WO2021125032A1

WO2021125032A1 - Sheet-like article and method for producing same

Info

Publication number: WO2021125032A1
Application number: PCT/JP2020/046009
Authority: WO
Inventors: 芝野卓也; 宿利隆司; 石井孝樹
Original assignee: 東レ株式会社
Priority date: 2019-12-20
Filing date: 2020-12-10
Publication date: 2021-06-24
Also published as: CN114729501B; CN114729501A; JPWO2021125032A1; JP6904493B1; TW202129118A; EP4079962A4; EP4079962A1; KR20220113689A; US20220380976A1

Abstract

The purpose of the present invention is to provide: a sheet-like article which has a good balance between soft texture and excellent light resistance; and a method for producing this sheet-like article.　In order to achieve this purpose, a sheet-like article according to the present invention has the following configuration. Specifically, a sheet-like article which contains a polymer elastic body in a fibrous base material, wherein: the fibrous base material is composed of ultrafine fibers that have an average single fiber diameter of from 0.1 μm to 10 μm; the polymer elastic body has a hydrophilic group, while containing a polyether diol as a constituent; the polymer elastic body internally has an N-acylurea bond and/or an isourea bond; and the condition 1 and the condition 2 described below are satisfied. Condition 1: The bending resistance in the lengthwise direction as determined in accordance with specific standards is from 40 mm to 140 mm. Condition 2: The abrasion weight loss after 20,000 cycles of a Martindale abrasion test set forth in JIS L 1096 (2005) after a light resistance test as performed under the conditions defined in accordance with specific standards is 25 mg or less.

Description

Sheet-shaped material and its manufacturing method

The present invention relates to a sheet-like material and a method for producing the same, particularly a sheet-like material having excellent flexibility and light resistance and a method for producing the same.

Sheet-like materials mainly composed of fibrous base materials such as non-woven fabrics and polyurethane have excellent characteristics not found in natural leather, and are widely used in various applications such as artificial leather. In particular, sheet-like materials using a polyester-based fibrous base material have excellent moldability, and are therefore expanding year by year to applications such as clothing, upholstery, and automobile interior materials.

In producing such a sheet, the fibrous base material is impregnated with an organic solvent solution of polyurethane, and then the obtained fibrous base material is immersed in water or an aqueous solution of an organic solvent which is a non-solvent of polyurethane. A combination of steps of wet-solidifying polyurethane is generally adopted. In this case, as the organic solvent which is the solvent of polyurethane, a water-miscible organic solvent such as N, N-dimethylformamide is used, but since the organic solvent is generally highly harmful to the environment, it is in the form of a sheet. There is a strong demand for a method that does not use an organic solvent in the production of.

As a specific solution, a method of using a water-dispersed polyurethane in which a polyurethane resin is dispersed in water is being studied instead of the conventional organic solvent-based polyurethane, but generally, a water-dispersed polyurethane is used. The solidified sheet-like material has a problem that the texture tends to be hard.

One of the main reasons is the difference between the two coagulation methods. That is, the coagulation method of polyurethane to which an organic solvent is applied is a so-called wet coagulation method in which polyurethane molecules dissolved in an organic solvent are solvent-substituted with water to coagulate. It is formed. Therefore, even when polyurethane is impregnated in the fibrous base material and solidified, the adhesive area between the fiber and polyurethane is reduced, and it is considered that a soft sheet-like material is formed.

On the other hand, the mainstream of water-dispersed polyurethane is a so-called moist heat coagulation method in which the hydrated state of the water-dispersed polyurethane dispersion is disrupted by heating and the polyurethane emulsions are coagulated to coagulate. The polyurethane film structure to be obtained is a dense non-porous film. Therefore, it is considered that the fibrous base material and the polyurethane are closely adhered to each other, and the entangled portion of the fibers is strongly gripped, so that the texture becomes hard.

So far, in order to obtain a sheet-like material having a soft texture using water-dispersible polyurethane, for example, a thickener has been added to a solution containing water-dispersible polyurethane, and the fibrous substrate impregnated with the solution has been heated. A method has been proposed in which a polyurethane film covering a fibrous base material is reduced in size by treatment with water to obtain a flexible texture (Patent Document 1).

As a method using the same coagulation method by hot water treatment, a method of obtaining a sheet-like material having excellent moisture and heat resistance by preventing deterioration of physical properties due to polyurethane swelling during dyeing by performing a cure treatment after dyeing (Patent Document 2). ) And water-dispersed polyurethane containing a hindered amine compound have been applied to obtain a sheet-like material having excellent light resistance and flexibility such as light yellowing resistance and light dyeing fastness (Patent Document 3).

In addition, by dissolving and mixing inorganic salts in the forcibly emulsified nonionic water-dispersed polyurethane, the heat-sensitive gelation temperature, which is the temperature at which the water-dispersed polyurethane gels, was adjusted and dispersed in water. A method has been proposed in which particles of a polymer emulsion are attracted by the movement of water and intensively adhere to the surface layer of a sheet-like material, that is, a so-called migration phenomenon is suppressed to obtain a flexible texture (a method for obtaining a flexible texture). Patent Document 4).

Further, a method has been proposed in which a sheet-like material is impregnated with water-dispersible polyurethane to which a polysaccharide is added, and the polymer elastic body is made into a porous structure by heating and drying at a two-step temperature to soften the texture. (Patent Document 5). In this method, the polymer elastic body is completely coagulated in the state where the polysaccharide grips the water in the first step drying, and the polymer is in the state where the polymer elastic body is completely coagulated in the second step drying. By evaporating the water held by the polysaccharide contained in the elastic body, the portion where the water held by the polysaccharide was present becomes a void, and a porous structure can be formed.

Alternatively, a method has been proposed in which a cross-linking agent is applied and heated to a sheet-like material obtained by coagulating water-dispersible polyurethane to cause a reaction to maintain the texture before the addition of the cross-linking agent (Patent Document 6). In this method, the water-dispersible polyurethane can be reacted with the cross-linking agent regardless of the method for coagulating the polyurethane, and a state close to the original coagulated structure of polyurethane can be maintained.

International Publication No. 2015/129602 JP-A-2017-172074 Japanese Unexamined Patent Publication No. 2000-265052 Japanese Unexamined Patent Publication No. 6-316877 Japanese Unexamined Patent Publication No. 2019-11274 International Publication No. 2016/052189

However, when the sheet-like material is used outdoors for automobile interior materials, there is a problem that the polyurethane that grips the fibers in the sheet-like material is decomposed by the ultraviolet rays contained in sunlight, and the sheet-like material deteriorates.

Normally, water-dispersible polyurethane is obtained by reacting a polymer polyol, an organic polyisocyanate, and a chain extender, and exhibits various properties depending on the components of the polymer polyol. There are two types of typical high molecular weight polyols, a polyether-based polyol and a polycarbonate-based polyol. A sheet-like product using a polyether-based applicable polyurethane can obtain a softer texture than a polycarbonate-based applicable polyurethane. It is inferior in light resistance. In order to achieve both a flexible texture and light resistance, it is necessary to improve the light resistance by using a polyether-based polyurethane in order to withstand actual use.

In the methods disclosed in Patent Documents 1 to 3, although the hardness of the texture can be improved by hot water coagulation to obtain a flexible texture to some extent, polyurethane does not sufficiently function as a binder and wear resistance. Insufficient sex. In the method disclosed in Patent Document 2, since the dye is heated at a high temperature after dyeing, the dye sublimates, so that there is a concern about discoloration in actual use, and the light resistance becomes insufficient. Further, in the method disclosed in Patent Document 3, although the light resistance is improved by containing the hindered amine compound, since the compound is contained in the polymer polyol, the physical characteristics of the film are deteriorated, the gripping force on the fiber is weak, and the material is in the form of a sheet. The wear resistance of the object is insufficient. Moreover, the flexibility is not sufficient.

Further, in the method disclosed in Patent Document 4, although a flexible texture can be achieved by suppressing migration, the fibers cannot be sufficiently gripped because the polyurethane resin is not three-dimensionally crosslinked. Insufficient wear resistance and light resistance.

On the other hand, in the method disclosed in Patent Document 5, a porous structure can be obtained by undergoing two-step drying, but the migration phenomenon cannot be completely suppressed and the texture is insufficient. Further, since the polyurethane resin is not three-dimensionally crosslinked, the fibers cannot be sufficiently gripped, resulting in insufficient wear resistance and light resistance.

Alternatively, in the method disclosed in Patent Document 6, the cross-linking agent is impregnated after the polyurethane is solidified, but the reaction between the polyurethane and the cross-linking agent does not proceed so much, so that the three-dimensional structure of the polyurethane and the cross-linking agent is sufficiently sufficient. It cannot be formed, resulting in insufficient wear resistance and light resistance.

Therefore, an object of the present invention is to provide a sheet-like material having both a flexible texture and excellent light resistance and a method for producing the same, in view of the background of the above-mentioned prior art.

