is preferably 15 to 35%. The method for measuring the area shrinkage is to use a rectangular sample to calculate the shrinkage in the longitudinal direction and the shrinkage in the direction from the length and width before and after processing in the shrinking step, and use the following calculation formula.

Length shrinkage ratio = length after shrinking processing / length before shrinking processing

Width shrinkage ratio = width after shrinking processing / width before shrinking processing

Area shrinkage (%) = (1- (1-length shrinkage) × (1-width shrinkage)) × 100.

As a method of shrinkage, methods such as hot water shrinkage, steam shrinkage, and dry heat shrinkage can be used. By making the area shrinkage rate higher than 15%, the quality caused by shrinkage is improved. In addition, by making the area shrinkage rate less than 35%, the polymer elastomer can be efficiently shrunk after being applied to the polymer elastomer. A better area shrinkage is in the range of 15 to 25%.

In addition, the core-sheath composite ultrafine fiber can be completed by removing the sea-component polymer (hereinafter referred to as "off-sea treatment") of the ultrafine fiber-phenotype fiber. Desalination treatment can be performed by immersing a fiber twisted body composed of ultrafine fiber phenotype fibers in a solvent, and pressing the liquid.

The sheet of the present invention is preferably made of a polymer elastomer. A polymer elastic body is provided to the fiber twist body containing the obtained ultrafine fiber, and a sheet-like material containing the polymer elastic body is obtained. By containing the polymer elastic body in the fiber twisted body, it is possible to obtain a leather-like sheet-like article having a full-feeling touch, a leather-like appearance, or a physical property capable of withstanding actual use.

The polymer elastomer is a polymer compound having elastic rubber elasticity. Examples thereof include polyurethane, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), and acrylic resin. From the viewpoint of achieving a balance between texture and physical properties, among them, a polymer elastomer having polyurethane as a main component is preferred. For example, a polymer elastomer containing 50% by mass or more of polyurethane is preferable.

For the polyurethane, the organic solvent-based polyurethane used in a state of being dissolved in an organic solvent, or the water-dispersible polyurethane used in a state of being dispersed in water can be used. In the present invention, both can be used.

As the polyurethane that can be used in the present invention, one obtained by reacting a polyol, a polyisocyanate, and a chain elongating agent can be used.

As the polyhydric alcohol, for example, a polycarbonate-based diol, a polyester-based diol, a polyether-based diol, a silicone-based diol, a fluorine-based diol, and a copolymer of these can be used. From the viewpoint of light resistance, it is preferable to use a polycarbonate-based diol, a polyester-based diol, or a mixture thereof. Moreover, from a viewpoint of hydrolysis resistance and heat resistance, a polycarbonate-type diol is preferable.

Polycarbonate-based diols can be produced by transesterification of alkanediol and carbonate, or by reaction of phosgene or chloroformate with alkanediol.

Examples of the alkanediol include the following.

Ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, etc. alcohol.

Neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol and other branched alkanes Alicyclic diols such as diols and 1,4-cyclohexanediol.

Other examples include aromatic diols such as bisphenol A, glycerol, trimethylolpropane, and neopentyl tetraol.

In the present invention, polycarbonate diols obtained from individual alkanediols may be used, and any copolymerized polycarbonate diols obtained from two or more kinds of alkanediols may be used.

Examples of the polyisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, or diphenylmethane diisocyanate, and Aromatic polyisocyanates such as toluene diisocyanate. These can be used in combination. When durability and heat resistance are important, an aromatic polyisocyanate, such as a diphenylmethane diisocyanate, is preferable. When light resistance is important, aliphatic polyisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferred.

Further, as the chain elongating agent, for example, an amine-based chain elongating agent such as ethylenediamine or methylenebisaniline, a glycol-based chain elongating agent such as ethylene glycol, or the like obtained by reacting polyisocyanate with water amine.

The polymer elastomer used in the present invention may contain polyester resins, polyamide resins, polyolefin resins, acrylic resins, and ethylene-acetic acid within a range that does not impair the performance or texture as an adhesive. Vinyl ester resin, etc.

