JP2015055023A - Sheet-like article and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-like article, especially a leather-like sheet-like article that achieves both flexibility and repulsive feeling and simultaneously has both characteristics.SOLUTION: The sheet-like article is composed of a nonwoven fabric sheet formed by entangling ultra fine fibers having a mean single fiber diameter of 0.3-7 μm and two or more different kinds of polymer elastomers including acrylic resin and polyurethane resin. The two or more different kinds of polymer elastomers are arranged in layers in a thickness direction of the inside of the nonwoven fabric sheet.

Description

  The present invention relates to a sheet-like material having both flexibility and resilience in leather-like sheet material and the like, and a method for producing the same.

  A sheet-like material mainly composed of ultrafine fibers and polyurethane has excellent characteristics not found in natural leather, and is widely used in various applications.

  In manufacturing such a sheet-like material, a fiber substrate such as a nonwoven sheet composed of ultrafine fiber-expressing fibers is subjected to ultrafine fiber treatment (sea removal treatment) and impregnated with an organic solvent solution of polyurethane. Generally, a manufacturing method comprising a step of wet coagulating the polyurethane by immersing the obtained fibrous base material in a polyurethane non-solvent water or a mixed solution of an organic solvent and water is generally employed. ing. However, the sheet-like material obtained by such a manufacturing method has a problem that the flexibility of the sheet itself is inferior.

  As means for solving the problem, for example, after applying polyvinyl alcohol (hereinafter sometimes referred to as PVA) to the fibrous base material before the sea removal treatment, the seawater treatment is performed and then immersed in hot water. And the manufacturing method which consists of the process of removing PVA is proposed (refer patent document 1). In the case of this proposal, sufficient flexibility can be imparted to the sheet by imparting voids to the locations where PVA was present, but the sheet resilience is inferior at the same time as the sheet flexibility is obtained. There is a problem. The resilience of the sheet-like material can be obtained by increasing the amount of polyurethane applied, but the amount of polyurethane increases, so that the sheet-like material becomes heavy and the flexibility becomes inferior.

  For this reason, a sheet-like material having high flexibility and resilience at the same time has not been obtained, and a sheet-like material having both flexibility and resilience is required.

JP 2002-249988 A

  That is, in the prior art, a sheet-like material having both flexibility and resilience and a manufacturing method thereof have not been obtained so far.

  Therefore, an object of the present invention is to provide a sheet-like material that has both properties at the same time while satisfying both flexibility and resilience in a sheet-like material, particularly a leather-like sheet material.

  Another object of the present invention is to provide a method for producing an environmentally friendly sheet-like material that does not use an organic solvent in the production process in the method for producing the sheet-like material.

  The present invention is to achieve the above-mentioned problem, and the sheet-like material of the present invention is a non-woven sheet formed by entanglement of ultrafine fibers having an average single fiber diameter of 0.3 to 7.0 μm, A sheet-like material composed of two or more different types of polymer elastic bodies, wherein the two or more different types of polymer elastic bodies are arranged in layers in the thickness direction inside the nonwoven fabric sheet.

  According to a preferred aspect of the present invention, the polymer elastic body is composed of two types of acrylic resin and polyurethane resin.

  According to a preferred aspect of the present invention, the ratio of the acrylic resin to the polyurethane resin is 10:90 to 90:10.

  According to a preferred embodiment of the present invention, the glass transition temperature of the acrylic resin is less than 100 ° C.

  In addition, the method for producing a sheet-like product according to the present invention includes a step of applying a first polymer elastic body to a fibrous nonwoven sheet base material having an ultrafine fiber-expressing fiber as a main component, A step of expressing ultrafine fibers having an average single fiber diameter of 0.3 to 7.0 μm from a fibrous nonwoven sheet substrate provided with a molecular elastic body, and a fibrous nonwoven sheet base in which the ultrafine fibers are expressed A method for producing a sheet-like material comprising a step of applying a second polymer elastic body to a material.

  According to the present invention, it is possible to obtain a sheet-like product having both flexibility and resilience that can not be achieved by the prior art and having both characteristics at the same time.

  Moreover, according to the present invention, in the method for producing the sheet-like material, in the step of expressing the ultrafine fibers from the fibrous nonwoven sheet base material, the first polymer elastic body is provided, By improving the shape retention during the production process, a sheet-like material having elegant napping and a dense feeling can be obtained.

FIG. 1 is a schematic cross-sectional view for illustrating the range of 0 to 30% in the thickness direction from both surfaces of a fibrous nonwoven sheet base material.

  The sheet-like material of the present invention is a sheet-like material composed of a nonwoven fabric sheet in which ultrafine fibers having an average single fiber diameter of 0.3 to 7.0 μm are entangled and two or more different types of polymer elastic bodies. In addition, the two or more different types of polymer elastic bodies are a sheet-like material arranged in layers in the thickness direction inside the nonwoven fabric sheet.

  As the ultrafine fibers constituting the nonwoven fabric sheet used in the present invention, fibers made of a melt-spinnable thermoplastic resin can be used. Examples of the thermoplastic resin include polyethylene terephthalate, polybutylene terephthalate, polyester such as polytrimethylene terephthalate or polylactic acid, polyamide such as 6-nylon and 66-nylon, polyacryl, polyethylene and polypropylene, and thermoplastic cellulose. Can be mentioned. Among these, polyester fibers are preferably used from the viewpoints of strength, dimensional stability, and light resistance. Moreover, the nonwoven fabric sheet may be configured by mixing fibers of different materials.

  The cross-sectional shape of the ultrafine fibers constituting the nonwoven fabric sheet may be a round cross-section, but a polygonal shape such as an ellipse, a flat shape, and a triangle, and a deformed cross-section shape such as a sector shape and a cross shape may also be employed. It is important that the ultrafine fibers have an average single fiber diameter of 0.3 to 7 μm. By setting the average single fiber diameter of the ultrafine fibers to 7 μm or less, more preferably 6 μm or less, and even more preferably 5 μm or less, a sheet-like product having excellent flexibility and surface quality can be obtained. On the other hand, by setting the average single fiber diameter of the ultrafine fibers to 0.3 μm or more, more preferably 0.7 μm or more, and even more preferably 1 μm or more, the coloring property after dyeing or the napping treatment such as grinding with sandpaper can be used. Excellent dispersibility of bundled fibers and ease of judgment.

  The nonwoven fabric sheet composed of the ultrafine fibers may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric, but a short fiber nonwoven fabric is preferably used in terms of texture and quality.

  It is preferable that the fiber length of the short fiber used for said short fiber nonwoven fabric is 25-90 mm, More preferably, it is 30-80 mm. By setting the fiber length of the short fibers to 25 mm or more, a sheet-like material having excellent wear resistance can be obtained by entanglement. Further, by setting the fiber length of the short fibers to 90 mm or less, it is possible to obtain a sheet-like product with better texture and quality.

  The nonwoven fabric sheet has a structure in which bundles of ultrafine fibers (ultrafine fiber bundles) are entangled. Since the ultrafine fibers are entangled in a bundle state, the strength of the sheet-like material is improved. As will be described later, the nonwoven fabric sheet of such an embodiment can be obtained by causing the ultrafine fibers to be expressed after entanglement of the ultrafine fiber-expressing fibers in advance.

  When the above-mentioned ultrafine fiber or the ultrafine fiber bundle constitutes a nonwoven fabric sheet, a woven fabric or a knitted fabric can be inserted into the nonwoven fabric sheet for the purpose of improving the strength. The average single fiber diameter of the fibers constituting such a woven or knitted fabric is preferably about 0.3 to 10 μm.

When the basis weight of the nonwoven fabric sheet is too low, physical properties such as tensile strength and tear strength of the sheet-like material are weakened, and when it is too high, the texture of the sheet-like material is hardened, and is 50 to 2000 g / m ² . It is preferable.

  Further, if the thickness of the nonwoven fabric sheet is too thin, physical properties such as tensile strength and tearing strength of the sheet-like material become weak, and if it is too thick, the texture of the sheet-like material becomes hard, so that it is 0.1 to 5 mm. It is preferable.