As a result of repeated studies by the present inventors to achieve the above object, a polymer elastic material containing a polyether diol as a constituent component and a specific amount of a monovalent cation-containing inorganic salt and a cross-linking agent in combination is used. By adjusting the drying temperature in solidification, not only can a sheet-like material be manufactured in consideration of the environment, but also a sheet-like material having excellent texture and light resistance can be obtained as compared with a conventional sheet-like material. The heading led to the present invention.

That is, the present invention is intended to solve the above problems, and the sheet-like material of the present invention is a sheet-like material containing a polymer elastic body in a fibrous base material, and the fibrous base material is an average. It is composed of ultrafine fibers having a single fiber diameter of 0.1 μm or more and 10 μm or less, the polymer elastic body has a hydrophilic group, contains a polyether diol as a constituent component, and has an N-acylurea bond and an N-acylurea bond inside the polymer elastic body. / Or a sheet-like substance having an isourea bond and satisfying the following conditions 1 and 2.
Condition 1: JIS L 1096: 2010 The longitudinal stiffness specified by method A (45 ° cantilever method) described in "Fabric test method for woven fabrics and knitted fabrics" is 40 mm or more and 140 mm or less Condition 2: JIS L 0843: 2006 lightfastness measurement of xenon arc amount 110 mJ / ^{m 2} conditions after light resistance test was measured by JIS L 1096: abrasion loss in Martindale abrasion test 20,000 times defined by 2005 is less than 25mg According to a preferred embodiment of the sheet-like material of the present invention, the wear loss in the sheet-like material before the light resistance test in the Martindale wear test 20,000 times defined by JIS L 1096: 2010 is 20 mg or less.

According to a preferred embodiment of the sheet-like material of the present invention, the polymer elastic body is contained in an amount of 10% by mass or more.

According to a preferred embodiment of the sheet-like material of the present invention, the sheet-like material further satisfies the following condition 3.
Condition 3: The retention rate of the L value when the raised surface of the sheet-like material is placed on a hot plate heated to 150 ° C. and pressed for 10 seconds with a pressing load of 2.5 kPa is 90% or more and 100% or less. The method for producing a sheet-like material of the present invention is a method for producing a sheet-like material, which comprises the following steps (1) to (4) in this order.
(1) A fibrous base material made of ultrafine fiber-expressing fibers is impregnated with an aqueous dispersion containing a polymer elastic body, a monovalent cation-containing inorganic salt, and a cross-linking agent, and then at 120 ° C. or higher and 180 ° C. or lower. A polymer elastic body impregnation step in which heat treatment is performed at a temperature, wherein the polymer elastic body has a hydrophilic group, contains polyetherdiol as a constituent component, and contains monovalent cations in the aqueous dispersion. Polymer elastic body impregnation step in which the content of the inorganic salt is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer elastic body (2) The ultrafine fiber-expressing type fiber is alkali-treated to be an ultrafine fiber. (3) Heat treatment at a temperature of 120 ° C. or higher and 180 ° C. or lower, drying step (4) Raising at least one surface of the unraised sheet-like material to form naps on the surface. Step According to a preferred embodiment of the method for producing a sheet-like material of the present invention, a dyeing step of dyeing an unbrushed sheet-like material or a sheet-like material after the drying step is included.

According to a preferred embodiment of the method for producing a sheet-like product of the present invention, the monovalent cation-containing inorganic salt is sodium chloride and / or sodium sulfate.

According to a preferred embodiment of the method for producing a sheet-like product of the present invention, the cross-linking agent is a carbodiimide-based cross-linking agent.

According to the present invention, a sheet-like material having both a flexible texture and excellent light resistance can be obtained.

The sheet-like material of the present invention is a sheet-like material containing a polymer elastic body in a fibrous base material, and the fibrous base material is composed of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less, and is a polymer. The elastic body has a hydrophilic group, contains a polyether diol as a constituent component, has an N-acylurea bond and / or an isourea bond inside the polymer elastic body, and satisfies the following conditions 1 and 2. It is a sheet-like material.
Condition 1: The rigidity in the vertical direction defined by the method A (45 ° cantilever method) described in JIS L 1096: 2010 “Fabric test method for woven fabrics and knitted fabrics” is 40 mm or more and 140 mm or less.
Condition 2: JIS L 0843: 2006 The xenon arc amount of the light fastness measurement method is 110 MJ / m. The wear loss in the Martindale wear test 20,000 times specified in JIS L 1096: 2005 after the light resistance test measured under ^{2 conditions is} It is 25 mg or less.

This component will be described in detail below, but the present invention is not limited to the scope described below as long as the gist of the present invention is not exceeded.

[Ultrafine fiber]
Examples of the resin that can be used for the ultrafine fibers used in the present invention include polyester resins and polyamide resins from the viewpoints of excellent durability, particularly mechanical strength, heat resistance and light resistance. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and the like. The polyester resin can be obtained from, for example, a dicarboxylic acid and / or an ester-forming derivative thereof and a diol.

Examples of the dicarboxylic acid and / or its ester-forming derivative used in the polyester resin include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid and its ester-forming derivative. Can be mentioned. The ester-forming derivative referred to in the present invention is a lower alkyl ester of a dicarboxylic acid, an acid anhydride, an acyl chloride or the like. Specifically, methyl ester, ethyl ester, hydroxy ethyl ester and the like are preferably used. A more preferred embodiment of the dicarboxylic acid and / or ester-forming derivative thereof used in the present invention is terephthalic acid and / or a dimethyl ester thereof.

Examples of the diol used in the polyester resin include ethylene glycol, 1,3-propanediol, 1,4-butanediol, cyclohexanedimethanol and the like. Of these, ethylene glycol is preferably used.

When a polyamide-based resin is used as the resin used for the ultrafine fibers, polyamide 6, polyamide 66, polyamide 56, polyamide 610, polyamide 11, polyamide 12, copolymerized polyamide and the like can be used.

The resin used for the ultrafine fibers contains inorganic particles such as titanium oxide particles, a lubricant, a pigment, a heat stabilizer, an ultraviolet absorber, a conductive agent, a heat storage agent, an antibacterial agent, and the like, depending on various purposes. Can be done.

Further, it is preferable that the resin used for the ultrafine fiber contains a component derived from a biomass resource.

When a polyester-based resin is used as the resin used for the ultrafine fibers, the component derived from the biomass resource may be a component derived from the biomass resource as a component dicarboxylic acid or an ester-forming derivative thereof, or a diol. However, from the viewpoint of reducing the environmental load, it is preferable to use the component derived from the biomass resource for both the dicarboxylic acid or its ester-forming derivative and the diol.

When a polyamide resin is used as the resin used for the ultrafine fibers, the components derived from the biomass resource include polyamide 56, polyamide 610, and polyamide 56, polyamide 610, from the viewpoint of economically advantageous availability of a raw material derived from the biomass resource and the physical characteristics of the fiber. Polyamide 11 is preferably used.

As the cross-sectional shape of the ultrafine fiber, either a round cross section or a deformed cross section can be adopted. Specific examples of the irregular cross section include polygons such as ellipses, flats, and triangles, sectors, and crosses.

In the present invention, it is important that the average single fiber diameter of the ultrafine fibers is 0.1 μm or more and 10 μm or less. When the average single fiber diameter of the ultrafine fibers is 10 μm or less, preferably 7 μm or less, more preferably 5 μm or less, the sheet-like material can be made more flexible. In addition, the quality of standing hair can be improved. On the other hand, when the average single fiber diameter of the ultrafine fibers is 0.1 μm or more, preferably 0.3 μm or more, more preferably 0.7 μm or more, a sheet-like material having excellent color development after dyeing is performed. Can be. Further, when the raising treatment by buffing is performed, it is possible to improve the ease of dispersing and the ease of handling of the ultrafine fibers existing in a bundle.

The average single fiber diameter referred to in the present invention is measured by the following method. That is,
(1) The cross section of the sheet-like material cut in the thickness direction is observed with a scanning electron microscope (SEM).
(2) The fiber diameters of any 50 ultrafine fibers in the observation surface are measured in three directions in each ultrafine fiber cross section. However, when ultrafine fibers having a modified cross section are used, the cross-sectional area of the single fiber is first measured, and the diameter of the circle having the cross-sectional area is calculated by the following formula. The diameter obtained from this is taken as the single fiber diameter of the single fiber.
-Single fiber diameter (μm) = (4 x (single fiber cross-sectional area (μm ² )) / π) ^1/2
(3) Calculate the arithmetic mean value (μm) of the total of 150 points obtained, and round off to the second decimal place.

[Fibrous base material]
The fibrous base material used in the present invention comprises the ultrafine fibers. It is permissible for the fibrous base material to be a mixture of ultrafine fibers made of different raw materials.

