TW201615704A - Sheet-shaped material and method for producing same - Google Patents

Abstract

The present invention provides a sheet-shaped material, specifically a leathery sheet-shaped material having appropriate elasticity excelling in drape properties and soft texture like natural suede that could not conventionally be realized, and a method for manufacturing the same. This sheet-shaped material contains a polymer elastomer in a fibrous base material formed by including ultra-fine fibers in average single fiber diameter of 0.3-7 [mu]m, and has nap raising on at least one surface, wherein the compression rate P of the sheet-shaped material obtained by expression 1 with regard to the thickness T0 of the sheet-shaped material when an initial load of 0.5 kPa is applied following a JIS L1913 method, the thickness T1 of the sheet-shaped material when a load of 30 kPa is applied, and the thickness T2 of the sheet-shaped material when the load is then restored to the initial load of 0.5 kPa, is 7-14% inclusive, and further a compressive elastic modulus Pe obtained by expression 2 is 30-70% inclusive. Expression 1: Compression rate P (%) = 100*(T0 - T1)/T0 Expression 2: Compressive elastic modulus Pe (%) = 100*(T2 - T1)/(T0 - T1).

Description

Sheet material and method of manufacturing same

The present invention relates to a sheet material and a method for producing the same, and in particular to a leather sheet material having a moderate elasticity excellent in drape feeling and a conventional soft texture, and a method for producing the same.

A leather-like sheet material mainly comprising a fibrous base material and a polymeric elastomer such as polyurethane, which has excellent characteristics not found in natural leather, and is widely used in various applications. In particular, a leather-like sheet material using a polyester-based fibrous base material is excellent in light resistance, and thus it is expanding its use year by year in terms of clothing materials, chair skins, and automotive interior materials.

In view of such a leather-like sheet, a moderate elasticity excellent in drape feeling is required, and a soft hand such as natural suede is required, and various reviews have been conducted so far.

A method of impregnating a sheet-like material with a polyfluorene-based resin is proposed as a means for exhibiting the elasticity of the leather-like sheet material (see Patent Document 1). However, this proposal has a problem that the feel of the sheet material becomes hard due to the excessive elasticity of the polyoxymethylene resin.

In addition, a method of softening a sheet material by subjecting a sheet material containing a polyester fiber and a polymer elastomer to alkali reduction treatment has been proposed (see Patent Document 2). However, as proposed in this proposal, a sheet containing a polymeric elastomer is applied. In the method of alkali reduction treatment, there is a problem that the deterioration of the polymer elastomer causes deterioration of the abrasion resistance of the sheet material.

In other words, in the case of producing a sheet material in the present case, it is not possible to obtain a leather-like sheet material which has both moderate elasticity excellent in drape feeling and soft hand feeling like natural suede.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-235644

[Patent Document 2] Japanese Patent Laid-Open No. 1-229882

It is an object of the present invention to provide a sheet-like material, in particular, a leather-like sheet material having a moderate elasticity excellent in drape feeling and a soft hand feeling which is not practically made of natural suede, and a method for producing the same.

The sheet material of the present invention contains a polymeric elastomer in a fibrous substrate composed of ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm, and at least one side surface is provided with a raised sheet material; The sheet material was subjected to a sheet material thickness T0 at an initial load of 0.5 kPa according to the method of JIS L1913, a sheet-like material thickness T1 at a load of 30 kPa, and a sheet-like shape when the initial load was 0.5 kPa. The material thickness T2 is a compression ratio P obtained by the following formula 1 of 7% or more and 14% or less, and the compression elastic modulus Pe obtained according to the following formula 2 is 30% or more and 70% or less; Equation 1: Compression ratio P (%) = 100 × (T0 - T1) / T0

Formula 2: Compressive elastic modulus Pe (%) = 100 × (T2-T1) / (T0 - T1).

According to a preferred aspect of the sheet material of the present invention, the above sheet material contains a woven fabric.

Furthermore, the method for producing a sheet material of the present invention is characterized by comprising the following steps (1) to (3): (1) a fibrous substrate containing ultrafine fibers. a step of imparting a polyvinyl alcohol at a temperature of 5 ° C or more and 90 ° C or less; (2) applying a polymer elastomer to the fibrous base material obtained by the above 1 step to produce a sheet material. Step; (3). Performing a step of raising the at least one side of the obtained sheet.

According to a preferred aspect of the method for producing a sheet material according to the present invention, there is provided a step of imparting a polyvinyl alcohol adjusted to a temperature of 50 ° C or higher and 75 ° C or lower after dissolving polyvinyl alcohol at a temperature of 95 ° C or higher. .

According to a preferred aspect of the method for producing a sheet material of the present invention, the degree of polymerization of the polyvinyl alcohol is 400 or more and 600 or less.

According to a preferred embodiment of the method for producing a sheet material of the present invention, in the step (3), a polymer elastomer dissolved in an organic solvent is used to impart a polymer elastomer.

The method for producing a sheet material according to the present invention is characterized by comprising the method for producing a sheet material having the following steps (1) to (3): (1) putting a fibrous substrate containing extremely fine fibers into a viscosity of 10 a step of imparting polyvinyl alcohol in an aqueous solution of ~50 mPa ‧ polyvinyl alcohol; (2) imparting polymer elasticity to the fibrous substrate obtained after the above 1 step a step of producing a sheet material; and (3) a step of performing a raising treatment on at least one side of the obtained sheet material.

According to a preferred aspect of the method for producing a sheet material of the present invention, the degree of polymerization of the polyvinyl alcohol is 400 or more and 600 or less.

According to a preferred embodiment of the method for producing a sheet material of the present invention, in the step 2, a polymer elastomer dissolved in an organic solvent is used to impart a polymer elastomer.

According to a preferred aspect of the method for producing a sheet material according to the present invention, the fibrous substrate containing the ultrafine fibers in the above step 1 is obtained by removing the sea component of the fibrous substrate sheet containing the sea-island type fibers, so as to exhibit extremely fine Made of fiber.

According to the present invention, it is possible to obtain a sheet-like article, in particular, a leather-like sheet material which has a moderate elasticity which is excellent in drape feeling and which is not practically capable of realizing a soft hand feeling such as natural suede.