  In the present invention, two or more different types of polymer elastic bodies are used as the polymer elastic body. Here, two or more different types of polymer elastic bodies are described as a first polymer elastic body and a second polymer elastic body as follows.

  As the first polymer elastic body used in the present invention, it is important that the resin film has excellent resilience. Examples of such resins include acrylic resins, styrene / butadiene rubber resins, Examples thereof include nitrile rubber resins, acrylonitrile / styrene / butadiene resins, epoxy resins, polyester resins, and nylon resins. Among these, acrylic resin is preferably used from the viewpoint of process passability and chemical resistance in post-processing. Here, “excellent resilience” means that the resin film prepared by desolvating the polymer elastic body solution has a high compression recovery rate, and the compression modulus is preferably 80% or more. By setting the compression elastic modulus to 80% or more, it is possible to impart sufficient resilience to the sheet.

  These first polymer elastic bodies used in the present invention preferably have a glass transition temperature of less than 100 ° C. By making the glass transition temperature lower than 100 ° C., the first polymer elastic body itself can be prevented from becoming too hard, the sheet can be prevented from becoming too hard, and the flexibility of the sheet-like material can be maintained. .

  The first polymer elastic body used in the present invention includes various additives, for example, pigments such as carbon black, phosphorus-based, halogen-based, silicone-based and inorganic flame retardants, phenol-based, sulfur-based and phosphorus-based materials. Antioxidants such as benzotriazoles, UV absorbers such as benzotriazoles, benzophenones, salicylates, cyanoacrylates and oxalic acid anilides, light stabilizers such as hindered amines and benzoates, and water resistance such as polycarbodiimides Decomposition stabilizers, plasticizers, antistatic agents, surfactants, softeners, water repellents, coagulation regulators, dyes, preservatives, antibacterial agents, deodorants, fillers such as cellulose particles, or silica or titanium oxide Inorganic particles such as can be contained alone or in any combination.

  The first polymer elastic body used in the present invention preferably has a mass reduction rate of 10% or less after being immersed in a 10% by mass sodium hydroxide aqueous solution at a temperature of 90 ° C. for 10 minutes.

  In the ultrafine fiber expression type fiber ultrafine treatment in the present invention, which will be described later, when using an alkaline aqueous solution such as hot water or sodium hydroxide, the viewpoint of maintaining the resilience of the fibrous nonwoven sheet base or the sheet shape From the viewpoint of maintaining the shape of the object, the mass reduction rate is preferably low, and the mass reduction rate is more preferably 5% by mass or less.

  In the present invention, the second polymer elastic body is applied to the fibrous nonwoven sheet base material in which ultrafine fibers are expressed as described later. It is important that the second polymer elastic body is excellent in flexibility, and examples thereof include polyurethane, polyurea, polyurethane-polyurea elastomer, and the like. Among these, polyurethane elastomers such as polyurethane and polyurethane / polyurea elastomer are preferably used.

  The polyurethane used as the main component of the second polymer elastic body may be either an organic solvent type polyurethane or a water dispersion type polyurethane, but a water dispersion type polyurethane is preferably used from the viewpoint of environmental considerations.

  As the polyurethane used in the present invention, those obtained by reaction of a polymer diol, an organic diisocyanate and a chain extender are preferable.

  As the polymer diol used in the present invention, for example, polycarbonate-based, polyester-based, polyether-based, silicone-based and fluorine-based diols can be employed, and a copolymer combining these may be used. . As the polymer diol, polycarbonate-based diols and polyether-based diols are preferably used from the viewpoint of hydrolysis resistance. From the viewpoint of light resistance and heat resistance, polycarbonate diols and polyester diols are preferably used. Furthermore, from the viewpoint of the balance between hydrolysis resistance, heat resistance, and light resistance, a polycarbonate diol and a polyester diol are more preferable, and a polycarbonate diol is particularly preferably used.

  The polycarbonate diol can be produced by transesterification of alkylene glycol and carbonate, or reaction of phosgene or chloroformate with alkylene glycol.

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

  Examples of the polyester diol include polyester diols obtained by condensing various low molecular weight polyols and polybasic acids.

  Examples of the low molecular weight polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, and 2,2-dimethyl-1,3. -Propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol And one or more selected from cyclohexane-1,4-dimethanol can be used. Further, addition products obtained by adding various alkylene oxides to bisphenol A can also be used.

  Examples of the polybasic acid include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and One type or two or more types selected from hexahydroisophthalic acid can be used.

  Examples of the polyether-based diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized diols combining them.

  The number average molecular weight of the polymer diol used in the present invention is preferably 500 to 4000. By setting the number average molecular weight to 500 or more, more preferably 1500 or more, it is possible to prevent the texture from becoming hard. Moreover, the intensity | strength as a polyurethane is maintainable by making a number average molecular weight into 4000 or less, More preferably, 3000 or less.

  Examples of the organic diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, and aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. You may use combining these. Among these, aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate are preferably used from the viewpoint of light resistance.

  Examples of the chain extender include amine chain extenders such as ethylenediamine and methylenebisaniline, and diol chain extenders such as ethylene glycol. Moreover, the polyamine obtained by making polyisocyanate and water react can also be used as a chain extender.

  If desired, a crosslinking agent can be used in combination with the second polymer elastic body for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like. The cross-linking agent may be an external cross-linking agent added as a third component to the second polymer elastic body, or an internal cross-link that introduces a reaction point that becomes a cross-linked structure in advance in the second polymer elastic body molecular structure. An agent may be used. In the present invention, it is preferable to use an internal cross-linking agent from the viewpoint that the cross-linking points can be formed more uniformly in the second polymer elastic body molecular structure and the reduction in flexibility can be reduced.

  As said crosslinking agent, the compound which has an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group, etc. can be used. However, when the crosslinking proceeds excessively, the polyurethane tends to be hardened and the texture of the sheet-like material tends to be hard, so that a compound having a silanol group is preferably used in terms of the balance between reactivity and flexibility.

  Moreover, it is preferable that the 2nd polymer elastic body used by this invention has a hydrophilic group in molecular structure. By having a hydrophilic group in the molecular structure, the dispersibility and stability of the water-dispersed polymer elastic body can be improved.

  Examples of the aqueous group include cationic systems such as quaternary amine salts, anionic systems such as sulfonates and carboxylates, nonionic systems such as polyethylene glycol, combinations of cationic systems and nonionic systems, and anionic systems. Any hydrophilic group in a nonionic combination can be employed. Among these, nonionic hydrophilic groups that are free from fear of yellowing by light and harmful effects due to a neutralizing agent are particularly preferably used.

  In the case of an anionic hydrophilic group, a neutralizing agent is required. For example, the neutralizing agent is a tertiary amine such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine and dimethylethanolamine. In this case, amine is generated and volatilized by heat during film formation or drying, and released outside the system. For this reason, in order to suppress the release of air and the deterioration of the working environment, it is essential to introduce a device for recovering volatile amines. In addition, if the amine does not volatilize by heating and remains in the final product sheet, it may be discharged to the environment when the product is incinerated. On the other hand, in the case of a nonionic hydrophilic group, it is not necessary to introduce an amine recovery device because a neutralizing agent is not used, and there is no fear of residual amine in the sheet-like material, so that it is preferably used. it can.

  Further, when the anionic hydrophilic group neutralizing agent is an alkali metal such as sodium hydroxide, potassium hydroxide and calcium hydroxide, or a hydroxide of an alkaline earth metal, the polyurethane part is wetted with water. Although it shows alkalinity, in the case of a nonionic hydrophilic group, since a neutralizing agent is not used, there is no need to worry about deterioration due to hydrolysis of polyurethane.

  The second polymer elastic body used in the present invention may contain various additives, for example, pigments such as carbon black, flame retardants such as phosphorus, halogen, silicone, and inorganic, phenolic, sulfur -Based and phosphorus-based antioxidants, benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based and oxalic acid anilide-based UV absorbers, hindered amine-based and benzoate-based light stabilizers, polycarbodiimide, etc. Hydrolysis-resistant stabilizers, plasticizers, antistatic agents, surfactants, softeners, water repellents, coagulation regulators, dyes, antiseptics, antibacterial agents, deodorants, cellulose particles and fillers such as microballoons , And inorganic particles such as silica and titanium oxide.