In addition, the polymer elastomer may contain various additives, for example, pigments such as carbon black, flame retardants such as phosphorus-based, halogen-based and inorganic-based, antioxidants such as phenol-based, sulfur-based and phosphorus-based, and benzotriene. UV absorbers such as azole, benzophenone, salicylate, cyanoacrylate and oxalic acid anilide, light stabilizers such as hindered amine or benzoate , Polycarbodiimide, hydrolysis-resistant stabilizers, plasticizers, antistatic agents, surfactants, coagulation regulators, and dyes. The content of the additives can be appropriately adjusted in consideration of the type, manufacturing method, and texture of the polymer elastomer used.

In addition, when performing the application of the polymer elastomer after performing the treatment of the ultrafine fibers, it is preferable to provide a step of applying a water-soluble resin between the two steps. By providing this step of imparting a water-soluble resin, the surface of the fiber is protected by the water-soluble resin. Here, the direct joints with the fibers and the polymer elastomer become discontinuous, and they are intermittently present, and the bonding area can be appropriately suppressed. As a result, it is possible to obtain a sheet having a good grip feeling due to a polymer elastomer.

As the aforementioned water-soluble resin, polyvinyl alcohol, polyethylene glycol, sugars, starch, and the like can be used. Among them, polyvinyl alcohol derived from polyvinyl acetate and having a degree of saponification of 80% or more is preferably used.

The amount of the water-soluble resin to be applied is preferably 1 to 30% by mass based on the mass of the fiber twisted body immediately before the application. By setting the applied amount to 1% by mass or more, a good texture is obtained. Further, by setting the amount to be 30% by mass or less, a sheet having good processability and good physical properties such as abrasion resistance is obtained. In the subsequent steps, more polymer elastomers can be imparted to the fiber twisted body. As a result, the density of the sheet-like object and the densification of the touch can be increased.

In the method for producing a sheet-like article of the present invention, a step of cutting the precursor of the sheet-like article provided with the polymer elastomer in half in a planar direction may be performed. By including the halving step, the productivity of the sheet can be improved.

The sheet of the present invention preferably has fluff on at least one side.

The fluff treatment can be performed by polishing the surface with a non-woven fabric using sandpaper or a roller sander. In particular, by using sandpaper, uniform and dense fluff can be formed. Furthermore, in order to form uniform fluff on the surface, it is preferable to reduce the polishing load.

Dyeing can be performed at the stage of the sheet or precursor of the half-cutting of the present invention. Dyeing is performed using disperse dyes, cationic dyes, or other reactive dyes, and in order to soften the texture of the dyed sheet precursor, it is preferably performed by a high-temperature and high-pressure dyeing machine.

Furthermore, if necessary, finishing treatments such as silicone softeners, antistatic agents, water repellents, flame retardants, and lightfasteners can be performed. The aforementioned finishing treatments can be performed after dyeing, or they can be dyed Performed in the same bath. For flame retardant treatment, halogen-based flame retardants such as bromine or chlorine or non-halogen-based flame retardants such as phosphorus can be used. After dyeing, it can be imparted by impregnation, or it can be coated by knife coating or roll screen Back coating is provided.

The sheet of the present invention is excellent in black color and friction characteristics, and can be widely and suitably used for furniture, chairs, and vehicle interior materials to clothing used for the conventional use of suede artificial leather and pearl artificial leather.

    [Example]    

Next, the sheet | seat of this invention and its manufacturing method are demonstrated more concretely using an Example. The evaluation methods and measurement conditions used in the examples are as follows.

(1) Average single fiber diameter of ultrafine fibers

Using a cross section obtained by cutting the sheet in the thickness direction as an observation surface, observation was performed with a scanning electron microscope (KEY-7 VE-7800), and the single fiber diameter of ultrafine fibers at any 100 points was measured, and the average value was calculated. , As the average single fiber diameter.

(2) Color fastness to friction when the sheet is wet:

The test was performed in accordance with JIS L0849 (2005) (scientific vibration test method) for a sheet in a wet state to evaluate the grade of the sample.