The sheet material of the present invention contains a polymeric elastomer in a fibrous base material composed of ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm, and at least one side of the surface is provided with a raised sheet material.

The fiber constituting the fibrous substrate used in the present invention may be a polyester comprising polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate or polylactic acid; Polyamides such as 6-nylon or 66-nylon; polyolefins such as polyacrylic acid, polyethylene or polypropylene, and thermoplastics such as thermoplastic cellulose Fiber of resin. Among them, polyester fibers are preferably used from the viewpoint of strength, dimensional stability, and light resistance. Further, the fibrous substrate may be composed of a mixture of different other materials.

The cross-sectional shape of the fiber used in the present invention may be a circular cross-section, but fibers of a polygonal cross-section such as an ellipse, a flat, a triangle, or the like may be used.

The average fiber diameter of the fibers constituting the fibrous substrate formed of the ultrafine fibers used in the present invention is 0.3 to 7 μm. By setting the average single fiber diameter to 7 μm or less, more preferably 6 μm or less, and particularly preferably 5 μm or less, a sheet having excellent flexibility and raising properties can be obtained. On the other hand, when the average single fiber diameter is set to 0.3 μm or more, more preferably 0.7 μm or more, and particularly preferably 1 μm or more, color development after dyeing or raising by sanding or the like can be obtained. The sheet-like fiber is excellent in dispersibility and is excellent in soft hand.

Further, if the average single fiber diameter of the fiber is more than 7 μm, an excellent surface feel cannot be obtained, and the texture of the sheet is hardened. Further, when the average single fiber diameter of the fiber is less than 0.3 μm, the fiber is weak and the fuzzing is small, and a good surface quality cannot be obtained.

The average fiber diameter of the fibers constituting the fibrous substrate can be determined in the following manner. That is, when the cross section of the fiber is circular or nearly circular, the scanning electron microscope (SEM) photograph of the surface of the fibrous substrate or sheet is taken at a magnification of 2000 times, and 100 fibers are randomly selected and measured. The single fiber diameter was calculated and the average single fiber diameter was calculated and set as the average single fiber diameter.

The form of the fibrous base material containing the ultrafine fibers used in the present invention may be a knitted fabric, a knitted fabric, a non-woven fabric or the like. Wherein, the sheet is raised from the surface From the viewpoint that the surface quality of the material is good, it is preferred to use a non-woven fabric.

As the non-woven fabric, any of a short fiber nonwoven fabric and a long fiber nonwoven fabric can be used, but a short fiber nonwoven fabric is preferably used from the viewpoint of hand feeling or quality.

The short fiber of the short fiber non-woven fabric preferably has a fiber length of 25 to 90 mm. By setting the fiber length to 25 mm or more, it is possible to obtain a sheet material excellent in abrasion resistance by entanglement. Moreover, by setting the fiber length to 90 mm or less, a sheet material having a more excellent hand feeling or quality can be obtained. The fiber length is preferably 35 to 75 mm.

When the fibrous base material containing the ultrafine fibers is a non-woven fabric, the nonwoven fabric preferably has a structure in which a bundle of extremely fine fibers (very fine fiber bundle) is entangled. The strength of the sheet material is increased by the state in which the ultrafine fibers are entangled in a bundled state. Such a non-woven fabric is obtained by previously entanglement of the ultrafine fiber constituting fibers to form a fibrous base sheet, and then exhibiting extremely fine fibers by the ultrafine fiber constituting fibers.

When the ultrafine fibers or the ultrafine fiber bundles thereof constitute a non-woven fabric, the knitted fabric or the knitted fabric can be inserted for the purpose of improving the internal strength thereof and/or suppressing the dimensional change during processing. In this case, the knitted fabric structure may be a plain weave structure, a twill weave, a satin weave or the like, and a plain weave structure is preferably used from the viewpoint of cost. Further, examples of the woven structure include a circular knitting structure, a tricot, and a Raschel. The average single fiber diameter of the fibers constituting such a knitted fabric or knitted fabric is preferably about 0.3 to 10 μm.

The polymer elastic system used in the present invention may, for example, be a polyurethane resin, an acrylic resin or a polyoxyxylene resin, or may be used in combination with these resins. Among them, the present invention is more preferably a polyurethane resin from the viewpoint of exhibiting durability in a leather state such as artificial leather. Among the polyurethane resins, an elastic and soft hand having excellent drape feeling can be obtained. It is preferred to use a solution type polyurethane resin ("CRISVON" (registered trademark) MP-812NB, manufactured by DIC Co., Ltd.) dissolved in an organic solvent. Further, an aqueous polyurethane resin ("HYDRAN" (registered trademark) WLI-602, manufactured by DIC Corporation) or the like can be used.

The ratio of the sheet-like polymer elastomer of the present invention to the sheet material is preferably 10% by mass or more and 80% by mass or less, more preferably 15% by mass or more and 55% by mass or less. By setting the ratio of the polymeric elastomer to 10% by mass or more, the sheet strength can be obtained and the fibers can be prevented from falling off. In addition, by setting the ratio of the polymeric elastomer to 50% by mass or less, it is possible to prevent the hand from becoming hard and to obtain a good hand.

The polyurethane resin is preferably a polyurethane resin obtained by a reaction of a polymer diol, an organic diisocyanate, and a chain extender.

As the polymer diol, for example, a polycarbonate-based, polyester-based, polyether-based, polyfluorene-based or fluorine-based diol can be used, and a copolymer of these combinations can also be used.

Further, from the viewpoint of hydrolysis resistance, a polycarbonate-based or polyether-based diol is preferably used. Further, from the viewpoints of light resistance and heat resistance, a polycarbonate-based or polyester-based diol is preferably used. Further, from the viewpoint of balance between hydrolysis resistance, heat resistance and light resistance, a polycarbonate-based and polyester-based diol is preferably used, and a polycarbonate-based diol is particularly preferably used.

The polycarbonate diol system can be produced by a transesterification reaction of an alkylene glycol with a carbonate or a reaction of phosgene or a chloroformate with an alkylene glycol.