  In order to further increase the gap between the ultrafine fiber and the second polymer elastic body, an inorganic organic foaming agent such as sodium hydrogen carbonate, or 2,2 ′ is added to the second polymer elastic body. Organic foaming agents such as -azobis [2-methyl-N- (2-hydroxyethyl) propionamide] can be contained.

  Here, different polymer elastic bodies mean different polymer types and viscoelastic properties. In general, a polymer elastic body has viscosity characteristics and elastic characteristics, and the first polymer elastic body of the present invention preferably has excellent elastic characteristics because it is important that the resilience of the resin film is excellent. . On the other hand, since it is important that the second polymer elastic body is excellent in flexibility of the resin film, it is preferable that the second polymer elastic body is excellent in viscosity characteristics.

  Here, an acrylic resin is mentioned as a typical polymer excellent in the above elastic characteristics, and a polyurethane resin is mentioned as a typical polymer excellent in the viscosity characteristics. Acrylic resins and polyurethane resins are excellent in elasticity or viscosity properties, and are excellent in durability. Therefore, they are excellent in durability when used in sheet form, and are particularly preferably used in the present invention.

  The mass ratio of the first polymer elastic body and the second polymer elastic body used in the present invention is preferably in the range of 10:90 to 90:10, more preferably 20:80 to 80: 20. By setting the mass ratio of the first polymer elastic body and the second polymer elastic body to 10:90 or more, more preferably 20:80 or more, a sufficient repulsion can be given to the sheet-like material, By setting it to 90:10 or less, more preferably 80:20 or less, sufficient flexibility can be given to the sheet-like material.

  The total amount of the first polymer elastic body and the second polymer elastic body in the sheet-like material is preferably 0.5 to 50% by mass, more preferably based on the ultrafine fiber mass of the nonwoven fabric sheet. 0.5 to 40% by mass. By setting the application amount to 0.5% by mass or more, sufficient mechanical properties can be obtained, and by setting the application amount to 50% by mass or less, the influence of a decrease in flexibility is reduced.

  In the sheet-like material of the present invention, it is important that the first polymer elastic body and the second polymer elastic body are arranged in layers in the thickness direction inside the nonwoven fabric sheet. The first polymer elastic body is formed by arranging the first polymer elastic body and the second polymer elastic body in layers in the thickness direction inside the nonwoven fabric sheet, and forming a two-layer structure of the polymer elastic body. Both the rebound feeling due to and the flexibility due to the second polymer elastic body can be expressed. Furthermore, the flexibility and rebound of the sheet-like material can be controlled by the mass ratio of the first polymer elastic body to be applied and the second polymer elastic body. The two-layer structure in the thickness direction inside the nonwoven fabric sheet here is not a two-layer structure formed by applying a polymer elastic body to the surface of the sheet-like material, but in the nonwoven fabric sheet made of ultrafine fibers. 1 shows a structure composed of a layer provided with one polymer elastic body and a layer provided with a second polymer elastic body in a nonwoven fabric sheet made of ultrafine fibers.

  The sheet-like material of the present invention can also be provided with a third polymer elastic body or a fourth polymer elastic body for the purpose of providing functionality.

  The thickness of the sheet-like material of the present invention is preferably 0.1 to 5 mm, more preferably 0.5 to 2 mm. By setting the thickness of the sheet-like material to 0.1 mm or more, mechanical properties such as tensile strength and tearing strength can be obtained, and by setting the thickness to 5 mm or less, the texture of the sheet can be prevented from becoming hard. .

  The thickness of the layer of the first polymer elastic body of the present invention is preferably 0.05 to 4.5 mm, more preferably 0.1 to 1.5 mm. By setting the thickness of the first polymer elastic body layer to 0.05 mm or more, sufficient mechanical properties can be obtained, and by setting the thickness to 4.5 mm or less, the influence of a decrease in flexibility is reduced.

  The thickness of the layer of the second polymeric elastic body of the present invention is preferably 0.05 to 4.5 mm, more preferably 0.1 to 1.5 mm. By setting the thickness of the second polymer elastic body layer to 0.05 mm or more, sufficient mechanical properties can be obtained, and by setting the thickness to 4.5 mm or less, the texture is lowered due to the sheet becoming heavier. Impact is reduced.

  Next, the manufacturing method of the sheet-like material of this invention is described. In the method for producing a sheet-like material of the present invention, the first polymer elastic body is imparted to the fibrous nonwoven sheet base material, and then the ultrafine fibers are expressed from the fibrous nonwoven sheet base material. 2 polymer elastic body is provided.

  Specifically, in the method for producing a sheet-like material of the present invention, the first polymer elastic body is applied to a fibrous nonwoven sheet base material having an ultrafine fiber-expressing fiber as a main constituent, the first A step of developing an ultrafine fiber having an average single fiber diameter of 0.3 to 7.0 μm from a fibrous nonwoven sheet base material to which the polymer elastic body is applied, and a fibrous nonwoven fabric in which the ultrafine fiber is developed In this method, the step of applying the second polymer elastic body to the sheet substrate is performed in the order of these steps.

  As a means for forming ultrafine fibers from a fibrous nonwoven sheet substrate, it is preferable to use ultrafine fiber expression type fibers. By using the ultrafine fiber expression type fiber, a form in which the ultrafine fiber bundles are entangled can be stably obtained.

  As ultrafine fiber expression type fibers, two component thermoplastic resins with different solvent solubility are used as sea component and island component, and the sea component is dissolved and removed using a solvent or the like, so that the remaining island component is used as ultrafine fiber. It is possible to employ sea-island type fibers or peelable composite fibers that are split into ultrafine fibers by arranging two components of thermoplastic resin alternately or radially in the fiber cross section and separating and separating each component. it can. Among them, the sea-island type fiber can be preferably used also from the viewpoint of flexibility and texture of the sheet-like material because it can provide an appropriate gap between the island components, that is, between the ultrafine fibers, by removing the sea component.

  For the sea-island type fiber, a sea-island type compound base is used, and the sea-island type composite fiber that spins the sea component and the island component by mutual arrangement and the sea component and the island component are mixed and spun. There are spinning fibers. Sea-island type composite fibers are preferably used from the viewpoint that ultrafine fibers having a uniform fineness can be obtained, and that a sufficiently long ultrafine fiber is obtained and contributes to the strength of the sheet-like material.

  As the sea component of the sea-island fiber, polyethylene, polypropylene, polystyrene, copolymer polyester obtained by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, or the like, polylactic acid, polyvinyl alcohol, or the like can be used. Among them, alkali-degradable, copolyester or polylactic acid copolymerized with sodium sulfoisophthalic acid or polyethylene glycol, which can be decomposed without using an organic solvent, and polyvinyl alcohol capable of removing sea components with hot water are preferable. Used.

  Examples of the fibrous base material composed of the above-mentioned ultrafine fibers include woven fabrics, knitted fabrics, and nonwoven fabrics. Among them, the surface quality of the sheet-like material when the surface raising treatment is performed, particularly the fineness of the surface fibers is good. Because of this, a non-woven sheet is used. The nonwoven fabric sheet may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric, but a short fiber nonwoven fabric is preferably used in terms of texture and quality.

  For example, a needle punch or a water jet punch can be employed as a method of entanglement of fibers or fiber bundles in a fibrous nonwoven sheet substrate used as a fibrous substrate.

  In the present invention, as a method for imparting the first polymer elastic body to the fibrous nonwoven sheet substrate, various methods usually used in the field can be employed. From the viewpoint that it can be applied uniformly, a method in which the first polymer elastic body is dissolved or dispersed in water, impregnated into a fibrous nonwoven sheet base material, and dried by heating is preferably used.

  The solid content mass concentration of the aqueous solution or aqueous dispersion when the first polymer elastic body is applied to the fibrous nonwoven sheet base material is preferably 0.1 to 40% by mass. If the solid content mass concentration is too low, the applied amount of the first polymer elastic body is difficult to reach the required amount, and if the solid content mass concentration is too high, the first to the both surfaces of the fibrous nonwoven sheet base material described later. It becomes difficult for the polymer elastic body 1 to be unevenly distributed. The solid content mass concentration is more preferably 0.5 to 30% by mass.