(3) Abrasion test of flakes:

The Martindale abrasion test evaluates the flakes after abrasion 20,000 times in the abrasion test in which the abrasion test (E method, Martindale method) according to JIS L1096 (2005) measures the load (12kPa) of furniture. Weight loss.

(4) Black color of the sheet (L value):

Black hair color (L value). Using the fluffy surface of the sheet as the measurement surface, the reflectance was measured by CR-310 manufactured by KONICA MINOLTA, and the L value was obtained from the color difference formula of Lab. The smaller the value is, the deeper the black is, and a value of 19 or less is regarded as acceptable.

(5) Evaluation of the surface feel of the sheet:

Evaluation was performed based on the sensory examination of 10 subjects. It is judged that 6 or more people judge that they have the same touch as natural leather, 3 to 5 people judge it as normal, and 2 people or less judge it as bad. Make Liang good. This judgment is a high judgment that a touch with a natural leather is included.

    [Example 1]    

(Raw cotton)

As the core component polymer, polyethylene terephthalate (PET) containing 2% by mass of carbon black with respect to the core component was used. As the sheath component polymer, polyethylene terephthalate (PET) to which 0.05% by mass of titanium oxide was added was used. As the sea component polymer, polystyrene (PSt) was used. A sea-island type composite spinning nozzle with 16 islands was used to melt-spin a fiber having a structure including an island component having a core-sheath structure. The structure is based on the number of cores per island, the core / sheath mass ratio is 50/50, and the core and sheath / sea mass ratio is 80/20. The obtained fiber was drawn. After that, a crimping process is performed. The obtained fiber was cut to a length of 51 mm to obtain raw cotton of an ultrafine fiber phenotype fiber having an average single fiber diameter of 26 μm.

(Filament twisted body composed of ultrafine fiber expression fibers)

Using the raw cotton of the above-mentioned ultrafine fiber expression type fibers, through a carding and folding machine step, a laminated fiber web is formed, and needle rolling is performed at a needle density of 2800 counts / cm ² to obtain a basis weight of 583 g / m ² and a thickness of 2.5 mm. It is a fiber twist composed of ultrafine fiber expression fibers.

(Flake precursor)

The fiber twist was treated with hot water at a temperature of 98 ° C to shrink it, and then impregnated with an aqueous solution of polyvinyl alcohol (hereinafter referred to as "PVA") to obtain a mass of PVA containing the mass of the fiber twist. A fiber twist of 30% by mass of ultrafine fiber-phenotype fibers. The fiber twisted body obtained as described above was immersed in trichloroethylene, and the sea component was dissolved and removed to obtain a fiber twisted body composed of a core-sheath composite ultrafine fiber. The fiber twist obtained as described above was immersed in a dimethylformamide solution of a polycarbonate polyurethane having a concentration of 12%, and then the polyurethane was subjected to an aqueous solution. solidification. This sample was immersed in hot water to remove PVA. Drying with hot air at a temperature of 110 ° C. for 10 minutes, a precursor sheet containing a core-sheath composite ultrafine fiber and a polyurethane sheet was obtained. The polyurethane adhered to the precursor sheet was 37% by mass based on the core-sheath composite ultrafine fiber.

After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320 grit sandpaper to form a fluff surface.

(Flaky)

The ground precursor sheet was subjected to a crimping performance treatment at a temperature of 130 ° C. using a liquid flow dyeing machine, and then dried using a dryer to obtain a sheet. The average single fiber diameter of the contained core-sheath composite ultrafine fibers was 4.4 μm. In the evaluation of the surface touch, 8 places were judged to be the same as the touch of natural leather. The L value representing the color of black hair is 18.2, and it has excellent black color. The rubbing color fastness is 4 when wet, and the Martindale abrasion loss is 6.1mg, which is excellent. The results are shown in Table 1.

    [Example 2]    

(Raw cotton)

Except that polyethylene terephthalate was used as the core component polymer so that the amount of carbon black added to the core component was 1% by mass, the same procedure was performed as in Example 1 to obtain an average single fiber diameter of 26 μm Raw cotton of superfine fiber expression type fiber (3-component composite fiber).