As a specific form of the fibrous base material, a non-woven fabric formed by entwining each of the ultrafine fibers or a non-woven fabric formed by entwining fiber bundles of ultrafine fibers can be used. Among them, a non-woven fabric formed by entwining fiber bundles of ultrafine fibers is preferably used from the viewpoint of strength and texture of a sheet-like material. From the viewpoint of flexibility and texture, a non-woven fabric in which the ultrafine fibers constituting the fiber bundle of the ultrafine fibers are appropriately separated from each other and has voids is preferably used. As described above, the non-woven fabric in which the fiber bundles of the ultrafine fibers are entangled can be obtained, for example, by entwining the ultrafine fiber-expressing fibers in advance and then expressing the ultrafine fibers. Further, the non-woven fabric in which the ultrafine fibers constituting the fiber bundle of the ultrafine fibers are appropriately separated from each other and have voids is, for example, a sea-island type composite fiber capable of forming voids between the island components by removing the sea component. It can be obtained by using it.

The non-woven fabric may be either a short-fiber non-woven fabric or a long-fiber non-woven fabric, but the short-fiber non-woven fabric is more preferably used from the viewpoint of the texture and quality of the sheet-like material.

When a short fiber non-woven fabric is used, the fiber length of the short fiber is preferably in the range of 25 mm or more and 90 mm or less. By setting the fiber length to 25 mm or more, more preferably 35 mm or more, still more preferably 40 mm or more, it becomes easy to obtain a sheet-like material having excellent wear resistance due to entanglement. Further, by setting the fiber length to 90 mm or less, more preferably 80 mm or less, still more preferably 70 mm or less, a sheet-like material having more excellent texture and quality can be obtained.

In the present invention, when a non-woven fabric is used as the fibrous base material, the non-woven fabric or knitted fabric can be inserted, laminated, or lined inside the non-woven fabric for the purpose of improving the strength. The average single fiber diameter of the fibers constituting such a woven fabric or knitted fabric is more preferably 0.3 μm or more and 10 μm or less because damage at the time of needle punching can be suppressed and strength can be maintained.

The fibers constituting the woven fabric or knitted fabric include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid, synthetic fibers such as polyamides such as 6-nylon and 66-nylon, and cellulose-based polymers. Recycled fibers, natural fibers such as cotton and linen can be used.

[Polymer elastic body]
In the sheet-like material of the present invention, examples of the polymer elastic body include an aqueous dispersion type silicone resin, an aqueous dispersion type acrylic resin, an aqueous dispersion type urethane resin, and a copolymer thereof. Among them, a water-dispersible polyurethane resin is preferably used from the viewpoint of texture.

As the water-dispersible polyurethane resin, a resin obtained by reacting a polymer polyol having a number average molecular weight of preferably 500 or more and 5,000 or less, an organic polyisocyanate, and a chain extender is preferably used. Further, in order to improve the stability of the water-dispersed polyurethane dispersion, it is preferable to use a hydrophilic group-containing active hydrogen component in combination. By setting the number average molecular weight of the polymer polyol to 500 or more, more preferably 1,500 or more, it is possible to easily prevent the texture from becoming hard. Further, by setting the number average molecular weight to 5,000 or less, more preferably 4,000 or less, it is possible to easily maintain the strength of polyurethane as a binder. The case where a water-dispersible polyurethane resin is used as the polymer elastic body will be described below.

(1) Each reaction component of the water-dispersible polyurethane resin First, each reaction component of the water-dispersible polyurethane resin will be described.

(1-1) Polymer Polyol In the sheet-like material of the present invention, the polymer elastic body contains a polyether diol as a constituent component. The content of the polyether diol in the polymer polyol is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more of the total polymer polyol. Specific examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like, and copolymerized polyether diols in combination thereof. In addition, in this specification, "included as a constituent component" means that it is contained as a monomer component and an oligomer component constituting a polymer elastic body. Since the degree of freedom of the ether bond of the polyether diol is high, the glass transition temperature is low and the cohesive force is weak, so that polyurethane having excellent flexibility can be easily obtained.

(1-2) Organic diisocyanates The organic diisocyanates used in the present invention include aromatic diisocyanates having 6 or more and 20 or less carbon atoms (excluding carbons in NCO groups, the same applies hereinafter) and 2 or more and 18 or less carbon atoms. Aliphatic diisocyanates, alicyclic diisocyanates having 4 to 15 carbon atoms, aromatic aliphatic diisocyanates having 8 to 15 carbon atoms, modified products of these diisocyanates (carbodiimide modified products, urethane modified products, uretdione modified products, etc.). ) And a mixture of two or more of these.

Specific examples of the aromatic diisocyanate having 6 or more and 20 or less carbon atoms include 1,3- and / or 1,4-phenylenediocyanate, 2,4- and / 2,6-tolylene diisocyanate, and 2,4'. -And / or 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'- Examples thereof include dimethyl-4,4'-diisocyanatodiphenylmethane, and 1,5-naphthylene diisocyanate.

Specific examples of the aliphatic diisocyanate having 2 or more and 18 or less carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6. -Diisocyanatomethyl caproate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexaate and the like.

Specific examples of the alicyclic diisocyanate having 4 or more and 15 or less carbon atoms include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanatoethyl)-. Included are 4-cyclohexylene-1,2-dicarboxylate, and 2,5- and / or 2,6-norbornane diisocyanate.

Specific examples of the aromatic aliphatic diisocyanate having 8 or more and 15 or less carbon atoms include m- and / or p-xylylene diisocyanate, α, α, α', and α'-tetramethylxylylene diisocyanate. ..

Of these, the preferred organic diisocyanate is an alicyclic diisocyanate. A particularly preferable organic diisocyanate is dicyclohexylmethane-4,4'-diisocyanate.

(1-3) Chain extender Examples of the chain extender used in the present invention include water, "ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, and diethylene glycol." And neopentyl glycol, etc., low molecular weight diols, 1,4-bis (hydroxymethyl) cyclohexane, etc., alicyclic diols, 1,4-bis (hydroxyethyl) benzene, etc., aromatic diols, ethylenediamine, etc. Aliphatic diamines such as "isofolone diamines", alicyclic diamines such as "isophorone diamines", aromatic diamines "4,4-diaminodiphenylmethane", aromatic aliphatic diamines "xylene diamines", alkanols "ethanolamine etc." Examples include amines, hydrazines, dihydrazides such as "dihydrazide adipate", and mixtures of two or more of these.

Of these, preferred chain extenders are water, low molecular weight diols, aromatic diamines, more preferably water, ethylene glycol, 1,4-butanediol, 4,4'-diaminodiphenylmethane and two or more of these. Examples include mixtures.

(2) Additives for water-dispersed polyurethane resin In the present invention, it is important to add a monovalent cation-containing inorganic salt to a solution containing water-dispersed polyurethane for the reason described later. In addition, if necessary, colorants such as titanium oxide, UV absorbers (benzophenone-based, benzotriazole-based, etc.) and antioxidants [4,5-butylidene-bis (3-methyl-6-1-butylphenol), etc. Dophenol; organic phosphite such as triphenyl phosphite, trichloroethyl phosphite, etc.] and other stabilizers, inorganic fillers (calcium carbonate, etc.) and the like can be contained.

(3) Composition of Water-Dispersible Polyurethane Resin In the water-dispersible polyurethane used in the present invention, examples of the component that causes the polyurethane to contain a hydrophilic group include a hydrophilic group-containing active hydrogen component. Examples of the hydrophilic group-containing active hydrogen component include compounds containing a nonionic group and / or an anionic group and / or a cationic group and active hydrogen.

The compound having a nonionic group and active hydrogen contains two or more active hydrogen components or two or more isocyanate groups, and has a polyoxyethylene glycol group having a molecular weight of 250 to 9,000 in the side chain. Examples thereof include compounds and triols such as trimethylolpropane and trimethylolbutane.

Examples of the compound having an anionic group and active hydrogen include carboxyl group-containing compounds such as 2,2-dimethylol propionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylol valerate and their derivatives, and 1 , 3-Phenylenediamine-4,6-disulfonic acid, 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and other compounds containing sulfonic acid groups and their derivatives, and neutralizing these compounds. Examples include salts neutralized with an agent.

Examples of the compound containing a cationic group and active hydrogen include a tertiary amino group-containing compound such as 3-dimethylaminopropanol, N-methyldiethanolamine, and N-propyldiethanolamine, and derivatives thereof.

The hydrophilic group-containing active hydrogen component can also be used in the state of a salt neutralized with a neutralizing agent.

The hydrophilic group-containing active hydrogen component used in the polyurethane molecule is 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and from the viewpoint of mechanical strength and dispersion stability of the water-dispersed polyurethane resin. It is preferable to use these neutralizing salts.

In the present invention, the hydrophilic group in the polymer elastic body is a group having active hydrogen. Specific examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group and the like.