  It is preferable that the application amount of the first polymeric elastic body after drying with respect to the fibrous nonwoven sheet substrate is 0.05 to 45% by mass. By setting the application amount of the first polymer elastic body to 0.05% by mass or more, sufficient rebound is obtained, and by setting the application amount to 45% by mass or less, the influence of the decrease in flexibility is reduced. .

  The first polymer elastic body fluid impregnated in the non-woven sheet is preferably solidified and then unevenly distributed after shifting from both surfaces of the fibrous nonwoven sheet base material to the range of 0-30% in the thickness direction, which will be described later. By performing heat treatment at the drying temperature and drying time, solidify after shifting from both surfaces of the fiber-based nonwoven sheet material to the inside in the thickness direction in the range of 0 to 30%, more preferably in the range of 0 to 20%. Can be made.

  FIG. 1 is a schematic cross-sectional view for illustrating the range of 0 to 30% in the thickness direction from both surfaces of the fibrous nonwoven sheet substrate.

In FIG. 1, out of the entire range A in the thickness direction of the fibrous nonwoven sheet substrate, ranges B and C of 0 to 30% in the thickness direction from both surfaces of the fibrous nonwoven sheet substrate are shown. . Here, the relational expression of A, B, and C is B = C = A × 0.3.
As a result, a large amount of the first polymer elastic body can be disposed on the both surface sides of the sheet, and a small amount of the first polymer elastic body can be disposed inside, thereby forming a layer of the first polymer elastic body in the product.

  Moreover, since drying time will become long when drying temperature is too low, and there exists a possibility that a 1st polymeric elastic body may deteriorate when temperature is too high, it is preferable to dry at the temperature of 80-160 degreeC, The drying temperature is more preferably 110 to 150 ° C. Moreover, drying time is about 1 to 20 minutes normally, From a workability viewpoint, Preferably it is 1 to 10 minutes, More preferably, it is 1 to 5 minutes.

  The sea removal treatment when sea-island fibers are used is performed after the application of the first polymer elastic body to the fibrous nonwoven sheet substrate. When the sea removal treatment is performed after the application of the first polymer elastic body, the first polymer elastic body serves as a reinforcing material, and the shape retention during the sea removal treatment is obtained.

  The method of expressing ultrafine fibers from ultrafine fiber-expressing fibers such as sea-island fibers can be carried out by immersing and squeezing sea-island fibers in a solvent. Moreover, it can implement also by performing heat processing, such as wet heat, after squeezing.

  The sea removal treatment for eluting and removing sea components from the sea-island fiber can be performed by immersing the sea-island fiber in a solvent and squeezing it. As the 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. Further, when the sea component is a copolyester or polylactic acid, an alkaline aqueous solution such as sodium hydroxide can be used, and when the sea component is polyvinyl alcohol, hot water can be used.

  From the viewpoint of environmental considerations in the process, a seawater-dissolving treatment with an alkaline aqueous solution such as sodium hydroxide or hot water is preferably used as the solvent for dissolving sea components.

  In the present invention, the second polymer elastic body is applied to the fibrous nonwoven sheet base material to which the first polymer elastic body is applied to express ultrafine fibers. The second polymer elastic body to be applied may be either an organic solvent type or a water dispersion type, but a water dispersion type polymer elastic body is preferably used from the viewpoint of environmental considerations.

  As a method of applying the second polymer elastic body to the fibrous nonwoven sheet base material, the second polymeric elastic body fluid is impregnated into the fibrous nonwoven sheet base material, applied, solidified, and then heated and dried. The method is preferably used because the second polymer elastic body can be uniformly applied to the fibrous nonwoven sheet base material.

  The concentration of the second polymer elastic body fluid (content of the second polymer elastic body with respect to the second polymer elastic body fluid) is 10 to 50 mass from the viewpoint of the storage stability of the second polymer elastic body. % Is preferable, and more preferably 15 to 40% by mass.

  In addition, the second polymer elastic body fluid used in the present invention contains a water-soluble organic solvent in an amount of 40% by mass or less based on the second polymer elastic body fluid in order to improve storage stability and film forming property. However, the content of the organic solvent is preferably 1% by mass or less from the viewpoint of the preservation of the film forming environment.

  Moreover, as the 2nd polymer elastic body liquid used by this invention, what has heat-sensitive coagulation property is preferable. By using the second polymer elastic body fluid having heat-sensitive coagulation properties, it is difficult for the fibrous base material to be unevenly distributed on both surfaces, and the first polymer elastic body layer and the second polymer elastic body A layer can be formed.

  In the present invention, the heat-sensitive coagulation property refers to the property that when the second polymer elastic body fluid is heated, the fluidity of the second polymer elastic body fluid decreases and solidifies when reaching a certain temperature (thermal coagulation temperature). Say that. In the production of the second sheet with a polymer elastic body, after applying the second polymer elastic body fluid to the fibrous nonwoven sheet substrate, it is subjected to dry heat coagulation, wet heat coagulation, wet coagulation, or these The second polymer elastic body is imparted to the fibrous nonwoven sheet base material by solidifying by combination and drying. As a method for coagulating the second polymer elastic body fluid that does not exhibit heat-sensitive coagulation, dry coagulation is practical in industrial production. In that case, the second layer is not formed on the surface layer of the fibrous nonwoven sheet substrate. A migration phenomenon in which the polymer elastic body concentrates occurs, making it difficult to form the two-layer structure of the present invention.

  The heat-sensitive coagulation temperature of the second polymer elastic body fluid used in the present invention is preferably 40 to 90 ° C. By setting the heat-sensitive coagulation temperature to 40 ° C. or higher, the stability during storage of the second polymer elastic body fluid is improved, and adhesion of the second polymer elastic body to the machine during operation can be suppressed. it can. Moreover, the migration phenomenon of the 2nd polymeric elastic body in a fibrous nonwoven sheet base material can be suppressed by making heat-sensitive coagulation temperature into 90 degrees C or less.

  In one embodiment of the present invention, a thermal coagulant can be added as appropriate in order to set the thermal coagulation temperature as described above. Examples of heat-sensitive coagulants include inorganic salts such as sodium sulfate, magnesium sulfate, calcium sulfate, and calcium chloride; radical reactions such as sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and benzoyl peroxide. An initiator etc. are mentioned.

  The moist heat coagulation temperature is preferably equal to or higher than the thermosensitive coagulation temperature of the second polymer elastic body, more preferably 40 to 200 ° C. By setting the wet heat solidification temperature to preferably 40 ° C. or higher, more preferably 80 ° C. or higher, the time to solidification of the second polymer elastic body can be shortened to further suppress the migration phenomenon. The polymer elastic body can be solidified inside the sheet, and the two-layer structure intended in the present invention can be obtained. On the other hand, when the temperature of wet heat solidification is preferably 200 ° C. or less, more preferably 160 ° C. or less, thermal degradation of the first polymer elastic body and the second polymer elastic body can be prevented.

  The wet coagulation temperature is not less than the heat-sensitive coagulation temperature of the second polymer elastic body and is preferably 40 to 100 ° C. By setting the temperature of wet coagulation in hot water to preferably 40 ° C. or higher, more preferably 80 ° C. or higher, the time until solidification of the second polymer elastic body is shortened to further suppress the migration phenomenon. The second polymer elastic body can be solidified inside the sheet, and the two-layer structure intended in the present invention can be obtained.

  The dry solidification temperature and the drying temperature are preferably 80 to 200 ° C. Productivity is excellent when the dry coagulation temperature and the drying temperature are preferably 80 ° C. or higher, more preferably 90 ° C. or higher. On the other hand, when the dry coagulation temperature and the drying temperature are preferably 200 ° C. or less, more preferably 160 ° C. or less, thermal deterioration of the first polymer elastic body and the second polymer elastic body can be prevented.

  It is preferable that the application amount of the second polymer elastic body after drying with respect to the fibrous nonwoven sheet substrate is 0.05 to 45% by mass. By setting the application amount of the second polymer elastic body to 0.05% by mass or more, sufficient mechanical properties can be obtained, and by setting the application amount to 45% by mass or less, the texture decreases due to the sheet becoming heavier. Less influence.