(Filament twisted body composed of ultrafine fiber expression fibers)

The raw cotton of the ultrafine fiber expression type fiber was used in the same manner as in Example 1 except that a fiber twisted body composed of the ultrafine fiber expression type fiber having a basis weight of 571 g / m ² and a thickness of 2.5 mm was obtained.

(Flake precursor)

Except having used the said fiber twisted body, it carried out similarly to Example 1, and obtained the precursor sheet of 38 mass% of polyurethane based on the ultrafine composite ultrafine fiber. After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320 grit sandpaper to form a fluff surface.

(Flaky)

Except having used the said precursor sheet, it carried out similarly to Example 1, and obtained the sheet-like object. The average single fiber diameter of the core-sheath composite ultrafine fibers constituting the obtained sheet was 4.4 μm. In the evaluation of the surface touch, 8 places were judged to be the same as the touch of natural leather. The L value was 18.5, and it had almost the same excellent black color properties as in Example 1. The rubbing color fastness is 4 when wet, and the Martindale abrasion loss is 5.8mg, which is excellent. The results are shown in Table 1.

    [Example 3]    

(Raw cotton)

Except that the following points were changed, raw cotton was obtained in the same manner as in Example 1 to obtain ultrafine fiber expression fibers (three-component composite fibers).

As the sheath component polymer, polyethylene terephthalate having 0.01% by mass of titanium oxide added to the sheath component was used.

In order to reduce the average single fiber diameter, the amount of sea component polymer discharged per spinning nozzle was reduced from 56 g / min to 28 g / minute, and the amount of core sheath polymer discharged was reduced from 227 g / minute to 114 g /minute.

The average single fiber diameter of the raw cotton is 18 μm.

(Non-woven fabric composed of microfiber expressing fibers)

The raw cotton of the ultrafine fiber expression type fiber was used in the same manner as in Example 1 except that a fiber twisted body composed of the ultrafine fiber expression type fiber having a basis weight of 591 g / m ² and a thickness of 2.5 mm was obtained.

(Flake precursor)

A precursor sheet having a polyurethane mass of 38% by mass was obtained in the same manner as in Example 1 except that the fiber twisted product was used. After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320-grit sandpaper to form a fluff surface.

(Flaky)

Except having used the said precursor sheet, it carried out similarly to Example 1, and obtained the sheet-like object. The average single fiber diameter of the core-sheath composite ultrafine fibers constituting the obtained sheet was 3.1 μm. In the evaluation of the surface texture, 9 places were judged to be the same as the texture of natural leather. The L value was 18.8, which was slightly inferior to that of Example 1, but had excellent black hair color properties. The rubbing color fastness is 4 when wet, and the Martindale abrasion loss is 6.5mg, which is excellent. The results are shown in Table 1.

    [Example 4]    

(Raw cotton)

A raw cotton having extremely fine fiber expression type fibers (three-component composite fibers) was obtained in the same manner as in Example 3 except that polyethylene terephthalate was used as the sheath component polymer.

(Filament twisted body composed of ultrafine fiber expression fibers)

It carried out similarly to Example 3, and obtained the fiber twisted body which consists of an ultrafine fiber phenotype fiber with a basis weight of 588 g / m <^2> and a thickness of 2.5 mm.

(Flake precursor)

Except having used the said fiber twisted body, it carried out similarly to Example 3, and obtained the precursor sheet of the sheet-like thing with a polyurethane mass of 38 mass%. After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320-grit sandpaper to form a fluff surface.

(Flaky)

Except having used the said precursor sheet, it carried out similarly to Example 3, and obtained the sheet | seat. The average single fiber diameter of the core-sheath composite ultrafine fibers constituting the obtained sheet was 3.1 μm. In the evaluation of the surface texture, 9 places were judged to be the same as the texture of natural leather. The L value was 18.6, which was more excellent than that of Example 3. The rubbing color fastness is 4 when wet, and the Martindale abrasion loss is 6.3mg, which is excellent. The results are shown in Table 1.