In the present invention, the polymer elastic body has an N-acylurea bond and / or an isourea bond. Here, having an N-acylurea bond and / or an isourea bond inside the polymer elastic body means that the polymer elastic body has an N-acylurea bond and / or an isourea bond. When an aqueous dispersion type polyurethane resin is used as the polymer elastic body, the N-acylurea bond and / or isourea bond is, for example, a carbodiimide-based crosslink with a hydroxyl group and / or a carboxyl group existing as the above-mentioned hydrophilic group-containing active hydrogen component. It can be formed by reacting with an agent. As a result, a three-dimensional crosslinked structure by N-acylurea bond and / or isourea bond, which is excellent in physical properties such as light resistance, heat resistance, and abrasion resistance, and / or isourea bond, is imparted into the molecule of the polymer elastic body, and the sheet-like material is formed. It is possible to dramatically improve physical properties such as wear resistance while maintaining the flexibility of the above.

The presence of the above N-acylurea group and isourea group in the polymer elastic body means that the cross section of the sheet-like material is mapped by, for example, time-of-flight secondary ion mass spectrometry (TOF-SIMS analysis). Processing (for example, "TOF.SIMS 5" manufactured by ION-TOF as an analytical instrument) and infrared spectroscopic analysis (for example, "FT / IR 4000 series" manufactured by Nippon Spectroscopy Co., Ltd. as an analytical instrument) It can be analyzed if done.

The number average molecular weight of the polymer elastic body used in the present invention is preferably 20,000 or more from the viewpoint of resin strength, and preferably 500,000 or less from the viewpoint of viscosity stability and workability. .. The number average molecular weight is more preferably 30,000 or more and 150,000 or less.

The number average molecular weight of the polymer elastic body can be determined by gel permeation chromatography, and is measured, for example, under the following conditions.
・ Equipment: HLC-8220 manufactured by Tosoh Corporation
-Column: Tosoh TSKgel α-M
-Solvent: N, N-dimethylformamide (DMF)
・ Temperature: 40 ℃
-Calibration: Polystyrene The polymer elastic material used in the present invention appropriately grips fibers in a sheet-like material, and preferably is a fibrous base material from the viewpoint of having fluff on at least one side of the sheet-like material. It is a preferred embodiment that it exists inside.

[Sheet-like material]
The sheet-like material of the present invention has a longitudinal rigidity of 40 mm or more and 140 mm or less specified by the method A (45 ° cantilever method) described in JIS L 1096: 2010 “Fabric test method for woven fabrics and knitted fabrics”. It is important to be. By setting the rigidity and softness in the above range, it is possible to have appropriate flexibility and resilience. The rigidity is preferably 50 mm or more, more preferably 55 mm or more from the viewpoint of obtaining a repulsive sheet-like material, and preferably 120 mm or less from the viewpoint of obtaining a flexible sheet-like material. , More preferably 110 mm or less.

The vertical direction in the sheet-like material of the present invention means the direction in which the sheet-like material is brushed. As a method of searching for the direction in which the brushing treatment is performed, it can be appropriately adopted depending on the constituent components of the sheet-like material such as visual confirmation when tracing with a finger and SEM photography. That is, when traced with a finger, the direction in which the fluffy fibers can be laid down or erected is the vertical direction. Further, by SEM-imaging the surface of the sheet-like object traced with a finger, the direction in which the lying nap fibers are most oriented becomes the vertical direction. On the other hand, the horizontal direction in the sheet-like object of the present invention is the direction perpendicular to the vertical direction as the horizontal direction.

Further, the sheet-like material of the present invention is a Martindale wear test specified by JIS L 1096: 2005 after the light resistance test in which the xenon arc amount of the JIS L 0843: 2006 light fastness measurement method is measured under the ^{condition of 110 MJ / m 2.} It is important that the wear loss at 20,000 times is 25 mg or less. By setting the wear weight loss after the light resistance test within the above range, deterioration of the polymer elastic body can be suppressed even when used for a long period of time in a harsh environment exposed to sunlight, and the appearance of the sheet-like material can be maintained. Can be done. The wear weight loss is preferably 23 mg or less, and more preferably 20 mg or less, from the viewpoint of suppressing deterioration of the appearance of the sheet-like material.

The sheet-like material of the present invention preferably has a wear weight loss of 20 mg or less in the Martindale wear test 20,000 times specified in JIS L 1096: 2010 in the sheet-like material before the light resistance test. By setting the wear weight loss before the light resistance test within the above range, it becomes easy to suppress fluffing and deterioration of the appearance in actual use. The wear weight loss is preferably 18 mg or less, more preferably 15 mg or less, from the viewpoint of further suppressing fluffing in actual use.

The sheet-like material of the present invention preferably contains a polymer elastic body in an amount of 10% by mass or more. From the viewpoint of suppressing breakage due to tension in the manufacturing process and fluffing in actual use, the content is more preferably 12% by mass or more, and further preferably 15% by mass or more. The upper limit of the content is not particularly limited, but is usually 50% by mass or less, preferably 40% by mass or less, and more preferably 35% by mass or less.

It is preferable that the sheet-like material of the present invention further satisfies the following condition 3.
Condition 3: The L value retention rate when the raised surface of the sheet-like material is placed on a hot plate heated to 150 ° C. and pressed for 10 seconds with a pressing load of 2.5 kPa (hereinafter, simply abbreviated as L value retention rate). Is 90% or more and 100% or less.

Among them, when the L value retention rate is 90% or more, more preferably 92% or more, still more preferably 95% or more, the sheet-like material has high heat resistance.

In the present invention, the "brushed surface of the sheet-like material" refers to the surface of the sheet-like material that has been brushed. The L value is an L value defined by the Commission International on Illumination (CIE), but the L value retention rate in the present invention is a change in brightness under heating / pressing conditions. Is a small ratio, that is, it is an index indicating how much a sheet-like material having a dark color before heating / pressing does not become bright after heating / pressing.

In the present invention, the L value retention rate refers to a value measured and calculated by the procedure as follows.
(1) The sheet-like material is cut, and the L value of the cut test piece is measured using a color difference meter (for example, "CR-410" manufactured by Konica Minolta Co., Ltd.).
(2) The test piece is placed on a hot plate heated to 150 ° C. (for example, "CHP-250DN" manufactured by AS ONE Corporation) with the raised surface of the test piece facing down.
(3) An indenter adjusted so that the pressing load is 2.5 kPa is placed on the test piece and held for 10 seconds.
(4) Remove the indenter on the test piece, and measure the L value of the raised surface of the test piece with the above-mentioned color difference meter.
(5) The L value retention rate is calculated from the following formula.

L value retention rate (%) = (L value measured in (1)) / (L value measured in (4)) × 100
In order to keep the abrasion weight loss and the L value retention rate within the above ranges before the rigidity and light resistance test and after the light resistance test, for example, a polymer elastic body impregnation step, an ultrafine fiber expression step, and a drying step described later are performed. It is possible to manufacture a sheet-like product through the process. By impregnating the polymer elastic body and then passing through the process of expressing the ultrafine fibers, it can be formed in the gap between the ultrafine fibers and the polymer elastic body, and a flexible texture can be easily obtained. Further, for example, in the drying step, heat treatment (cure treatment) is performed at a temperature of 120 ° C. or higher and 180 ° C. or lower to agglomerate the particles of the polymer elastic body, and it is easy to improve light resistance, abrasion resistance, and heat resistance. Can be done. Further, by setting the heat-sensitive coagulation temperature of the aqueous dispersion in the range described later, uneven distribution (migration) of polyurethane on the surface of the sheet-like material due to water evaporation can be suppressed, and the L value retention rate can be increased.

[Manufacturing method of sheet-like material]
Next, the method for producing the sheet-like material of the present invention will be described.

The method for producing a sheet-like product of the present invention includes the following steps (1) to (4) in this order.
(1) A fibrous base material made of ultrafine fiber-expressing fibers is impregnated with an aqueous dispersion containing a polymer elastic body, a monovalent cation-containing inorganic salt, and a cross-linking agent, and then at 120 ° C. or higher and 180 ° C. or lower. A polymer elastic body impregnation step in which heat treatment is performed at a temperature, wherein the polymer elastic body has a hydrophilic group, contains a polyether diol as a constituent component, and contains monovalent cations in the aqueous dispersion. Polymer elastic body impregnation step in which the content of the inorganic salt is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer elastic body (2) The ultrafine fiber-expressing fiber is alkali-treated and the ultrafine fiber is treated. (3) Heat treatment at a temperature of 120 ° C. or higher and 180 ° C. or lower, drying step (4) Raising at least one surface of the unraised sheet-like material to form naps on the surface. Process.

In the present invention, the "unraised sheet-like material" refers to a sheet-like material before the raising treatment obtained by a method including at least the above steps (1) to (3) in this order.

In the present invention, as a means for obtaining ultrafine fibers, it is a preferable embodiment to use ultrafine fiber-expressing fibers. By entwining the ultrafine fiber-expressing fibers in advance to form a non-woven fabric and then ultrafine the fibers, a non-woven fabric in which the ultrafine fiber bundles are entangled can be obtained.