  In the present invention, the PVA can be applied to the fibrous non-woven sheet substrate that has been subjected to ultrafine processing, and then the second polymer elastic body can be applied, and then the PVA can be removed. By applying PVA before applying the second polymer elastic body, PVA is attached to the periphery of the ultrafine fiber, and further, the second polymer elastic body is attached to the periphery thereof, and then PVA is removed. Thus, a space is formed between the ultrafine fiber and the second polymer elastic body, and flexibility can be expressed in the sheet-like material. PVA here is not a polymer elastic body but a resin used as a spacer for expressing a space between the second polymer elastic body and the fiber.

  As described above, a sheet-like material composed of the nonwoven fabric sheet of the present invention and two or more different polymer elastic bodies is obtained.

  The raising treatment of the sheet-like material of the present invention can be performed using a sandpaper or a roll sander. In particular, by using sandpaper, uniform and dense napping can be formed. Furthermore, in order to form the above-mentioned uniform ultrafine fiber napping on the surface of the sheet material, the ratio between the diameter of the ultrafine fiber and the abrasive grain size of the sandpaper used, the sandpaper and the leather-like sheet material It is preferable to control the speed ratio, grinding amount, grinding load, and the like within an appropriate range. In order to reduce the grinding load, multi-stage buffing with 3 or more buff stages is used, with 70 to 90% of the total grinding amount in the first and second stages or more and 30 to 10% in the final stage. It is preferable to carry out and prepare the surface.

  By buffing the sheet-like material under the above conditions, the ultrafine fibers combined with the polymer elastic body are efficiently dug up, and the dispersibility of the surface fibers is ensured. By buffing grinding, it becomes possible to form a surface state in which the above-mentioned nappings composed of the ultrafine fiber bundles are densely arranged on the surface.

  In the method for producing a sheet-like material of the present invention, at least after applying the second polymer elastic body to the fibrous nonwoven sheet base material provided with the first polymer elastic body, the sheet is cut in the thickness direction of the sheet. The process of carrying out may be included. Thus, production efficiency can be improved by including the process of half-cutting in the sheet thickness direction.

  In the sheet-like material of the present invention, the third or fourth high-strength is added to the nonwoven sheet provided with the second polymer elastic body on the fibrous nonwoven sheet base material provided with at least the first polymer elastic body. A molecular elastic body may be provided. By providing the third or fourth polymer elastic body, functionality for various uses such as fluff prevention can be imparted.

  The sheet-like material can be dyed. As a dyeing method, it is preferable to use a liquid dyeing machine because the sheet-like material can be softened by dyeing the sheet-like material and at the same time giving a stagnation effect.

  The temperature at the time of dyeing is preferably 80 to 150 ° C., although it depends on the type of fiber. By setting the dyeing temperature to preferably 80 ° C. or higher, more preferably 110 ° C. or higher, it is possible to efficiently dye the fibers. On the other hand, when the dyeing temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower, deterioration of the first polymer elastic body or the second polymer elastic body can be prevented.

  The dye used for the above dyeing can be selected according to the type of fiber constituting the fibrous base material. For example, a disperse dye is used for a polyester fiber, and an acid dye or a containing dye is used for a polyamide fiber. Gold dyes can be used, and further combinations thereof can be used. When dyeing with a disperse dye, reduction washing can be performed after dyeing.

  It is also a preferred embodiment to use a dyeing assistant during dyeing. By using a dyeing assistant, the uniformity and reproducibility of dyeing can be improved. In addition, a finishing treatment using a softening agent such as silicone, an antistatic agent, a water repellent, a flame retardant, a light proofing agent, and an antibacterial agent can be performed in the same bath or after dyeing.

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

  Next, the sheet-like material of the present invention and the method for producing the same will be described in more detail with reference to examples. However, the present invention is not limited to these examples, and many modifications are possible. It is possible by those who have ordinary knowledge in the field within the idea.

[Evaluation method]
(1) Average single fiber diameter measurement:
The average single fiber diameter was obtained by taking a scanning electron microscope (SEM) photograph of a cross section of a fibrous nonwoven sheet base or sheet-like material at a magnification of 2000 times, randomly selecting 100 fibers, and measuring the single fiber diameter. The average value was calculated.

  When the fiber which comprises a fibrous nonwoven sheet base material or a sheet-like object is an irregular cross section, the outer periphery circular diameter of an irregular cross section is computed as a single fiber diameter. Also, when the circular cross section and the irregular cross section are mixed, or when the single fiber diameters are greatly different, etc., the number of samplings corresponding to each existing number ratio is selected and calculated to be a total of 100. To do. However, if a reinforcing woven fabric or knitted fabric is inserted into the fibrous nonwoven sheet base material, the fibers of the reinforcing woven fabric or knitted fabric are excluded from sampling in the measurement of the average single fiber diameter. To do.

(2) Observation of layered structure of sheet-like material:
The cross-sectional structure of the sheet-like material was observed with a color photograph taken at a magnification of 100 using a microscope with a cross-section of the sheet-like material. The layer structure is confirmed by the hue difference between the first polymer elastic body and the second polymer elastic body using the pigment contained in the second polymer elastic body, and the first polymer elastic body layer Ten layers of each of the polymer elastic bodies were measured, and the average value was calculated.

(3) Measurement of glass transition temperature (Tg) of the first polymer elastic body:
Using a differential scanning calorimeter (RDC220 (Seiko Instruments)), a nitrogen flow rate of 20 mL / min in a nitrogen atmosphere, a first polymer elastic body dry film (using a hot air dryer at a temperature of 100 ° C., 5 It was calculated from the DSC curve measured by weighing 5 mg (prepared under conditions of drying for 5 minutes).

(4) Compression elastic modulus of the first polymer elastic resin film:
The compression elastic modulus of the first polymer elastic resin film was measured according to JIS L1913 (2005) 6.12 compression elastic modulus measurement. First, five 5 cm × 5 cm resin films are stacked, an initial load of 0.5 kPa is applied, and an initial thickness T0 is measured. Next, a load of 30 kPa is applied for 1 minute, and the thickness T1 when 30 kPa is applied is measured. Thereafter, the load was removed, and the thickness when the load of 0.5 kPa was applied again after being left for 1 minute was defined as T′0, and calculated from the following formula.
Compression elastic modulus = (T′0−T1) / (T0−T1) × 100 (%).

(5) Mass reduction rate of the first polymer elastic body:
10% by mass of the non-woven fabric to which the first polymer elastic body is applied so that the total mass after drying is 5 g with respect to 2 g of polypropylene non-woven fabric, and the liquid temperature is 90 ° C. in a thermostatic bath. After immersing the nonwoven fabric provided with the first polymer elastic body in 300 mL of an aqueous sodium solution for 10 minutes, the weight of the nonwoven fabric after drying for 20 minutes with a hot air drier at a temperature of 120 ° C. is determined as W1 g by the following formula. It was.
Mass reduction rate = (W0−W1) / (W0−2) × 100 (%).

(6) Flexibility of sheet-like material:
The flexibility of the sheet-like material was evaluated based on the bending resistance. The bending resistance conforms to JIS L1096 (1999) 8.19.4 D method (heart loop method), and a 2 cm × 25 cm test piece is attached to a horizontal bar grip in a heart loop shape (effective length: 20 cm). The distance L (mm) between the vertex of the horizontal bar after the lapse of minutes and the lowest point of the loop was measured as the bending resistance. A softness of 6 cm or more in bending resistance was considered good.

(7) Rebound of sheet-like material:
The rebound feeling of the sheet-like material was evaluated by the following five levels by sensory evaluation with 10 adult males and 10 adult females each in good health condition, with a total of 20 as evaluators. It was a feeling. The rebound feeling made the 3rd-5th grade favorable.
Grade 5: Excellent rebound feeling when gripping a sheet-like material.
Grade 4: Evaluation between grade 5 and grade 3.
Third grade: There is a slight resilience when a sheet-like object is gripped, and it is reasonably good.
Second grade: An evaluation between the third grade and the first grade.
First grade: There is no repulsion when gripping a sheet-like object, and it is defective.