    [Comparative Example 1]    

(Raw cotton)

As the core component polymer, 4% by mass of polyethylene terephthalate with carbon black as the core component was used in the same manner as in Example 1. An ultrafine fiber phenotype having an average single fiber diameter of 26 μm was obtained. Raw cotton of fibers (sea-island type composite fibers).

(Filament twisted body composed of ultrafine fiber expression fibers)

The raw cotton of the ultrafine fiber expression type fiber was used in the same manner as in Example 1 except that a fiber twisted body composed of the ultrafine fiber expression type fiber having a basis weight of 563 g / m ² and a thickness of 2.3 mm was obtained.

(Flake precursor)

A precursor sheet having a polyurethane mass of 37% by mass was obtained in the same manner as in Example 1 except that the fiber twisted body was used. After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320-grit sandpaper to form a fluff surface.

(Flaky)

Except having used the said precursor sheet, it carried out similarly to Example 1, and obtained the sheet-like object. The average single fiber diameter of the ultrafine fibers constituting the obtained sheet was 4.4 μm. In the evaluation of the surface touch, 8 places were judged to be the same as the touch of natural leather. The L value was 17.5, which was excellent in black hair color, but the Martindale abrasion loss was 10.1 mg, which was inferior to Example 1. The results are shown in Table 1.

    [Comparative Example 2]    

(Raw cotton)

The raw cotton of the ultrafine fiber expression type fiber was obtained like Example 1 except having changed the following points.

In order to increase the average single fiber diameter, a sea-island composite spinning nozzle with 6 islands was used to increase the amount of sea component polymer discharged from each spinning nozzle from 56 g / minute to 600 g / minute to make the core sheath The amount of component polymer discharged increased from 227 g / min to 2490 g / min.

The average single fiber diameter of the ultrafine fiber phenotype fibers was 72 μm.

(Filament twisted body composed of ultrafine fiber expression fibers)

The raw cotton of the ultrafine fiber expression type fiber was used in the same manner as in Example 1 except that a fiber twisted body composed of the ultrafine fiber expression type fiber having a basis weight of 589 g / m ² and a thickness of 2.7 mm was obtained.

(Flake precursor)

A precursor sheet having a polyurethane mass of 37% by mass was obtained in the same manner as in Example 1 except that the fiber twisted body was used. After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320-grit sandpaper to form a fluff surface.

(Flaky)

Except having used the said precursor sheet, it carried out similarly to Example 1, and obtained the sheet-like object. The average single fiber diameter of the ultrafine fibers constituting the obtained sheet was 12.1 μm. The L value was 16.2, and although it had excellent black hair color properties, in the evaluation of the surface texture, two people judged that the texture was the same as that of natural leather, and the texture was different from that of natural leather. The results are shown in Table 1.

    [Comparative Example 3]    

(Raw cotton)

As the core component polymer, except that carbon black was not used, polyethylene terephthalate was used in the same manner as in Example 1 to obtain ultrafine fiber expression fibers (3-component composite fibers having an average single fiber diameter of 26 μm). ) Of raw cotton.

(Filament twisted body composed of ultrafine fiber expression fibers)

The raw cotton of the above-mentioned ultrafine fiber expression type fiber was used in the same manner as in Example 1 except that a fiber twisted body composed of the ultrafine fiber expression type fiber having a basis weight of 560 g / m ² and a thickness of 2.5 mm was obtained.

(Flake precursor)

A precursor sheet having a polyurethane mass of 37% by mass was obtained in the same manner as in Example 1 except that the fiber twisted body was used. After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320-grit sandpaper to form a fluff surface.

(Flaky)

Except having used the said precursor sheet, it carried out similarly to Example 1, and obtained the sheet-like object. The average single fiber diameter of the ultrafine fibers constituting the obtained sheet was 4.4 μm. In the evaluation of the surface texture, 8 digits were judged to be the same as the texture of natural leather, but the L value was 23.0, and the black color was lacking. The rubbing color fastness is 4 when wet, and the Martindale abrasion loss is 6.0mg, which is excellent. The results are shown in Table 1.