Examples of the alkylene glycol system include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and a linear alkylene glycol such as 10-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane Alcohol, branched alkyl diol such as 2-methyl-1,8-octanediol; alicyclic diol such as 1,4-cyclohexane diol; aromatic diol such as bisphenol A; glycerin, three Hydroxymethylpropane, pentaerythritol, and the like. Any of a polycarbonate diol obtained from each of the individual alkylene glycols or a copolymerized polycarbonate diol obtained from two or more alkylene glycols can be used.

The polyester diol type is a polyester diol obtained by condensing various low molecular weight polyols and a polybasic acid.

As the low molecular weight polyol, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, 2,2-dimethyl-1 can be used. , 3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, One or more of cyclohexane-1,4-diol and cyclohexane-1,4-dimethanol are selected. Further, an adduct of various alkylene oxides may be added to bisphenol A.

Further, examples of the polybasic acid include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, and dodecanedicarboxylic acid. One or more of phthalic acid, isophthalic acid, terephthalic acid, and hexahydroisophthalic acid are selected.

Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and a copolymerized diol derived from the combination.

The number average molecular weight of the polymer diol is preferably from 500 to 4,000. By setting the number average molecular weight to 500 or more, and more preferably 1500 or more, it is possible to prevent the hand from becoming hard. Further, by setting the number average molecular weight to 4,000 or less, more preferably 3,000 or less, the strength at the time of becoming a polyurethane can be maintained.

Examples of the organic diisocyanate include hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene. An aliphatic diisocyanate such as an isocyanate; an aromatic diisocyanate such as diphenylmethane diisocyanate or toluene diisocyanate may be used. Among them, from the viewpoint of light resistance, aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferably used.

As the chain extender, an amine chain extender such as ethylenediamine or methylenebisaniline or a glycol chain extender such as ethylene glycol can be used. Further, a polyamine obtained by reacting a polyisocyanate with water can also be used as a chain extender.

In the polyurethane, a crosslinking agent can be used in combination for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like. As the crosslinking agent, an external crosslinking agent added as a third component with respect to the polyurethane resin may be used, or an internal crosslinking agent which introduces a reaction point which becomes a crosslinking structure in the molecular structure of the polyurethane in advance may be used. From the viewpoint of more uniform topographical distribution in the molecular structure of the polyurethane and a reduction in flexibility, it is preferred to use an internal crosslinking agent.

The crosslinking agent can be used with an isocyanate group, A compound such as an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, or a sterol group. However, if the crosslinking is excessively carried out, the polyurethane tends to be hardened and the texture of the sheet material tends to be hard. Therefore, from the viewpoint of balance between reactivity and flexibility, a compound having a decyl group is preferably used.

Further, the polyurethane resin used in the present invention may contain a hydrophilic group in the molecular structure. By having a hydrophilic group in the molecular structure, when a water-dispersible polyurethane resin is used, the dispersibility and stability can be improved.

The hydrophilic group may, for example, be a cationic system such as a quaternary amine salt; an anionic system such as a sulfonate or a carboxylate; a nonionic system such as polyethylene glycol; a combination of a cationic system and a nonionic system; and an anionic system. Any combination of hydrophilicity with a nonionic system base. Among them, a nonionic hydrophilic group which does not cause yellowing due to light or a concern due to a neutralizing agent is used.

That is, in the case of an anionic hydrophilic group, a neutralizing agent is required, but when, for example, a neutralizing agent is a tertiary amine such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine or dimethylethanolamine, The amine will be volatilized due to heat during film formation or drying, and the amine will be released out of the system. Therefore, in order to suppress the release of the atmosphere or the deterioration of the working environment, it is necessary to introduce a device for recovering the volatile amine. Further, when the amine does not volatilize by heating and remains in the sheet material of the final product, it is considered that it is discharged to the environment when the product is incinerated or the like. On the other hand, in the case of a nonionic hydrophilic group, since the neutralizing agent is not used, it is not necessary to introduce an amine recovery device, and there is no fear that the amine will remain in the sheet material.

Further, the neutralizing agent is an alkali metal such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or a hydroxide of an alkaline earth metal, etc., and the polyurethane moiety is alkaline if wetted by water, but when it is nonionic In the case of a hydrophilic group, since no neutralizing agent is used, there is no fear of deterioration due to hydrolysis of the polyurethane resin.

The polyurethane resin may contain various additives such as pigments such as carbon black; flame retardants such as phosphorus, halogen, polyoxane, and inorganic; antioxidants such as phenol, sulfur, and phosphorus; and benzene. And a UV absorber such as a triazole-based, a diphenylketone-based, a salicylate-based, a cyanoacrylate-based or an oxalic acid aniline; a hindered amine-based or benzoic acid-based light stabilizer; Hydrolysis-resistant stabilizer such as diterpenoid; plasticizer, antistatic agent, surfactant, softener, water repellent, coagulation regulator, dye, preservative, antibacterial agent, deodorant, cellulose particle and other fillers And inorganic particles such as cerium oxide or titanium oxide.

The sheet material of the present invention is in accordance with the method of JIS L1913, with respect to The thickness T0 of the sheet material when the initial load was 0.5 kPa, the thickness T2 of the sheet material when the load was applied at 30 kPa, and the thickness T2 of the sheet material when the initial load was 0.5 kPa, was obtained according to the following formula 1. The compression ratio P is 7% or more and 14% or less, and the compression elastic modulus Pe obtained according to the following formula 2 is 30% or more and 70% or less, and the moderate elasticity which is excellent in drape feeling is not realized. It is important to be soft like a natural suede.

Equation 1: Compression ratio P (%) = 100 × (T0 - T1) / T0

Formula 2: Compressive elastic modulus Pe (%) = 100 × (T2-T1) / (T0 - T1).

The difference between the thickness of the sheet material at the initial load of 0.5 kPa and the thickness T1 of the sheet material when the load is applied at 30 kPa is the action when the finger is pressed into the sheet, and the difference is larger. The more the finger sinks, the softer the feel.