[Example 1]
(Fiber nonwoven sheet base material)
As the sea component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used, and as the island component, polyethylene terephthalate is used. The sea component is 20% by mass, the island component is 80% by mass, and the number of islands is 16 / 1 filament, sea island type composite fiber having an average single fiber diameter of 21 μm was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a fibrous nonwoven sheet base material. The obtained fibrous nonwoven sheet base material had a basis weight of 750 g / m ² and a thickness of 2.20 mm.

(Adjustment of the first polymer elastic body fluid)
An acrylic resin having a Tg of −31 ° C. (“Boncoat” (registered trademark) LX874 manufactured by Nippon Zeon Co., Ltd.) was adjusted to an aqueous solution having a solid content of 8% by mass to obtain a first polymer elastic body fluid. The mass reduction rate of the first polymer elastic body was 6%.

(Addition of first polymer elastic body)
The fibrous nonwoven sheet base material is impregnated with the first polymer elastic body fluid, and is heated and dried at a temperature of 140 ° C. for 10 minutes. The sheet | seat provided with the 1st polymer elastic body was obtained so that the adhesion amount of a polymer elastic body might be 15 mass%.

(Fiber miniaturization (sea removal))
The first polymer elastic body-applied sheet is immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 5 minutes to remove the sea component of the sea-island composite fiber. A sea removal sheet comprising an elastic body and ultrafine fibers was obtained. The average single fiber diameter of the sea removal sheet was 4.4 μm.

(Preparation of PVA solution)
PVA having a saponification degree of 99% and a polymerization degree of 1400 (NM-14 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.

(PVA liquid application)
The seawater-removed sheet was impregnated with the PVA liquid, and heat-dried at a temperature of 140 ° C. for 10 minutes to obtain a PVA-coated sheet having a PVA adhesion amount of 10 mass% with respect to the fiber mass of the seawater-removed sheet.

(Preparation of second polymer elastic body fluid)
To 100 parts by mass of the solid content of a polycarbonate-based self-emulsifying polyurethane liquid in which polyhexamethylene carbonate is applied to the polyol and dicyclohexylmethane diisocyanate is applied to the isocyanate, 2 parts by mass of ammonium persulfate (APS) is added as a thermal coagulant, 1 part by mass of carbon black was added as a pigment, and the whole was adjusted to a solid content concentration of 10% by mass with water to obtain a second polymer elastic body fluid. The thermal coagulation temperature was 72 ° C.

(Application of second elastic polymer fluid)
The PVA-given sheet is impregnated with the second polymer elastic body fluid, treated in a moist and hot atmosphere at a temperature of 100 ° C. for 5 minutes, then dried with hot air at a drying temperature of 120 ° C. for 5 minutes, and further 150 ° C. By performing a dry heat treatment at a temperature of 2 minutes, a sheet provided with the second polymer elastic body was obtained so that the adhesion amount of the second polymer elastic body to the mass of ultrafine fibers was 15% by mass.

(Removal of PVA)
Said 2nd polymeric elastic body provision sheet | seat was immersed in the water heated to the temperature of 95 degreeC, and it processed for 10 minutes, and obtained the sheet | seat which removed the provided PVA.

(Half court)
The sheet from which the PVA was removed was cut in half in the thickness direction. The half cut was good.

(Brushed)
The surface of the half-cut surface of the above-mentioned half-cut sheet was subjected to raising treatment by three-stage grinding using a 240 mesh endless sandpaper.

(Dyeing / reduction cleaning)
The above raised sheet was dyed with a disperse dye using a circular dyeing machine and subjected to reduction cleaning to obtain a sheet. Table 1 shows the evaluation results of the obtained sheet-like material. In the cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body was 300 μm and the thickness of the second polymer elastic body was 500 μm was confirmed. The flexibility and resilience of the obtained sheet were good.

[Example 2]
(Fiber nonwoven sheet base material)
In the same manner as in Example 1, a fibrous nonwoven sheet substrate was obtained.

(Adjustment of the first polymer elastic body fluid)
A first polymer elastic body fluid was obtained in the same manner as in Example 1 except that the solid content concentration was adjusted to 5% by mass.

(Addition of first polymer elastic body)
The fibrous nonwoven sheet base material is impregnated with the first polymer elastic body fluid, and is heated and dried at a temperature of 140 ° C. for 10 minutes. The sheet | seat which provided the 1st polymer elastic body so that the adhesion amount of the polymer elastic body might be 10 mass% was obtained.

(Fiber miniaturization (sea removal))
In the same manner as in Example 1, a seawater-removal sheet was obtained from the first polymer elastic body-applied sheet.

(Preparation and provision of PVA solution)
In the same manner as in Example 1, a PVA-added sheet having a PVA adhesion amount of 10% by mass with respect to the fiber mass of the sea-sealed sheet was obtained.

(Preparation of second polymer elastic body fluid)
A second polymer elastic body fluid was obtained in the same manner as in Example 1 except that the solid content concentration was 13% by mass.

(Application of second elastic polymer fluid)
The above-mentioned PVA application sheet is impregnated with the above-mentioned second polymer elastic body fluid, and the second polymer elastic body is attached so that the adhesion amount of the second polymer elastic body to the ultrafine fiber mass becomes 20% by mass. A given sheet was obtained.

(PVA removal, half-cut, brushed, dyeing, reduction cleaning)
A sheet-like material was obtained in the same manner as Example 1. Table 1 shows the evaluation results of the obtained sheet-like material. In a cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 150 μm and the thickness of the second polymer elastic body layer was 650 μm was confirmed. The obtained sheet-like material was slightly inferior to that of Example 1, but had good flexibility.

[Example 3]
(Fiber nonwoven sheet base material)
In the same manner as in Example 1, a fibrous nonwoven sheet substrate was obtained.

(Adjustment of the first polymer elastic body fluid)
Except having prepared so that solid content concentration might be 10 mass%, it carried out similarly to Example 1, and obtained the 1st polymer elastic body fluid.

(Addition of first polymer elastic body)
The fibrous nonwoven sheet base material is impregnated with the first polymer elastic body fluid, and is heated and dried at a temperature of 140 ° C. for 10 minutes. The sheet | seat which provided the 1st polymer elastic body so that the adhesion amount of the polymer elastic body might be 20 mass% was obtained.

(Fiber miniaturization (sea removal))
A sea removal sheet was obtained in the same manner as in Example 1 on the sheet provided with the first polymer elastic body.

(Preparation and provision of PVA solution)
In the same manner as in Example 1, a sheet to which PVA having an adhesion amount of PVA of 10% by mass with respect to the fiber mass of the sea removal sheet was obtained.

(Preparation of second polymer elastic body fluid)
A second polymer elastic body fluid was obtained in the same manner as in Example 1 except that the solid content concentration was 7% by mass.

(Application of second elastic polymer fluid)
The above-mentioned PVA application sheet is impregnated with the above-mentioned second polymer elastic body fluid, and the second polymer elastic body is attached so that the adhesion amount of the second polymer elastic body to the mass of ultrafine fibers becomes 10% by mass. A given sheet was obtained.

(PVA removal, half-cut, brushed, dyeing, reduction cleaning)
A sheet-like material was obtained in the same manner as Example 1. Table 1 shows the evaluation results of the obtained sheet-like material. In cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 500 μm and the thickness of the second polymer elastic body layer was 300 μm was confirmed. Although the obtained sheet-like material was slightly inferior to that of Example 1, the resilience was good.

[Example 4]
(Fiber nonwoven sheet base material)
In the same manner as in Example 1, a fibrous nonwoven sheet substrate was obtained.

(Adjustment of the first polymer elastic body fluid)
A first polymer elastic body fluid was obtained in the same manner as in Example 1 except that the solid content concentration was adjusted to 1% by mass.

(Addition of first polymer elastic body)
The fibrous nonwoven sheet base material is impregnated with the first polymer elastic body fluid, and is heated and dried at a temperature of 140 ° C. for 10 minutes. The sheet | seat which provided the 1st polymer elastic body so that the adhesion amount of a polymer elastic body might be 2 mass% was obtained.

(Fiber miniaturization (sea removal))
In the same manner as in Example 1, a seawater-removal sheet was obtained from the first polymer elastic body-applied sheet.