As the ultrafine fiber-expressing fiber, a thermoplastic resin having two components (two or three components when the island fiber is a core-sheath composite fiber) having different solvent solubility is used as a sea component and an island component, and the above sea component is used as a solvent. By using a sea-island type composite fiber in which the island component is an ultrafine fiber by dissolving and removing the sea component, an appropriate void is provided between the island components, that is, between the ultrafine fibers inside the fiber bundle when the sea component is removed. Therefore, it is preferable from the viewpoint of the texture and surface quality of the sheet-like material.

As the sea-island type composite fiber, a polymer mutual arrangement in which two components of the sea component and the island component (three components when the island fiber is a core-sheath composite fiber) are reciprocally arranged and spun using a sea-island type composite base is used. The method used is preferable from the viewpoint of obtaining ultrafine fibers having a uniform single fiber diameter.

As the sea component of the sea-island type composite fiber, polyethylene, polypropylene, polystyrene, copolymerized polyester obtained by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, etc., polylactic acid, etc. can be used. From this point of view, polystyrene and copolymerized polyester are preferably used.

It is preferable that the sea component is dissolved and removed after the polymer elastic body is applied. As will be described later.

The mass ratio of the sea component to the island component in the sea-island type composite fiber used in the present invention is preferably in the range of sea component: island component = 10:90 to 80:20. When the mass ratio of the sea component is 10% by mass or more, the island component is likely to be sufficiently refined. Further, when the mass ratio of the sea component is 80 mass or less, the ratio of the eluted component is small, so that the productivity is improved. The mass ratio of the sea component and the island component is more preferably in the range of sea component: island component = 20:80 to 70:30.

Further, the fiber entanglement preferably takes the form of a non-woven fabric, and as described above, either a short-fiber non-woven fabric or a long-fiber non-woven fabric can be used, but the short-fiber non-woven fabric faces the thickness direction of the fibrous base material. This is preferable because the number of fibers is larger than that of the long-fiber non-woven fabric, and a high degree of denseness can be obtained on the surface of the fibrous base material when raised.

When a short fiber non-woven fabric is used as the fiber entanglement, the obtained ultrafine fiber phenotype fiber is preferably crimped and cut to a predetermined length to obtain raw cotton. A known method can be used for the crimping process and the cutting process.

Next, the obtained raw cotton is made into a fiber web by a cloth wrapper or the like, and entangled to obtain a short fiber non-woven fabric. As a method of entwining the fiber webs to obtain a short fiber non-woven fabric, a needle punching process, a water jet punching process, or the like can be used.

Furthermore, the obtained short fiber non-woven fabric and woven fabric are laminated and entangled and integrated. To entangle and integrate the short-fiber non-woven fabric and the woven fabric, the woven fabric is laminated on one or both sides of the short-fiber non-woven fabric, or the woven fabric is sandwiched between multiple short-fiber non-woven fabric webs, and then needle punching or water jet is performed. The short fiber non-woven fabric and the fibers of the woven fabric can be entangled with each other by punching or the like.

Apparent density of the short-fiber nonwoven fabric composed of the composite fiber after needle punching or water jet punching (microfine fiber phenotype fibers) is preferably 0.15 g / cm ³ or more 0.45 g / cm ³ or less. By setting the apparent density to preferably 0.15 g / cm ³ or more, the fibrous substrate can obtain sufficient morphological stability and dimensional stability. On the other hand, by setting the apparent density to preferably 0.45 g / cm ³ or less, it is possible to maintain a sufficient space for imparting the polymer elastic body.

From the viewpoint of densification, the non-woven fabric thus obtained is preferably shrunk by dry heat, moist heat, or both to further increase the density. In addition, the non-woven fabric can be compressed in the thickness direction by calendar processing or the like.

In the method for producing a sheet-like product of the present invention, (1) an aqueous dispersion containing a polymer elastic body, a monovalent cation-containing inorganic salt, and a cross-linking agent is applied to a fibrous base material made of ultrafine fiber-expressing fibers. A polymer elastic body impregnation step in which impregnation is performed and then heat treatment is performed at a temperature of 120 ° C. or higher and 180 ° C. or lower, wherein the polymer elastic body has a hydrophilic group and contains a polyether diol as a constituent component. The polymer elastic body impregnation step is included in which the content of the monovalent cation-containing inorganic salt in the aqueous dispersion is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer elastic body.

In the method for producing a sheet-like product of the present invention, a polymer elastic body having a hydrophilic group and containing a polyether diol as a constituent component is imparted to a fibrous base material. When a non-woven fabric is used as the fibrous base material, the polymer elastic body can be applied to either the non-woven fabric made of composite fibers or the non-woven fabric made into ultrafine fibers.

In the method for producing a sheet-like product of the present invention, the polymer elastic body contains a polyether diol as a constituent component. The reason is as described in the above-mentioned item (1-1) Polymer polyol.

In the method for producing a sheet-like product of the present invention, a dry heat solidification method is used in which heat treatment is performed at a temperature of 120 ° C. or higher and 180 ° C. or lower for solidification after the polymer elastic body is applied. In another coagulation method, for example, a hot water coagulation method in which a polymer elastic body is coagulated in hot water, the polymer elastic body diffuses in hot water and partly falls off, so that there is a concern about workability. Further, in the acid coagulation method in which the polymer elastic body is coagulated with an acid, it is necessary to neutralize the acidic solution remaining in the sheet, which is not preferable in terms of processing operability. On the other hand, the dry heat coagulation method applied in the present invention is a very simple method of heat-treating a sheet impregnated with a polymer elastic body with a hot air dryer or the like, and there is no concern that the polymer elastic body may fall off. , It is a method with excellent workability.

In the method for producing a sheet-like product of the present invention, the heating temperature in dry heat coagulation is 120 ° C. or higher and 180 ° C. or lower. It is more preferable that the heating temperature is 140 ° C. or higher. This is because the polymer elastic body can be rapidly solidified and the uneven distribution of the polymer elastic body on the lower surface of the sheet due to its own weight can be suppressed. Further, although it is necessary to use it in combination with a cross-linking agent in the present invention, the above-mentioned temperature is used to sufficiently promote the cross-linking reaction, form a three-dimensional network structure, and improve physical properties, light resistance, and heat resistance. Can be done. More preferably, the heating temperature is 175 ° C. or lower. This is because the thermal deterioration of the polymer elastic body can be suppressed.

The concentration of the polymer elastic body in the aqueous dispersion (content of the polymer elastic in 100% by mass of the aqueous dispersion) is 10% by mass or more and 50% by mass or less from the viewpoint of storage stability of the aqueous dispersion. It is preferable, more preferably 15% by mass or more and 40% by mass or less.

The aqueous dispersion used in the present invention may contain a water-soluble organic solvent in an amount of 40% by mass or less in 100% by mass of the aqueous dispersion in order to improve storage stability and film-forming property. From the viewpoint of maintenance and the like, the content of the organic solvent is preferably 1% by mass or less.

In the method for producing a sheet-like product of the present invention, a monovalent cation-containing inorganic salt is contained in the aqueous dispersion. By containing a monovalent cation-containing inorganic salt, it is possible to impart heat-sensitive coagulation to the aqueous dispersion. In the present invention, the heat-sensitive coagulation property refers to the property that when the aqueous dispersion is heated, the fluidity of the aqueous dispersion decreases and solidifies when a certain temperature (heat-sensitive coagulation temperature) is reached.

In the method for producing a sheet-like material of the present invention, an aqueous dispersion is applied to a fibrous substrate, then heat-treated at a temperature of 120 ° C. or higher and 180 ° C. or lower to dry heat coagulate, thereby increasing the content of the fibrous substrate. Gives a molecular elastic body.

If the polymer elastic body does not have thermal coagulation properties, migration occurs in which the polymer elastic body migrates to the sheet surface as the water evaporates. Further, since the solidification proceeds in a state where the polymer elastic body is unevenly distributed around the fiber as the water evaporates, the polymer elastic body covers the circumference of the fiber, and the structure is such that the movement is strongly restrained. As a result, the texture of the sheet-like material is remarkably hardened.

The heat-sensitive coagulation temperature of the aqueous dispersion is preferably 55 ° C. or higher and 80 ° C. or lower. The heat-sensitive temperature is more preferably 60 ° C. or higher because the stability of the aqueous dispersion during storage is improved and the adhesion of the polymer elastic body to the machine during operation can be suppressed. It is possible to suppress the migration phenomenon of the polymer elastic body to the surface layer of the fibrous base material, and further, the solidification of the polymer elastic body proceeds before the water evaporates from the fibrous base material, so that the solvent-based polymer elasticity Since it is possible to form a structure similar to that obtained by wet-coagulating the body, that is, a structure in which the polymer elastic body strongly does not restrain the fibers, and it is possible to achieve good flexibility and a feeling of repulsion. It is more preferable that the heat-sensitive solidification temperature is 70 ° C. or lower.