The difference between the thickness T1 of the sheet material when the load was applied at 30 kPa and the thickness T2 of the sheet material when it was returned to the initial load of 0.5 kPa (T2-T1) was simulated by releasing the sheet material from the finger. The action of the time, the more the difference, the greater the thickness recovery, and the more the finger feels the elasticity.

The sheet material of the present invention is a very hard sheet material if the compression ratio is less than 7%, and a sheet material having a soft hand cannot be obtained. Further, when the compression ratio is more than 14%, not only a sheet material having no elasticity but also a drape feeling is obtained, and the mechanical properties are weak, which is unsuitable for practical use.

In addition, when the compression elastic modulus is less than 30%, the rebound property when the finger is pressed into the sheet material is weak, and the sheet material has no drape feeling. Further, when the compression elastic modulus is more than 70%, the hand feels very hard when the finger is pressed into the sheet.

In order to exhibit moderate elasticity with excellent drape and soft hand feel like natural suede, it is important to have a suitable compression ratio and compression bomb as described above. A sheet of sexual modulus.

The compression ratio is preferably 7.5% or more and 14% or less, more preferably 8% or more and 13% or less from the viewpoint of texture and elasticity. Further, the compression elastic modulus is preferably 35% or more and 65% or less. More preferably, it is 40% or more and 60% or less.

In the present invention, at least one side of the sheet material is subjected to a raising treatment to form a fuzz on the surface. As a method of forming the fluffing, various methods such as polishing using sandpaper or the like can be used.

Next, a method of producing the sheet material of the present invention will be described. The method for producing a sheet material of the present invention includes the production method of the following steps (1) to (3).

(1) a step of imparting a polyvinyl alcohol having a temperature of 5 ° C or higher and 90 ° C or lower to a fibrous substrate containing ultrafine fibers; (2) imparting a high degree to the fibrous substrate obtained by the above 1 step a step of producing a sheet material with a molecular elastomer; and (3) a step of raising the surface of at least one side of the obtained sheet material.

The method for producing a sheet material of the present invention is important in that polyvinyl alcohol is imparted to a fibrous substrate having extremely fine fibers at a temperature of 50 ° C or more and 75 ° C or less. Since the polymer elastomer causes the ultrafine fibers to be restrained and loses the degree of freedom, the preferred aspect is to impart polyvinyl alcohol before the polymer elastic body is imparted, and to dispose the polyvinyl alcohol around the ultrafine fibers to hinder the ultrafine fibers and the high fiber. The molecular elastomer is directly followed, thereby ensuring the ultrafine fiber freedom within the sheet.

The polyvinyl alcohol aqueous solution supplied to the fibrous base material containing the ultrafine fibers is mainly adjusted to a temperature of 5 ° C or more and 90 ° C or less in advance.

When the temperature of the aqueous solution of the polyvinyl alcohol is less than 5 ° C, the viscosity of the aqueous solution becomes extremely high, resulting in inability to be uniformly imparted, resulting in a decrease in the degree of freedom of the ultrafine fibers. This causes the elasticity of the sheet to deteriorate. Moreover, when the temperature of the polyvinyl alcohol aqueous solution is higher than 90 ° C, the viscosity of the aqueous solution becomes too low, and when the polyvinyl alcohol aqueous solution is applied to the fibrous substrate containing the ultrafine fibers, the polyvinyl alcohol is in the fibrous substrate. Moving, causing the feel of the sheet to harden. The temperature of the polyvinyl alcohol aqueous solution is more preferably 50° C. or higher and 75° C. or lower. By setting this temperature, it is possible to balance the moderate elasticity and the very soft hand having excellent drape feeling.

A better method for adjusting the temperature of the aqueous solution of polyvinyl alcohol is the following method.

The polyvinyl alcohol is dissolved well at 90 ° C or higher. However, when it is adjusted to a temperature of 50 ° C or more and 75 ° C or less, it is dissolved by temporarily raising the temperature to 90 ° C or higher, and then adjusted to 50 ° C. Above and below 75 ° C, a uniformly dissolved polyvinyl alcohol solution can be obtained.

It is important that the temperature of the adjusted polyvinyl alcohol solution is maintained until the temperature is given to the fibrous substrate, and the temperature at the time of application is 50 ° C or more and 75 ° C or less. The method is to provide a polyvinyl alcohol solution adjusted to 50° C. or higher and 75° C. or lower, and put it into a container having a heat insulating function, and then, after maintaining a certain temperature, the fibrous substrate is placed in the container and then reused. a method in which a nip roll is extruded, or a method in which a polyvinyl alcohol solution having a constant temperature is applied to a fibrous substrate, but from the viewpoint of uniformly imparting a fibrous substrate containing extremely fine fibers, it is preferred to After the fibrous base material is introduced into the polyvinyl alcohol solution, the nip roll is used for extrusion.

Further, the degree of polymerization of the polyvinyl alcohol to be added is preferably 400 or more and 600 or less. If the degree of polymerization is less than 400, the viscosity of the aqueous solution is too low, and when the polyvinyl alcohol aqueous solution is applied to the fibrous substrate containing the ultrafine fibers, the polyvinyl alcohol moves in the fibrous substrate, causing the feeling of the sheet. Harden. If the degree of polymerization is greater than 600, Then, the viscosity of the aqueous solution becomes extremely high, and the degree of freedom of the ultrafine fibers of the fibrous base material to which the polyvinyl alcohol is imparted is lowered, and the elasticity of the sheet-like material from which the polyvinyl alcohol is removed after the addition of the polyurethane is deteriorated. Examples of the polyvinyl alcohol having a degree of polymerization of 400 or more and 600 or less include DENKA POVAL B-04, B-05, and K-05 manufactured by Denki Kagaku Kogyo Co., Ltd., and GOHSENOL GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd., and the like.

Further, the polyvinyl alcohol to be applied is preferably a polyvinyl alcohol aqueous solution having a viscosity of 10 to 50 mPa ‧ . When the viscosity is less than 10 mPa‧s, when the polyvinyl alcohol aqueous solution is applied to the fibrous base material containing the ultrafine fibers, the polyvinyl alcohol moves in the fibrous base material, and the texture of the sheet material becomes hard. When the viscosity is more than 50 mPa ‧ s, the degree of freedom of the ultrafine fibers of the fibrous base material to which polyvinyl alcohol is imparted is lowered, and the elasticity of the sheet material from which the polyvinyl alcohol is removed after imparting the polyurethane is deteriorated.