(Preparation and provision of PVA solution)
In the same manner as in Example 1, a sheet to which PVA having an adhesion amount of PVA of 10% by mass with respect to the fiber mass of the sea removal sheet was obtained.

(Preparation of second polymer elastic body fluid)
A second polymer elastic body fluid was obtained in the same manner as in Example 1 except that the solid content concentration was adjusted to 20% by mass.

(Application of second elastic polymer fluid)
The above-mentioned PVA application sheet is impregnated with the above-mentioned second polymer elastic body fluid, and the second polymer elastic body is attached so that the adhesion amount of the second polymer elastic body to the ultrafine fiber mass becomes 28% by mass. A given sheet was obtained.

(PVA removal, half-cut, brushed, dyeing, reduction cleaning)
A sheet-like material was obtained in the same manner as Example 1. Table 1 shows the evaluation results of the obtained sheet-like material. In cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 50 μm and the thickness of the first polymer elastic body layer was 750 μm was confirmed. Although the obtained sheet-like material was inferior in resilience to Example 1, the flexibility was very good.

[Example 5]
(Fiber nonwoven sheet base material)
In the same manner as in Example 1, a fibrous nonwoven sheet substrate was obtained.

(Adjustment of the first polymer elastic body fluid)
Except having prepared so that solid content concentration might be 15 mass%, it carried out similarly to Example 1, and obtained the 1st polymer elastic body fluid.

(Addition of first polymer elastic body)
The fibrous nonwoven sheet base material is impregnated with the first polymer elastic body fluid, and is heated and dried at a temperature of 140 ° C. for 10 minutes. The sheet | seat which provided the 1st polymer elastic body so that the adhesion amount of the polymer elastic body might be 28 mass% was obtained.

(Fiber miniaturization (sea removal))
In the same manner as in Example 1, a seawater-removal sheet was obtained from the first polymer elastic body-applied sheet.

(Preparation and provision of PVA solution)
In the same manner as in Example 1, a PVA-added sheet having a PVA adhesion amount of 10% by mass with respect to the fiber mass of the sea-sealed sheet was obtained.

(Preparation of second polymer elastic body fluid)
A second polymer elastic body fluid was obtained in the same manner as in Example 1 except that the solid content concentration was 2% by mass.

(Application of second elastic polymer fluid)
The PVA application sheet is impregnated with the first polymer elastic body fluid, and the second polymer elastic body is attached so that the amount of the second polymer elastic body attached to the ultrafine fiber mass is 2% by mass. A given sheet was obtained.

(PVA removal, half-cut, brushed, dyeing, reduction cleaning)
A sheet-like material was obtained in the same manner as Example 1. Table 1 shows the evaluation results of the obtained sheet-like material. In cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 700 μm and the thickness of the second polymer elastic body layer was 100 μm was confirmed. Although the obtained sheet-like material was inferior to Example 1 in flexibility, the rebound feeling was very good.

[Example 6]
A sheet-like material was obtained in the same manner as in Example 1 except that an SBR resin having a Tg of 58 ° C. (SBR resin 2507H manufactured by JSR Corporation, mass reduction rate 8%) was used for the first polymer elastic body. Obtained. The evaluation results of the obtained sheet are shown in Table 1 below. In cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 300 μm and the thickness of the second polymer elastic body layer was 500 μm was confirmed. Although the obtained sheet-like material was slightly inferior to Examples 1-5 in flexibility and resilience, it was at a satisfactory level.

[Example 7]
Nylon copolymer resin having a Tg of 48 ° C. (nylon copolymer resin “Sepoljon” (registered trademark) PA200, mass reduction rate 7%) manufactured by Sumitomo Seika Co., Ltd.) was used as the first polymer elastic body. Except for the above, a sheet-like material was obtained in the same manner as in Example 1. Table 2 shows the evaluation results of the obtained sheet-like material. In cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 300 μm and the thickness of the second polymer elastic body layer was 500 μm was confirmed. Although the obtained sheet-like material was slightly inferior to Examples 1-5 in flexibility and resilience, it was at a satisfactory level.

[Example 8]
(Fiber nonwoven sheet base material)
In the same manner as in Example 1, a fibrous nonwoven sheet substrate was obtained.

(Adjustment and application of the first polymer elastic body fluid)
The above-mentioned fibrous nonwoven sheet base material is impregnated with the first polymer elastic body fluid obtained in Example 1, and in the same manner as in Example 1, the polymer elasticity relative to the island component mass of the fibrous nonwoven sheet base material The sheet | seat which provided the 1st polymeric elastic body so that the adhesion amount of a body might be 15 mass% was obtained.

(Fiber miniaturization (sea removal))
In the same manner as in Example 1, a seawater-removal sheet was obtained from the first polymer elastic body-applied sheet.

(Preparation of PVA solution)
PVA having a saponification degree of 87% and a polymerization degree of 500 (GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 5% by mass to obtain a PVA liquid.

(PVA liquid application)
Using the above fibrous nonwoven sheet base material and the above PVA aqueous solution, a PVA application sheet having a PVA adhesion amount of 10% by mass with respect to the fiber mass of the fibrous nonwoven sheet base material is obtained in the same manner as in Example 1. It was.

(Preparation of second polymer elastic body fluid)
A 30% DMF aqueous solution in which a polyurethane (gel point: 4.2 ml) composed of 75% by mass of a polyether diol and 25% by mass of a polyester was adjusted to a solid content concentration of 12% by mass was obtained.

(Application of second polymer elastic body fluid / PVA removal)
The seawater-free sheet is impregnated with the second polymer elastic body fluid, adjusted so that the amount of the second polymer elastic body attached to the ultrafine fibers is 15% by mass, and polyurethane with water at a temperature of 35 ° C. Was solidified to remove DMF and PVA at the same time to obtain a sheet provided with a second polymer elastic body.

(Half-cut, brushed, dyed, reduced cleaning)
A sheet-like material was obtained in the same manner as Example 1. Table 2 shows the evaluation results of the obtained sheet-like material. In cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 300 μm and the thickness of the second polymer elastic body layer was 500 μm was confirmed. The flexibility and resilience of the obtained sheet were good.

[Example 9]
(Fiber nonwoven sheet base material)
As the sea component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used, and as the island component, polyethylene terephthalate is used. The sea component is 50% by mass and the island component is 50% by mass. / 1 filament, sea-island type composite fiber having an average single fiber diameter of 18 μm was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material. The obtained fibrous nonwoven sheet base material had a basis weight of 600 g / m ² and a thickness of 1.80 mm.

(Adjustment and application of the first polymer elastic body fluid)
In the same manner as in Example 1, a sheet provided with the first polymer elastic body was obtained so that the adhesion amount of the first polymer elastic body was 15 parts by mass.

(Fiber miniaturization (sea removal))
The first polymer elastic body-applied sheet is immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 5 minutes to remove the sea component of the sea-island composite fiber. A sea removal sheet comprising an elastic body and ultrafine fibers was obtained. The average single fiber diameter of the sea removal sheet was 2.1 μm.

(Preparation and provision of PVA solution)
In the same manner as in Example 1, a sheet to which PVA having an adhesion amount of PVA of 10% by mass with respect to the fiber mass of the sea removal sheet was obtained.

(Preparation and application of the second polymer elastic body fluid)
In the same manner as in Example 1, a sheet to which the second polymer elastic body was applied was obtained so that the amount of the second polymer elastic body attached to the ultrafine fiber mass was 15% by mass.

(PVA removal, half-cut, brushed, dyeing, reduction cleaning)
A sheet-like material was obtained in the same manner as Example 1. The evaluation results of the obtained sheet are shown in Table 2 below. In cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 300 μm and the thickness of the second polymer elastic body layer was 500 μm was confirmed. The flexibility and resilience of the obtained sheet were good.

[Example 10]
(Fiber nonwoven sheet base material)
As the sea component, polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate is used. As the island component, polyethylene terephthalate is used. The sea component is 60% by mass and the island component is 40% by mass. / 1 filament, sea-island type composite fiber having an average single fiber diameter of 18 μm was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material. The obtained fibrous nonwoven sheet base material had a basis weight of 700 g / m ² and a thickness of 2.20 mm.