In the present invention, it is important to use a monovalent cation-containing inorganic salt as the inorganic salt used as the heat-sensitive coagulant. The monovalent cation-containing inorganic salt is preferably sodium chloride and / or sodium sulfate. In the conventional method, inorganic salts having divalent cations such as magnesium sulfate and calcium chloride have been preferably used as the heat-sensitive coagulant, but these inorganic salts can improve the stability of the aqueous dispersion even when added in a small amount. Since it has a large effect, it is difficult to strictly control the heat-sensitive gelation temperature by adjusting the amount of the polymer elastic material added, and there are problems such as concerns about gelation during preparation and storage of the aqueous dispersion. there were. On the other hand, the monovalent cation-containing inorganic salt having a small ionic valence has a small effect on the stability of the aqueous dispersion, and heat-sensing while ensuring the stability of the aqueous dispersion by adjusting the addition amount. The solidification temperature can be strictly controlled.

Further, in the present invention, it is important that the content of the monovalent cation-containing inorganic salt in the aqueous dispersion is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer elastic body. By setting the content to 10 parts by mass or more, a large amount of ions present in the aqueous dispersion act uniformly on the polymer elastic particles, so that coagulation can be completed quickly at a specific heat-sensitive coagulation temperature. Can be done. As a result, a more remarkable effect can be obtained in advancing the coagulation of the polymer elastic body in a state where the fibrous base material contains a large amount of water as described above. As a result, it is possible to form a structure very similar to that obtained by wet-solidifying a solvent-based polymer elastic body, and to achieve good flexibility and a feeling of repulsion. Further, by setting the addition amount as described above, the inorganic salt acts as an inhibitor in the fusion of the polymer elastic particles, and the curing of the polymer elastic body due to the formation of a continuous film can be suppressed. On the other hand, when the content is 50 parts by mass or less, an appropriate continuous coating structure of the polymer elastic body can be left, and deterioration of physical properties can be suppressed. In addition, the stability of the aqueous dispersion can be maintained.

In the method for producing a sheet-like product of the present invention, it is important that the aqueous dispersion contains a cross-linking agent. By introducing a three-dimensional network structure into the polymer elastic body with a cross-linking agent, physical properties such as wear resistance can be improved. Furthermore, by using in combination with the above-mentioned monovalent cation-containing inorganic salt, the coagulation of the polymer elastic body and the reaction between the polymer elastic body and the cross-linking agent proceed simultaneously, thereby forming a dense three-dimensional network structure and forming a fiber. At the same time as making the sheet-like material flexible by controlling the adhesive structure, it is possible to achieve high physical properties, high light resistance, and high heat resistance of the sheet-like material. That is, in order to improve the physical characteristics, light resistance, and heat resistance of the sheet-like material, it is indispensable to use a monovalent cation-containing inorganic salt, a cross-linking agent, and control of the heating temperature in dry heat coagulation together.

Since the polymer elastic body obtained after the reaction has excellent light resistance, heat resistance, and abrasion resistance, and also has good flexibility, it is preferable that the cross-linking agent is a carbodiimide-based cross-linking agent.

The method for producing a sheet-like product of the present invention includes (2) an ultrafine fiber expression step of treating ultrafine fiber-expressing fibers with an alkali to express the ultrafine fibers. By performing the alkali treatment after applying the polymer elastic body, voids due to the components dissolved by the alkali treatment are generated between the polymer elastic body and the ultrafine fibers, so that the polymer elastic body can directly grip the ultrafine fibers. The texture of the sheet-like material becomes more flexible without it.

When a sea-island type composite fiber is used as the ultra-fine fiber-expressing type fiber, the fiber ultrafine treatment (desealing treatment) can be performed, for example, by immersing the sea-island type composite fiber in a solvent and squeezing the liquid. As the solvent for dissolving the sea component, an alkaline aqueous solution such as sodium hydroxide or hot water can be used.

In the ultrafine fiber expression step, devices such as a continuous dyeing machine, a vibro washer type dewatering machine, a liquid flow dyeing machine, a Wins dyeing machine and a Jigger dyeing machine can be used.

After the ultrafine fiber expression step, it is preferable to perform a sufficient washing step after the alkali treatment. By going through the cleaning process, it is possible to process the sheet without leaving alkali or monovalent cation-containing inorganic salt adhering to the sheet on the sheet, and it can be processed without affecting the production equipment. It is preferable to use water as the cleaning liquid in consideration of the environment and safety.

The method for producing a sheet-like product of the present invention includes (3) a drying step of performing heat treatment at a temperature of 120 ° C. or higher and 180 ° C. or lower. During the process of expressing ultrafine fibers, the bonds of the polymer elastic body are partially decomposed by the solvent that dissolves the components other than the ultrafine fibers in the ultrafine fiber expression type fiber. Therefore, the polymer elastic body is cured by drying. It is possible to further improve physical properties such as light resistance, abrasion resistance, and heat resistance by aggregating the particles of the above.

In the method for producing a sheet-like product of the present invention, the heating temperature in the curing treatment by drying is 120 ° C. or higher and 180 ° C. or lower. The temperature is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, in order to enhance the effect of the cure treatment and to improve the physical properties such as light resistance, abrasion resistance, and heat resistance. In order to suppress thermal deterioration of the polymer elastic body, the temperature is preferably 175 ° C. or lower, more preferably 170 ° C. or lower.

The method for producing a sheet-like material of the present invention preferably includes a dyeing step of dyeing the unbrushed sheet-like material or the sheet-like material after the drying step. As this dyeing treatment, various methods usually used in the art can be adopted, for example, a liquid flow dyeing treatment using a jigger dyeing machine or a liquid flow dyeing machine, a thermosol dyeing treatment using a continuous dyeing machine, and the like. Dyeing treatment, roller printing, screen printing, inkjet printing, sublimation printing, vacuum sublimation printing, or the like can be used. Above all, it is preferable to use a liquid flow dyeing machine because it is possible to soften the unbrushed sheet-like material or the sheet-like material by giving a kneading effect at the same time as dyeing the unbrushed sheet-like material or the sheet-like material. Further, if necessary, various resin finishing processes can be applied after dyeing.

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

The dye used in the present invention may be selected according to the type of fiber constituting the fibrous base material and is not particularly limited. For example, if it is a polyester fiber, a disperse dye can be used, and a polyamide fiber can be used. If so, acid dyes and gold-containing dyes can be used, and combinations thereof can be used. When dyed with a disperse dye, reduction cleaning may be performed after dyeing.

It is also a preferable aspect to use a dyeing aid at the time of dyeing. By using a dyeing aid, the uniformity and reproducibility of dyeing can be improved. In addition, a finishing agent treatment using, for example, a softener such as silicone, an antistatic agent, a water repellent agent, a flame retardant, a light resistant agent, an antibacterial agent, or the like can be applied in the same bath as the dyeing or after the dyeing.

In the present invention, it is also a preferable aspect to cut in half in the thickness direction from the viewpoint of manufacturing efficiency regardless of before or after the dyeing step.

The method for producing a sheet-like material of the present invention includes (4) a brushing step of raising at least one surface of the unbrushed sheet-like material to form naps on the surface regardless of before and after the dyeing step. The method for forming the naps is not particularly limited, and various methods usually used in the art such as buffing with sandpaper or the like can be used. If the fluff length is too short, it is difficult to obtain an elegant appearance, and if it is too long, pilling tends to occur. Therefore, the fluff length is preferably 0.2 mm or more and 1.0 mm or less.

Further, in one aspect of the present invention, silicone or the like may be applied as a lubricant to the unbrushed sheet-like material before the raising treatment. By applying a lubricant, raising by surface grinding becomes possible easily, and the surface quality becomes very good, which is preferable. Further, an antistatic agent may be applied before the raising treatment. This is a preferable embodiment because the application of the antistatic agent makes it difficult for the grinding powder generated from the sheet-like material to be deposited on the sandpaper.

Further, in one aspect of the present invention, the surface thereof can be designed as needed. For example, post-processing such as perforation and other drilling, embossing, laser processing, pinsonic processing, and printing can be performed.

Next, the sheet-like material of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Evaluation method]
(1) Average single fiber diameter of sheet-like material:
A cross section perpendicular to the thickness direction containing the fibers of the sheet-like material was observed at 3000 times using a scanning electron microscope (SEM, VE-7800 type manufactured by KEYENCE CORPORATION), and was randomly observed within a field of view of 30 μm × 30 μm. The diameters of the 50 single fibers extracted in 1 were measured in μm units up to the first fraction.

This was done at 3 locations, the diameters of a total of 150 single fibers were measured, and the average value was calculated up to the first decimal place. When fibers having a fiber diameter of more than 50 μm are mixed, the fibers are excluded from the measurement target of the average fiber diameter because they do not correspond to ultrafine fibers. Further, when the ultrafine fiber has a deformed cross section, as described above, the diameter of the single fiber is obtained by first measuring the cross-sectional area of the single fiber and calculating the diameter when the cross section is regarded as a circle. The average value using this as the population was calculated and used as the average single fiber diameter.