Further, it is preferred that the polyvinyl alcohol aqueous solution is adjusted to have a viscosity of 10 to 50 mPa·s in a container, and then the fibrous substrate is placed in a container and supplied. This method imparts uniform impartment of polyvinyl alcohol to the ultrafine fibers in the fibrous substrate. More preferably 15~40mPa‧s. After the fibrous base material is placed in a container to which the polyvinyl alcohol aqueous solution has been placed and supplied, the amount of polyvinyl alcohol to be applied can be adjusted by pressing with a nip roll.

As means for forming the ultrafine fibers of the fibrous substrate, it is preferred to use ultrafine fiber styling fibers. By using the ultrafine fiber characterization fiber, the form in which the ultrafine fiber bundle is entangled can be stably obtained.

In the ultrafine fiber phenotype fiber type, a sea component and an island component are formed by a two-component thermoplastic resin having a solvent solubility, and a seawater component is dissolved and removed by using a solvent or the like to form an island-in-the-sea fiber having an island component as an ultrafine fiber; In the two-component thermoplastic resin, the fiber cross-section is arranged in a radial or multi-layered manner, and the split fibers are separated into fine fibers. Among them, island type By removing the sea component, the fiber system can provide an appropriate gap between the island components, that is, between the ultrafine fibers, and thus can be preferably used from the viewpoint of flexibility or hand feeling of the sheet material.

The island-in-the-sea type fiber system includes an island-in-sea type composite fiber in which a sea-component component and a island component 2 component are mutually arranged and spun by using a sea-island composite spinning opening, or a mixture of sea component and island component 2 component and spun yarn. Spinning fibers, etc. The sea-island type composite fiber is preferably used from the viewpoint of obtaining a fine fiber having a uniform fineness and contributing to the strength of a sheet obtained from a sufficiently long ultrafine fiber.

The sea component of the sea-island type fiber may be a copolymerized polyester or a polylactic acid obtained by copolymerizing polyethylene, polypropylene, polystyrene, sodium isophthalate or polyethylene glycol. Among them, from the viewpoint of environmental concerns, it is preferred to use a copolymerized polyester or polylactic acid which is copolymerized with an alkali-decomposable sodium isophthalate sulfonate or polyethylene glycol which can be decomposed without using an organic solvent. .

The sea-removing treatment in the case of using the sea-island type fiber can be performed by immersing the sea-island type fiber in a solvent and performing a squeezing liquid, or providing a solvent necessary for the sea-removing in the fibrous base material, and then performing heat treatment to remove the sea by rinsing. The method of ingredients, etc. As a solvent for dissolving the sea component, when the sea component is polyethylene, polypropylene or polystyrene, an organic solvent such as toluene or trichloroethylene can be used; when the sea component is a copolymerized polyester or polylactic acid, it can be used. An aqueous alkali solution such as sodium hydroxide. From the viewpoint of the environmental concerns of the process, it is preferred to carry out the sea removal treatment using an aqueous alkali solution such as sodium hydroxide.

After being expressed by the ultrafine fibers, the application of the aqueous polyvinyl alcohol solution was carried out as described above. The method of imparting the aqueous solution of polyvinyl alcohol is preferably a method in which a substrate containing extremely fine fibers or a sheet after sea removal can be uniformly imparted. For example, a method in which a polyvinyl alcohol aqueous solution is impregnated and then squeezed by a nip roll, a method of applying by a spray, or a method using a knife coater or a gravure roll coater is applied.

After the polymeric elastomer is applied to the fibrous base material to which polyvinyl alcohol is added, extraction and removal of polyvinyl alcohol are carried out. By performing the removal, a void can be formed between the ultrafine fibers and the polyurethane resin, and the degree of freedom of the ultrafine fibers can be ensured.

The application of the polymeric elastomer is preferably carried out by adjusting the polymeric elastomer to an appropriate concentration using an organic solvent. The polymer elastomer dissolved in the organic solvent, particularly the polyurethane dissolved in the organic solvent, is more likely to exhibit the elasticity of the sheet material than the water-dispersible polyurethane, and thus it is preferred to The polyvinyl ester dissolved in the organic solvent is adjusted to a moderate concentration with the same organic solvent, and then the fibrous substrate to which the polyvinyl alcohol has been imparted is imparted.

After the polyurethane substrate is provided with a polyurethane, the sheet to which the polyurethane is added is cut in the thickness direction of the sheet. Thereby, the production efficiency can be improved, and when the sheet material contains the knitted fabric or the knitted fabric, the sheet having the dense appearance quality can be obtained by performing the following raising treatment on the cut half surface of the sheet thickness direction. Material.

In order to form fluff on the surface of the sheet, a raising treatment can be performed. The raising treatment can be carried out by a method of performing grinding using a sandpaper or a belt machine or the like. Moreover, it is easy to apply the pilling by the surface grinding before the raising process, and the surface quality is excellent.

The sheet material can be dyed. The dyeing method is preferably a liquid flow dyeing machine from the viewpoint of imparting a softening effect to the softening effect of the sheet material while softening the sheet material.

The dyeing temperature varies depending on the type of the fiber, and is preferably in the range of 80 to 150 °C. By setting the dyeing temperature to 80 ° C or higher, more preferably 110 ° C or higher, the dyeing can be performed with good fiber efficiency. On the other hand, by setting the dyeing temperature to 150 ° C or lower, more preferably 130 ° C or lower, deterioration of the polyurethane can be prevented.

The dye used in the present invention can be selected in accordance with the type of fiber constituting the fibrous substrate. For example, a disperse dye can be used for the polyester fiber, and an acid dye or a gold-containing dye can be used for the polyamide fiber, and a combination of these can be further used. When dyeing is carried out using a disperse dye, it may be subjected to reduction washing after dyeing.