(Adjustment and application of the first polymer elastic body fluid)
In the same manner as in Example 1, a sheet provided with the first polymer elastic body was obtained so that the adhesion amount of the first polymer elastic body was 15 parts by mass.

(Fiber miniaturization (sea removal))
The first polymer elastic body-applied sheet is immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 10 minutes to remove the sea component of the sea-island composite fiber. A sea removal sheet comprising an elastic body and ultrafine fibers was obtained. The average single fiber diameter of the sea removal sheet was 0.5 μm.

(Preparation and provision of PVA solution)
In the same manner as in Example 1, a sheet to which PVA having an adhesion amount of PVA of 10% by mass with respect to the fiber mass of the sea removal sheet was obtained.

(Preparation and application of the second polymer elastic body fluid)
In the same manner as in Example 1, a sheet to which the second polymer elastic body was applied was obtained so that the amount of the second polymer elastic body attached to the ultrafine fiber mass was 15% by mass.

(PVA removal, half-cut, brushed, dyeing, reduction cleaning)
A sheet-like material was obtained in the same manner as Example 1. The evaluation results of the obtained sheet are shown in Table 2 below. In the cross-sectional observation of the obtained sheet-like material, a two-layer structure in which the thickness of the first polymer elastic body layer was 200 μm and the thickness of the second polymer elastic body layer was 500 μm was confirmed. The flexibility and resilience of the obtained sheet were good.

[Comparative Example 1]
(Fiber nonwoven sheet base material)
In the same manner as in Example 1, a fibrous nonwoven sheet substrate was obtained.

(Fiber miniaturization (sea removal))
A seawater-removed sheet was obtained in the same manner as in Example 1 on the above fibrous nonwoven sheet base material.

(Preparation and application of PVA solution)
In the same manner as in Example 1, a sheet to which PVA having an adhesion amount of PVA of 10% by mass with respect to the fiber mass of the sea removal sheet was obtained.

(Preparation of second polymer elastic body fluid)
A second polymer elastic body fluid was obtained in the same manner as in Example 1 except that the solid content concentration was adjusted to 20% by mass.

(Application of second elastic polymer fluid)
The above-mentioned PVA application sheet is impregnated with the above-mentioned second polymer elastic body fluid, and the second polymer elastic body is attached so that the adhesion amount of the second polymer elastic body to the ultrafine fiber mass is 30% by mass. A given sheet was obtained.

(PVA removal, half-cut, brushed, dyeing, reduction cleaning)
A sheet-like material was obtained in the same manner as Example 1. Table 3 shows the evaluation results of the obtained sheet-like material. In the cross-sectional observation of the obtained sheet-like material, only the second polymer elastic body layer having a thickness of 800 μm was confirmed. The flexibility of the obtained sheet-like material was good, but there was no resilience, and the resilience was inferior to Examples 1-8, which was not a satisfactory level.

[Comparative Example 2]
(Fiber nonwoven sheet base material)
Polystyrene is used as the sea component, polyethylene terephthalate is used as the island component, a sea-island type composite with a sea ratio of 20 mass% and an island component of 80 mass%, 16 islands / 1 filament, average single fiber diameter of 21 μm. Fiber was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink and dried at a temperature of 100 ° C. for 5 minutes to obtain a fibrous nonwoven sheet base material.

(Preparation of PVA solution)
PVA having a saponification degree of 87% and a polymerization degree of 500 (GL-05 manufactured by Nippon Synthetic Chemical Co., Ltd.) was prepared as an aqueous solution having a solid content of 10% by mass to obtain a PVA liquid.

(PVA liquid application)
The sheet | seat which provided PVA with the adhesion amount of PVA with respect to the fiber mass of a fibrous nonwoven sheet base material 30 mass% similarly to Example 1 using said fibrous nonwoven sheet base material and said PVA aqueous solution. Got.

(Fiber miniaturization (sea removal))
Said PVA provision sheet | seat was immersed in the trichlorethylene, and the sea removal sheet which removed the sea component of the sea-island type composite fiber was obtained.

(Preparation of second polymer elastic body fluid)
A 30% DMF aqueous solution in which a polyurethane (gel point: 4.2 ml) composed of 75% by mass of a polyether diol and 25% by mass of a polyester was adjusted to a solid content concentration of 12% by mass was obtained.

(Application of second polymer elastic body fluid / PVA removal)
The seaweed sheet is impregnated with the second polymer elastic body fluid, adjusted so that the amount of polyurethane attached to the ultrafine fibers is 30% by mass, and the polyurethane is solidified with water at a temperature of 35 ° C. PVA was removed at the same time to obtain a sheet provided with the second polymer elastic body.

(Half-cut, brushed, dyed, reduced cleaning)
A sheet-like material was obtained in the same manner as Example 1. Table 3 shows the evaluation results of the obtained sheet-like material. In the cross-sectional observation of the obtained sheet-like material, only the second polymer elastic body layer having a thickness of 800 μm was confirmed. The flexibility of the obtained sheet-like material was good, but there was no resilience, and the resilience was inferior to Examples 1-8, which was not a satisfactory level.

[Comparative Example 3]
(Fiber nonwoven sheet base material)
A fibrous nonwoven sheet base material was obtained in the same manner as in Example 1.

(Adjustment of the first polymer elastic body fluid)
In the same manner as in Example 4, a first polymer elastic body fluid was obtained.

(Addition of first polymer elastic body)
The fibrous nonwoven sheet base material is impregnated with the first polymer elastic body fluid, and is heated and dried at a temperature of 140 ° C. for 10 minutes. The sheet | seat which provided the 1st polymer elastic body so that the adhesion amount of a polymer elastic body might be 30 mass% was obtained.

(Fiber miniaturization (sea removal))
A sea removal sheet was obtained in the same manner as in Example 1 on the sheet provided with the first polymer elastic body.

(Half-cut, brushed, dyed, reduced cleaning)
A sheet-like material was obtained from the sea removal sheet in the same manner as in Example 1. The evaluation results of the obtained sheet are shown in Table 3 below. In the cross-sectional observation of the obtained sheet-like material, only the first polymer elastic body layer having a thickness of 600 μm was confirmed. Although the resilience of the obtained sheet-like material was good, it was not flexible and was inferior in flexibility as compared with Examples 1 to 9, and was not at a satisfactory level.

  The evaluation results of the sheet-like materials obtained in the above Examples and Comparative Examples are shown in Table 3 below.

  The sheet-like materials obtained in Examples 1 to 9 all had good flexibility and resilience, and both flexibility and resilience were compatible. On the other hand, the sheet-like materials obtained in Comparative Examples 1 to 3 were not satisfactory because both flexibility and resilience were not achieved.

A: Full range in the thickness direction of the fibrous nonwoven sheet base material B: 0-30% range in the thickness direction of the fibrous nonwoven sheet base material C: 0-30 in the thickness direction of the fibrous nonwoven sheet base material % Range

Claims (5)

  There is a non-woven sheet in which ultrafine fibers having an average single fiber diameter of 0.3 to 7.0 μm are entangled, and a sheet-like material composed of two or more different types of polymer elastic bodies, and the two or more types of the different types A sheet-like product comprising a polymer elastic body arranged in layers in the thickness direction inside the nonwoven fabric sheet.   The sheet-like material according to claim 1, wherein the polymer elastic body is of two types, an acrylic resin and a polyurethane resin.   The sheet material according to claim 2, wherein the mass ratio of the acrylic resin and the polyurethane resin is 10:90 to 90:10.   The sheet-like material according to claim 2 or 3, wherein the glass transition temperature of the acrylic resin is less than 100 ° C.   A step of applying a first polymer elastic body in a thickness direction of 0 to 30% from both surfaces of the fibrous nonwoven sheet, to the fibrous nonwoven sheet base material having an ultrafine fiber-expressing fiber as a main component; A step of expressing an ultrafine fiber having an average single fiber diameter of 0.3 to 7.0 μm from a fibrous nonwoven sheet substrate provided with the first polymer elastic body, and a fiber in which the ultrafine fiber is expressed A method for producing a sheet-like material comprising the step of applying a second polymer elastic body to a textured nonwoven sheet substrate.