(2) Coagulation temperature of the aqueous dispersion Put 20 g of the aqueous dispersion containing the polymer elastic body prepared in each Example and Comparative Example into a test tube having an inner diameter of 12 mm, and place the thermometer at the tip below the liquid surface. After inserting the test tube so as to be, the test tube was sealed and immersed in a hot water bath having a temperature of 95 ° C. so that the liquid level of the water dispersion was lower than the liquid level of the hot water bath. While checking the temperature rise in the test tube with a thermometer, pull up the test tube for a time of 5 seconds or less each time and shake it to the extent that the presence or absence of fluidity of the liquid level of the water dispersion can be confirmed. The temperature at which the liquid level of No. 1 lost its fluidity was defined as the solidification temperature. This measurement was performed three times for each type of aqueous dispersion, and the average value was calculated.

(3) Evaluation of flexibility of sheet-like material:
2 x 15 cm in the vertical direction based on the A method (45 ° cantilever method) described in 8.21.1 of 8.21 "Stiffness and softness" of JIS L 1096: 2010 "Fabric test method for woven fabrics and knitted fabrics". Create 5 test pieces, place them on a horizontal table with a slope at an angle of 45 °, slide the test pieces, read the scale when the center point of one end of the test piece touches the slope, and read the average of the 5 pieces. The value was calculated.

(4) Wear evaluation of sheet-like material Wear evaluation was performed based on JIS L 1096: 2010. As a Martindale wear tester, James H.M. Heal & Co. Model 406 manufactured by the same company was used, and the company's ABRASTIVE CLOTH SM25 was used as a standard friction cloth. A load of 12 kPa was applied to the sheet-like material before and after the light resistance test described later, and the number of times of wear was 20,000 times. Using the mass of the sheet-like material before and after wear, the wear loss was calculated by the following formula.

Wear loss (mg) = mass before wear (mg) -mass after wear (mg)
For the wear loss, the value obtained by rounding off the value at the first decimal place was taken as the wear loss.

(5) Light resistance test of sheet-like material Conditions in which the measurement time is adjusted so that ^{the xenon arc irradiation amount is 110 MJ / m 2} according to the JIS L 0843: 2006 light fastness measurement method (B method, 5th exposure method). Irradiation was performed with.

(6) Identification of Bonded Species in Polymer Elastic Body The polymer elastic body separated from the above sheet-like material was identified by infrared spectroscopic analysis using FT / IR 4000 series manufactured by Nippon Spectroscopy Co., Ltd. ..

(7) L value retention rate Using "CHP-250DN" manufactured by AS ONE Corporation as a hot plate and "CR-410" manufactured by Konica Minolta Co., Ltd. as a color difference meter, measurement and calculation were performed by the above method. ..

(8) Measurement of inorganic salt species and content contained in the sheet-like material:
The sheet was immersed in N, N-dimethylformamide overnight, and the solution in which the polymer elastic and the inorganic salt were eluted was concentrated by heating and drying at 140 ° C. and solidified. Distilled water was added to the obtained solid material to elute only the inorganic salt. After heating and drying the aqueous solution containing the inorganic salt, the amount of the inorganic salt contained in the sheet was measured. Further, the solidified polymer elastic body was also heated and dried, and the mass was measured to calculate the mass of the inorganic salt as compared with the mass of the polymer elastic body. However, from the viewpoint of the effectiveness of the numerical value, less than 0.1% by mass with respect to the polymer elastic body is less than the lower limit of detection.

The type of inorganic salt was identified by using an ion chromatograph device of "ICS-3000 type" manufactured by Dionex Co., Ltd. for the aqueous solution containing the inorganic salt.

[Manufacturing method of non-woven fabric A for fibrous base material]
Using 8 mol% copolymerized polyester of SSIA (sodium 5-sulfoisophthalate) as the sea component and polyethylene terephthalate as the island component, the number of islands is a composite ratio of 20% by mass of the sea component and 80% by mass of the island component. A sea-island type composite fiber having 16 islands / 1 filament and an average single fiber diameter of 20 μm was obtained. The obtained sea-island type composite fiber is cut into a fiber length of 51 mm to make a staple, a fiber web is formed through a curd and a cross wrapper, and a non-woven fabric having ^{a basis weight of 700 g / m 2 and a thickness of 3.0 mm is processed by needle punching.} Manufactured. The non-woven 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 non-woven fabric A for a fibrous base material.

[Manufacturing method of non-woven fabric B for fibrous base material]
Using 8 mol% copolymerized polyester of SSIA (sodium 5-sulfoisophthalate) as the sea component and polyethylene terephthalate as the island component, the number of islands is a composite ratio of 43% by mass of the sea component and 57% by mass of the island component. A sea-island type composite fiber having 16 islands / 1 filament and an average single fiber diameter of 20 μm was obtained. The obtained sea-island type composite fiber is cut into a fiber length of 51 mm to make a staple, a fiber web is formed through a curd and a cross wrapper, and a non-woven fabric having ^{a basis weight of 550 g / m 2 and a thickness of 2.9 mm is formed by needle punching.} Manufactured. The non-woven 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 non-woven fabric B for a fibrous base material.

[Manufacturing method of polymer elastic body]
Polytetramethylene ether glycol (denoted as PTMG in the table) having a number average molecular weight (Mn) of 2,000 was used as the polyol, MDI was used as the isocyanate, and 2,2-dimethylolpropionic acid was used as a component containing a hydrophilic group. Prepolymers were made in toluene solvent. Ethylene glycol and ethylenediamine were added as chain extenders, and polyoxyethylene nonylphenyl ether and water were added as external emulsifiers, and the mixture was stirred. Toluene was removed by reducing the pressure to obtain an aqueous dispersion of a polymer elastic body.

[Example 1]
(Non-woven fabric)
As the non-woven fabric, the non-woven fabric A for a fibrous base material was used.

(Giving a polymer elastic body)
To 100 parts by mass of the polymer elastic body _{, 20 parts by mass of sodium sulfate (described as "Na 2} SO ₄ " in Table 1) was added as a heat-sensitive coagulant, 3 parts by mass of a carbodiimide-based cross-linking agent was added, and the whole was added with water. The solid content was adjusted to 12% by mass, and an aqueous dispersion containing a polymer elastic body was obtained. The heat-sensitive solidification temperature was 70 ° C. The obtained non-woven fabric A for a fibrous base material is immersed in the aqueous dispersion and then dried with hot air at a temperature of 160 ° C. for 20 minutes to form a sheet-like material in 100% by mass of the sheet-like material. A non-woven fabric with a polymer elastic material having a thickness of 2.10 mm was obtained, to which the polymer elastic material was added so that the polymer elastic material was 20% by mass.

(Ultrafine fiber expression treatment)
The obtained polymer elastic-imparted non-woven fabric was immersed in an aqueous sodium hydroxide solution having a concentration of 8 g / L heated to a temperature of 95 ° C. and treated for 5 minutes to remove the sea component of the sea-island type composite fiber. Then, the aqueous sodium hydroxide solution adhering to the non-woven fabric was immersed in water, washed for 30 minutes, and dried in a dryer at 160 ° C. for 30 minutes to obtain a sheet made of ultrafine fibers (polymer elastic body-imparting sheet).

(Dyeing / finishing)
The obtained polymer elastic body-imparting sheet after desealing was cut in half perpendicular to the thickness direction, and the opposite side of the half-cut surface was ground with sandpaper count 180 endless sandpaper to obtain a thickness of 0.75 mm. A sheet-like material having fluff was obtained.

The obtained sheet-like material having fluff was dyed with a black dye using a liquid flow dyeing machine under a temperature condition of 120 ° C. Then, it was dried with a drier to obtain a sheet-like material having an average single fiber diameter of 4.4 μm. The obtained sheet-like material had a rigidity of 80 mm, a wear loss before the light resistance test of 7 mg, and a wear loss after the light resistance test of 9 mg, and had a flexible texture and excellent light resistance and wear resistance. .. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 93%, the heat resistance was excellent, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Example 2]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The thermal coagulant was changed to sodium chloride (denoted as "NaCl" in Table 1). Further, the same procedure as in Example 1 was carried out except that the amount of the heat-sensitive coagulant added, the heating temperature by hot air, and the amount of the polymer elastic body applied were changed to obtain a polymer elastic body-imparted non-woven fabric.

(Ultrafine fiber expression treatment)
The procedure was the same as in Example 1 except that the drying temperature was changed.

(Dyeing / finishing)
This was done in the same manner as in Example 1. The obtained sheet-like material had a rigidity of 90 mm, a wear loss before the light resistance test of 6 mg, and a wear loss after the light resistance test of 8 mg, and had a flexible texture and excellent light resistance and wear resistance. .. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 91%, and it had excellent heat resistance, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Example 3]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The same procedure as in Example 1 was carried out except that the amount of the heat-sensitive coagulant added, the heating temperature by hot air, and the amount of the polymer elastic body applied were changed to obtain a polymer elastic body-imparted non-woven fabric.