Furthermore, it is also preferred to use a dyeing aid during dyeing. By using a dyeing aid, the uniformity or reproducibility of dyeing can be improved. Further, after the same bathing or dyeing, the finishing agent may be treated with a softening agent such as polyfluorene oxide, an antistatic agent, a water repellent, a flame retardant, a light stabilizer, and an antibacterial agent.

The sheet material obtained by the present invention can be suitably used as: furniture, chairs and wall materials; or seats in vehicles such as automobiles, trains, and airplanes; and skin materials such as ceilings and interiors, which have a very elegant appearance. Materials, or uppers, decorations, etc. for shoes, jackets, casual shoes, sports shoes, gentlemen's shoes, and women's shoes; bags, belts, wallets, etc., and materials used for clothing, wiping cloth, etc. Industrial materials such as abrasive cloth and CD jacket.

[Examples]

Next, the sheet material of the present invention and the method for producing the same will be described in more detail by way of examples, but the invention is not limited to the examples.

[Evaluation method]

(1) Average single fiber diameter:

The average single fiber diameter was taken by scanning electron microscopy (SEM) photographs of the surface of the fibrous substrate or sheet at a magnification of 2000 times, and 100 fine fibers were randomly selected, and the diameter of the single fibers was measured and the average value was calculated.

When a very fine fiber structure constituting a fibrous substrate or sheet is cut In the case of the surface, the diameter of the outer circumference of the profiled section is regarded as the diameter of the single fiber and is calculated. In addition, when the circular cross section is mixed with the irregular cross section, and the case where the single fiber diameter is different in mixing size, etc., the total number of sampling numbers in which the number of the respective number of strips is matched is 100, and the calculation is performed. However, in addition to the non-woven fabric containing the ultrafine fibers or the ultrafine fiber bundles, there is a case where the knitted fabric or the knitted fabric for reinforcement is inserted, and when the average single fiber diameter of the ultrafine fibers is measured, the knitted fabric or knitted fabric for reinforcement is used. The fibers are excluded from the sampled object.

(2) Compression ratio and compression modulus of sheet material:

The compression ratio of the sheet material and the compression elastic modulus were five random test pieces of 50 mm in length and 50 mm in width from the sheet material, and the thickness T0 at an initial load of 0.5 kPa was used in accordance with the method described in JIS L1913: 2010. The compression ratio was determined by the following formula 1 with the thickness T1 when the load was set to 30 kPa. Next, the thickness T2 when the load returned to the initial load of 0.5 kPa was measured, and the compression elastic modulus was obtained by the formula 2.

Equation 1: Compression ratio P (%) = 100 × (T0 - T1) / T0

Formula 2: Compressive elastic modulus Pe (%) = 100 × (T2-T1) / (T0 - T1).

(3) Elasticity of sheet material:

The elasticity of the sheet material was 10 in each of the adult males and the female females in good health, and 20 evaluators in total, repeated 3 times using the hand to grasp the sheet material and then loosened, and the elastic utilization functional evaluation of the hand was felt. Five-stage evaluation was performed in the following manner, and the most evaluation was made elastic. The elasticity system regards grades 3 to 5 as appropriate handles.

Level 5: Feel the comfort of the sheet.

Level 4: The evaluation is between level 5 and level 3.

Level 3: Feel the slight elasticity of the sheet.

Level 2: The evaluation is between level 3 and level 1.

Level 1: No feeling of the elasticity of the sheet.

(4) The feel of the sheet material:

The feel of the sheet was 10 in each of the adult males and the females in good health, and the total of 20 evaluators repeated the gripping of the sheet by hand 3 times and then released, using the functional evaluation according to the following manner 5 The softness of the sheet material was evaluated at the stage, and the most evaluation was set as the hand feeling. The feel of the hand is regarded as a proper hand feeling from level 3 to level 5.

Level 5: The sheet is very soft.

Level 4: The evaluation is between level 5 and level 3.

Level 3: The sheet is not hard.

Level 2: The evaluation is between level 3 and level 1.

Level 1: The sheet is too hard.

(5) Appearance quality of sheet material:

The appearance quality of the sheet material was 10 in each of adult males and females in good health, and a total of 20 evaluators were evaluated by visual and functional evaluation in the following manner, and the most evaluation was made into appearance quality. . Appearance quality is considered good from level 3 to level 5.

Grade 5: Uniform fiber fluffing, good fiber dispersion and good appearance.

Level 4: The evaluation is between level 5 and level 3.

Grade 3: Although there is a slightly poorer state of fiber dispersion, there is fiber fluffing and the appearance is still good.

Level 2: The evaluation is between level 3 and level 1.

Grade 1: The overall fiber dispersion state is very poor and the appearance is poor.

[Example 1]

(non-woven fabric for fibrous substrates)

The sea component is polyethylene terephthalate copolymerized with 8 mol% of sodium 5-isophthalate sulfonate, and the island component is polyethylene terephthalate, and the sea component is 45 mass%, island. The composite ratio of 55 mass% of the components was obtained, and the island-in-sea type composite fiber having an island number of 36 islands/1 monofilament and an average single fiber diameter of 17 μm was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a short fiber, and a fiber web was formed by a card and a cross-lapper, and a nonwoven fabric was formed by needle rolling. The nonwoven fabric obtained in this manner was immersed in hot water at a temperature of 98 ° C for 2 minutes to shrink, and then dried at a temperature of 100 ° C for 5 minutes to form a nonwoven fabric (sheet) for a fibrous substrate.

(off sea treatment)

The fibrous substrate was immersed in a non-woven fabric at a concentration of 10 g/L sodium hydroxide solution heated to a temperature of 95 ° C, and treated for 30 minutes to obtain a sea-removed sheet containing ultrafine fibers of a sea-incorporated composite fiber. (cellulosic substrate).

(giving by polyvinyl alcohol)

The dehydrated sheet (cellulosic substrate) was placed in a 12% polyvinyl alcohol aqueous solution adjusted to a polymerization degree of 500, a viscosity of 50 mPa ‧ and a temperature of 50 ° C, and impregnated with polyvinyl alcohol and extruded by a nip roll. Drying was carried out using a dryer at a temperature of 120 °C.