    [Comparative Example 4]    

(Raw cotton)

A raw cotton having extremely fine fiber expression type fibers was obtained in the same manner as in Comparative Example 2 except that polyethylene terephthalate was used as the sheath component polymer without adding titanium oxide.

(Filament twisted body composed of ultrafine fiber expression fibers)

The raw cotton of the ultrafine fiber expression type fiber was used in the same manner as in Comparative Example 2 except that the fiber twisted body composed of the ultrafine fiber expression type fiber having a basis weight of 581 g / m ² and a thickness of 2.7 mm was obtained.

(Flake precursor)

Except having used the said fiber twisted body, it carried out similarly to the comparative example 2, and obtained the precursor sheet of the sheet-like thing with a polyurethane mass of 37 mass%. After that, the above-mentioned precursor piece was cut in half in the thickness direction, and the cut half surface was polished with 320-grit sandpaper to form a fluff surface.

(Flaky)

Except having used the said precursor sheet, it carried out similarly to the comparative example 2, and obtained the sheet-like object. The average single fiber diameter of the ultrafine fibers constituting the obtained sheet was 12.1 μm. The L value was 16.0, and although it had excellent black hair color properties, in the evaluation of the surface texture, two people judged that the texture was the same as that of natural leather and the texture was different from that of natural leather. The results are shown in Table 1.

Examples 1 to 4 are all those having the same degree of touch as natural leather, and those with excellent Martindale abrasion loss and black hair color. In Comparative Example 1, compared with Example 1, carbon black was added at 4% by mass, the physical properties of the fibers were deteriorated, and the Martindale abrasion loss was increased. Comparative Example 2 has an average single fiber diameter larger than that of Example 1, and thus has a rough feel unlike natural leather. In Comparative Example 3, compared with Example 1, carbon black was not added, so black hair color was lacking. In Comparative Example 4, compared with Example 4, the average single fiber diameter became larger, so it had a rougher feel than natural leather.

Claims (8)

    A sheet-like material is a sheet-like material comprising a fiber structure having extremely fine fibers having an average single fiber diameter of 1 to 10 μm, the ultra-fine fibers are core-sheath composite fibers having a core-sheath structure, and the core of the core-sheath composite fibers The component is a polyester containing 0.1 to 3% by mass of a pigment, and the sheath component is a polyester containing no pigment contained in a core component.         The sheet according to claim 1, wherein the sheath component is a polyester containing no pigment of any kind.         As in the sheet of claim 1, wherein the core component of the core-sheath composite fiber does not contain titanium oxide, the sheath component contains only titanium oxide as a pigment component, and the content of titanium oxide is the sum of polyester and titanium oxide relative to the sheath component The content is more than 0% by mass and 0.01% by mass or less.         The sheet according to any one of claims 1 to 3, wherein the sheet includes a non-woven fabric composed of the ultrafine fibers and a polymer elastomer, and at least one side of the sheet is fleece.         The flake according to any one of claims 1 to 4, wherein the pigment is a black pigment and contains 0.1 to 3% by mass with respect to the core component.         The flake according to claim 5, wherein the black pigment is carbon black and contains 0.1 to 3% by mass based on the core component.         For example, the flakes according to any one of claims 1 to 6, which satisfy each of the following conditions (A) to (C); (A) the rubbing color fastness when wet is 4 or more; (B) The Martindale abrasion loss is 9.0 mg or less; (C) The reflectance of the surface with fluff is measured, and the L value calculated by the color difference formula of Lab is 19 or less.         A method for manufacturing a sheet, which is the method for manufacturing a sheet according to any one of claims 1 to 7, comprising: twisting a cross-sectional structure into a core-sheath structure and having a sea component surrounding the core-sheath structure; A step of obtaining a fiber twisted body of a non-woven fiber composed of ultrafine fiber expression type fibers; a step of immersing the fiber twisted body in a solvent and washing out the sea component to make the ultrafine fiber expression type fiber into a core-sheath composite fiber; A step of imparting a polymer structure to the fiber structure of the core-sheath composite fiber; and a step of performing a fluffing treatment on one or both sides of the fiber structure including the obtained polymer elastomer.