(giving the polymer elastomer)

The dehydrated sheet (cellulosic substrate) to which polyvinyl alcohol was imparted was impregnated with a DMF (N,N-dimethylformamide) solution of an ether-based polyurethane resin adjusted to a solid content of 12% by mass, and The polyurethane resin was solidified in an aqueous solution having a DMF concentration of 30% by mass. Then, the polyvinyl alcohol and the DMF were removed by hot water, and dried by hot air at a temperature of 120 ° C for 10 minutes, thereby obtaining a sheet material of the polyurethane resin in such a manner that the mass of the polyester component was 30% by mass based on the mass of the polyester resin. .

(cutting, raising, dyeing, reducing and washing)

The sheet material obtained by giving the above-mentioned fibrous base material to the polyurethane resin was cut in the thickness direction, and the back side surface of the cut surface was ground by using a 240-mesh circular sandpaper, and then subjected to raising treatment, and then used by a circulating dyeing machine. The disperse dye is subjected to dyeing and subjected to reduction washing to obtain a sheet. The compression ratio of the obtained sheet material was 10.2%, and the compression elastic modulus was 51%. Further, the obtained sheet-like material had a five-stage elasticity and a five-stage hand feeling, and the appearance quality was in a good state of five grades, and the drape feeling was excellent, and the hand feeling was very soft.

[Embodiment 2]

(non-woven fabric for fibrous substrate, sea removal treatment)

A sea-leaf sheet (cellulosic substrate) was obtained in the same manner as in Example 1.

(giving by polyvinyl alcohol)

In the same manner as in Example 1, the sea-leaf sheet (cellulosic substrate) was impregnated with a 12% polyvinyl alcohol aqueous solution adjusted to a polymerization degree of 300, a viscosity of 8 mPa ‧ and a temperature of 90 ° C, and Drying was carried out using a dryer at 120 °C.

(giving, halving, raising, dyeing, reducing and cleaning of polymeric elastomers)

Then, in the same manner as in Example 1, the application, the half-cutting, the raising, the dyeing, and the reduction washing of the polymeric elastomer were carried out to obtain a sheet. The compression ratio of the obtained sheet material was 7.1%, and the compression elastic modulus was 70%. In addition, the obtained sheet-like material had an elasticity of 5 grades, a hand-feeling grade of 3 grades, and an appearance quality of 5 grades, and was excellent in the drape feeling, and the handle feeling was not hard.

[Example 3]

(non-woven fabric for fibrous substrate, sea removal treatment)

A sea-leaf sheet (cellulosic substrate) was obtained in the same manner as in Example 1.

(giving by polyvinyl alcohol)

In the same manner as in Example 1, a dewatering sheet (cellulosic substrate) was impregnated with a 12% polyvinyl alcohol aqueous solution adjusted to a polymerization degree of 650, a viscosity of 60 mPa ‧ and a temperature of 4 ° C, and dried by a dryer at 120 ° C. .

(giving, halving, raising, dyeing, reducing and cleaning of polymeric elastomers)

Then, in the same manner as in Example 1, the application, the half-cutting, the raising, the dyeing, and the reduction washing of the polymeric elastomer were carried out to obtain a sheet. The compression ratio of the obtained sheet material was 14.0%, and the compression elastic modulus was 30%. Further, the obtained sheet-like material had three levels of elasticity, five levels of hand feeling, and four levels of appearance quality, and also had a drape feeling and exhibited a very soft hand.

[Example 4]

(non-woven fabric for fibrous substrate, sea removal treatment)

A sea-leaf sheet (cellulosic substrate) was obtained in the same manner as in Example 1.

(giving by polyvinyl alcohol)

The dehydrated sheet (cellulosic substrate) was impregnated with a 12% polyvinyl alcohol aqueous solution adjusted to a polymerization degree of 500, a viscosity of 10 mPa ‧ and a temperature of 75 ° C, and dried by a dryer at a temperature of 120 ° C.

(giving, halving, raising, dyeing, reducing and cleaning of polymeric elastomers)

Then, in the same manner as in Example 1, the application, the half-cutting, the raising, the dyeing, and the reduction washing of the polymeric elastomer were carried out to obtain a sheet. The compression ratio of the obtained sheet material was 8.4%, and the compression elastic modulus was 62%. Further, the obtained sheet-like material had a good grade of 5 grades, 4 grades of hand feeling, and 5 grades of appearance quality.

[Example 5]

(non-woven fabric for fibrous substrate, sea removal treatment)

A sea-leaf sheet (cellulosic substrate) was obtained in the same manner as in Example 1.

(giving by polyvinyl alcohol)

In the same manner as in Example 1, the dehydrated sheet (cellulosic substrate) was impregnated with a 12% polyvinyl alcohol aqueous solution adjusted to a polymerization degree of 650, a viscosity of 52 mPa ‧ and a temperature of 20 ° C, and was dried by a dryer at 120 ° C. dry.

(giving, halving, raising, dyeing, reducing and cleaning of polymeric elastomers)

Then, in the same manner as in Example 1, the application, the half-cutting, the raising, the dyeing, and the reduction washing of the polymeric elastomer were carried out to obtain a sheet. The obtained sheet had a compression ratio of 12.6% and a compression modulus of 43%. Further, the obtained sheet-like material had three levels of elasticity, five levels of hand feeling, and five grades of appearance quality, and the drape feeling was excellent and exhibited a soft hand.

[Embodiment 6]

A fiber web was formed in the same manner as in Example 1, and pin rolling was performed at 100 pieces/cm ² to form a pre-entangled nonwoven fabric. Except that the plain woven polyester tissue was superposed on both sides of the obtained pre-entangled nonwoven fabric, 2500 pieces/cm ² needle rolling was performed by using a felting needle to form a non-woven fabric for a fibrous substrate, and the rest were A sheet material to which a polyurethane resin was imparted was obtained in the same manner as in Example 1. Then, the sheet material to which the polyurethane resin was applied was cut in the thickness direction, and the surface of the cut surface was ground by a 240-mesh circular sandpaper to carry out a raising process, and then a sheet shape was obtained in the same manner as in Example 1. Things. The obtained sheet had a compression ratio of 9.8% and a compression modulus of 48%. Further, the obtained sheet-like material had a good grade of 4 grades of elasticity, 4 grades of hand feeling, and 5 grades of appearance quality. Excellent drape and a soft hand.

[Embodiment 7]

In the same manner as in Example 1, except that the island component of the obtained island-in-the-sea fiber 1 monofilament was 100 islands, a sheet material was obtained in the same manner as in Example 1. The single fiber diameter of the ultrafine fibers contained in the obtained sheet material was 0.3 μm. The compression ratio of the obtained sheet material was 11.1%, and the compression elastic modulus was 45%. Moreover, the obtained sheet-like material has a three-stage elasticity, a five-stage hand-feeling system, and an appearance quality of five grades, and also has a drape feeling. Presents a very soft hand.

[Embodiment 8]

In the same manner as in Example 1, except that the island component of the obtained island-in-the-sea fiber 1 monofilament was 8 islands, a sheet material was obtained in the same manner as in Example 1. The single fiber diameter of the ultrafine fibers contained in the obtained sheet material was 7.0 μm. The compression ratio of the obtained sheet material was 9.5%, and the compression elastic modulus was 60%. Further, the obtained sheet-like material had a fifth grade of elasticity, four grades of hand-feeling, and four grades of appearance quality, and was excellent in drape feeling and exhibited a soft hand.

[Comparative Example 1]

(non-woven fabric for fibrous substrate, sea removal treatment)

A sea-leaf sheet (cellulosic substrate) was obtained in the same manner as in Example 1.

(giving by polyvinyl alcohol)

In the same manner as in Example 1, the dehydrated sheet (cellulosic substrate) was impregnated with a polyvinyl alcohol aqueous solution having a polymerization degree of 700, a viscosity of 70 mPa ‧ and a temperature of 3 ° C of 12%, and a dryer having a temperature of 120 ° C was used. Drying is carried out. Then, in the same manner as in Example 1, the application of the polymeric elastomer, and the cutting, raising, dyeing, and reduction washing were carried out to obtain a sheet. The obtained sheet had a compression ratio of 16% and a compression modulus of 23%. Further, the obtained sheet-like material had a first grade of elasticity, a grade of 5, and an appearance quality of 4 grades, and was an ultra-soft sheet-like material, and had no elasticity, and good results were not obtained.

[Comparative Example 2]

(non-woven fabric for fibrous substrate, sea removal treatment)

A sea-leaf sheet (cellulosic substrate) was obtained in the same manner as in Example 1.

(Polyvinyl alcohol and polymeric elastomers are given, cut, raised, dyed, and washed)

In the same manner as in Example 1, the sea-leaf sheet (cellulosic substrate) was impregnated with a polyvinyl alcohol aqueous solution having a concentration of 12% adjusted to a polymerization degree of 350, a viscosity of 7 mPa ‧ and a temperature of 92 ° C, and a dryer having a temperature of 120 ° C was used. Drying is carried out. Then, in the same manner as in Example 1, the application, the half-cutting, the raising, the dyeing, and the reduction washing of the polymeric elastomer were carried out to obtain a sheet-like material. The compression ratio of the obtained sheet material was 6.8%, and the compression elastic modulus was 75%. Further, the obtained sheet-like material had a five-stage elasticity, a first-order texture, and three appearance qualities, and was a very hard sheet-like material, and good results could not be obtained.

The evaluation results of the sheet materials obtained in the above respective examples and comparative examples were summarized and shown in Table 1.

Claims (10)

A sheet material comprising a polymeric elastomer in a fibrous substrate composed of ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm, and at least one side surface provided with a raised sheet material, the characteristics of which are The thickness T0 of the sheet material when the initial load was 0.5 kPa was applied to the sheet material in accordance with the method of JIS L1913, and the thickness T1 of the sheet material when the load was applied at 30 kPa and the subsequent recovery to the initial load of 0.5 kPa. The sheet material thickness T2 is 7% or more and 14% or less in accordance with the following formula 1, and the compression elastic modulus Pe obtained according to the following formula 2 is 30% or more and 70% or less; : Compression ratio P (%) = 100 × (T0 - T1) / T0 Equation 2: Compression elastic modulus Pe (%) = 100 × (T2-T1) / (T0 - T1). A sheet material according to claim 1, wherein the sheet material contains a braid. A method for producing a sheet material includes the following steps (1) to (3): (1) applying a fibrous substrate having an ultrafine fiber at a temperature of 5 ° C or more and 90 ° C or less a step of producing polyvinyl alcohol; (2) a step of producing a sheet-like material by imparting a polymeric elastomer to the fibrous substrate obtained after the above step (1); (3) obtaining a sheet-like shape The step of raising the hair on at least one side of the object. The method for producing a sheet material according to claim 3, which comprises the step of: dissolving polyvinyl alcohol at a temperature of 95 ° C or higher, and then imparting a polyvinyl alcohol adjusted to a temperature of 50 ° C or higher and 75 ° C or lower. The method for producing a sheet material according to claim 3 or 4, wherein the degree of polymerization of the polyvinyl alcohol is 400 or more and 600 or less. A method of producing a sheet material according to any one of claims 3 to 5, wherein In the step 3, a polymer elastomer dissolved in an organic solvent is used to impart a polymer elastomer. A method for producing a sheet material comprises the following steps (1) to (3): (1). introducing a fibrous substrate containing ultrafine fibers into a polyvinyl alcohol aqueous solution having a viscosity of 10 to 50 mPa·s, and a step of imparting a polyvinyl alcohol; (2) a step of producing a sheet-like material by imparting a polymeric elastomer to the fibrous substrate obtained after the above-mentioned one step; (3). At least one side of the surface performs the step of raising the hair. The method for producing a sheet material according to claim 7, wherein the polyvinyl alcohol has a polymerization degree of 400 or more and 600 or less. The method for producing a sheet material according to claim 7 or 8, wherein in the step 2, a polymer elastomer dissolved in an organic solvent is used to impart a polymer elastomer. The method for producing a sheet material according to claim 3, wherein the fibrous substrate containing the ultrafine fibers in the above step 1 is obtained by removing the sea component of the fibrous substrate sheet containing the sea-island type fibers. Made of very fine fibers.