(Dyeing / finishing)
This was done in the same manner as in Example 1. The obtained sheet-like material had a rigidity of 55 mm, a wear loss before the light resistance test of 12 mg, and a wear loss after the light resistance test of 18 mg, and had a flexible texture and excellent light resistance and wear resistance. .. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 97%, and the polymer had excellent heat resistance, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Example 4]
(Non-woven fabric)
As the non-woven fabric, the non-woven fabric B for a fibrous base material was used.

(Giving a polymer elastic body)
The same procedure as in Example 2 was carried out except that the heating temperature by hot air and the amount of the polymer elastic body applied were changed to obtain a polymer elastic body-imparted non-woven fabric having a thickness of 2.05 mm.

(Ultrafine fiber expression treatment)
The obtained polymer elastic-imparted non-woven fabric was immersed in an aqueous sodium hydroxide solution having a concentration of 8 g / L heated to a temperature of 95 ° C. and treated for 10 minutes to remove the sea component of the sea-island type composite fiber. Then, the aqueous sodium hydroxide solution adhering to the non-woven fabric was immersed in water, washed for 30 minutes, and dried in a dryer at 170 ° C. for 30 minutes to obtain a sheet made of ultrafine fibers (polymer elastic body-imparting sheet).

(Dyeing / finishing)
The obtained polymer elastic body-imparting sheet after desealing was cut in half perpendicular to the thickness direction, and the opposite side of the half-cut surface was ground with sandpaper count 120 endless sandpaper to obtain a thickness of 0.75 mm. A sheet-like material having fluff was obtained.

The obtained sheet-like material having fluff was dyed with a black dye using a liquid flow dyeing machine under a temperature condition of 120 ° C. Then, it was dried with a drier to obtain a sheet-like material having an average single fiber diameter of 3.0 μm. The obtained sheet-like material had a rigidity of 75 mm, a wear loss before the light resistance test of 7 mg, and a wear loss after the light resistance test of 10 mg, and had a flexible texture and excellent light resistance and wear resistance. .. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 96%, and the polymer had excellent heat resistance, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Example 5]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The same procedure as in Example 1 was carried out except that the amount of the heat-sensitive coagulant and the heat-sensitive coagulant added and the amount of the polymer elastic body applied were changed to obtain a polymer elastic body-imparted non-woven fabric.

(Ultrafine fiber expression treatment)
This was done in the same manner as in Example 1.

(Dyeing / finishing)
This was done in the same manner as in Example 1. The obtained sheet-like material had a rigidity of 100 mm, a wear loss before the light resistance test of 6 mg, and a wear loss after the light resistance test of 8 mg, and had a flexible texture and excellent light resistance and wear resistance. .. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 94%, and the polymer had excellent heat resistance, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Example 6]
(Non-woven fabric)
As in Example 4, the non-woven fabric B for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The same procedure as in Example 4 was carried out to obtain a non-woven fabric with a polymer elastic body.

(Ultrafine fiber expression treatment)
This was done in the same manner as in Example 4.

(Dyeing / finishing)
The obtained polymer elastic body-imparting sheet after desealing was ground on both sides with sandpaper count 180 endless sandpaper to obtain a sheet-like material having fluff with a thickness of 1.50 mm.

The obtained sheet-like material having fluff was dyed with a black dye using a liquid flow dyeing machine under a temperature condition of 120 ° C. Then, after drying with a dryer, it was cut in half perpendicular to the thickness direction to obtain a sheet-like material having an average single fiber diameter of 3.0 μm.

The obtained sheet-like material had a rigidity of 80 mm, a wear loss before the light resistance test of 6 mg, and a wear loss after the light resistance test of 9 mg, and had a flexible texture and excellent light resistance and wear resistance. .. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 96%, and the polymer had excellent heat resistance, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 1]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
To 100 parts by mass of the polymer elastic body, 10 parts by mass of magnesium sulfate (described as "0054 ₄ " in Table 1) was added as a heat-sensitive coagulant, 3 parts by mass of a carbodiimide-based cross-linking agent was added, and the whole was solidified by water. It was adjusted to 12% by mass to obtain an aqueous dispersion containing a polymer elastic body, but gelation occurred on the surface of the non-woven fabric during processing, and the polymer elastic body could not be imparted to the non-woven fabric.

[Comparative Example 2]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The same procedure as in Example 1 was carried out except that the amount of the heat-sensitive coagulant added was changed to obtain a non-woven fabric with a polymer elastic body.

(Dyeing / finishing)
This was done in the same manner as in Example 1. Since the rigidity and softness of the obtained sheet-like material was larger than 150 mm, it could not be measured, and the texture was hard. The wear weight loss before the light resistance test was 15 mg, and the wear weight loss after the light resistance test was 25 mg. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 87%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 3]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Dyeing / finishing)
This was done in the same manner as in Example 1. Since the rigidity and softness of the obtained sheet-like material was larger than 150 mm, it could not be measured, and the texture was hard. The wear weight loss before the light resistance test was 16 mg, and the wear weight loss after the light resistance test was 28 mg, which were inferior in light resistance. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 89%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 4]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The same procedure as in Example 2 was carried out except that no cross-linking agent was applied, to obtain a non-woven fabric with a polymer elastic body.

(Ultrafine fiber expression treatment)
This was done in the same manner as in Example 2.

(Dyeing / finishing)
This was done in the same manner as in Example 1. Since the rigidity and softness of the obtained sheet-like material was larger than 150 mm, it could not be measured, and the texture was hard. The wear weight loss before the light resistance test was 21 mg, and the wear weight loss after the light resistance test was 32 mg, which were inferior in light resistance and wear resistance. In addition, the N-acylurea bond and the isourea bond did not exist inside the polymer elastic body. Further, the L value retention rate was 88%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 5]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
A non-woven fabric with a polymer elastic body was obtained in the same manner as in Example 1 except that the heating temperature was changed.

(Dyeing / finishing)
This was done in the same manner as in Example 1. The hardness and softness of the obtained sheet-like material was 120 mm, the wear loss before the light resistance test was 13 mg, and the wear loss after the light resistance test was 29 mg, and the light resistance was inferior. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 88%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 6]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The same procedure as in Example 1 was carried out to obtain a non-woven fabric with a polymer elastic body.

(Dyeing / finishing)
This was done in the same manner as in Example 1. The obtained sheet-like material had a rigidity of 130 mm, a wear loss before the light resistance test was 16 mg, and a wear loss after the light resistance test was 30 mg, and the light resistance was inferior. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 88%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 7]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
To 100 parts by mass of the polymer elastic body, 3 parts by mass of a carbodiimide-based cross-linking agent is added, and a nonionic thickener (guar gum) [“Neosoft G” manufactured by Taiyo Kagaku Co., Ltd.] is used as an active ingredient. It was added so as to be 1 part by mass with respect to 100 parts by mass, and the whole was adjusted to 13% by mass with water to obtain an aqueous dispersion containing a polymer elastic body. The obtained polymer is immersed in the aqueous dispersion, then treated in hot water at a temperature of 90 ° C. for 3 minutes, and then dried with hot air at a drying temperature of 160 ° C. for 30 minutes to form a sheet-like material 100. A polymer elastic body-imparted non-woven fabric having a thickness of 2.10 mm was obtained, in which the polymer elastic body was added so that the polymer elastic body was 20% by mass in mass%.

(Dyeing / finishing)
This was done in the same manner as in Example 1. The obtained sheet-like material had a rigidity of 90 mm, a wear loss before the light resistance test was 20 mg, and a wear loss after the light resistance test was 33 mg, and the light resistance and the wear resistance were inferior. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 87%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 8]
(Non-woven fabric)
Similar to Example 1, the non-woven fabric A for a fibrous base material was used as the non-woven fabric.

(Ultrafine fiber expression treatment)
The obtained polymer elastic-imparted non-woven fabric was immersed in an aqueous sodium hydroxide solution having a concentration of 8 g / L heated to a temperature of 95 ° C. and treated for 5 minutes to remove the sea component of the sea-island type composite fiber. Next, the aqueous sodium hydroxide solution adhering to the non-woven fabric was immersed in water, washed for 30 minutes, and dried in a dryer at 120 ° C. for 30 minutes. Then, water is added to the carbodiimide-based cross-linking agent, the sheet is impregnated with the cross-linking agent prepared to have a solid content of 2% by mass, and dried in a dryer at 160 ° C. for 30 minutes to form a sheet (polymer) made of ultrafine fibers. An elastic body imparting sheet) was obtained.

(Dyeing / finishing)
This was done in the same manner as in Example 1. Since the rigidity and softness of the obtained sheet-like material was larger than 150 mm, it could not be measured, and the texture was hard. The wear weight loss before the light resistance test was 20 mg, and the wear weight loss after the light resistance test was 30 mg, and the light resistance and the wear resistance were inferior. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 86%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

[Comparative Example 9]
(Non-woven fabric)
As in Example 4, the non-woven fabric B for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
The non-woven fabric is impregnated with a 10% by mass aqueous solution of PVA (NM-14 manufactured by Nippon Synthetic Chemical Co., Ltd.) having a degree of saponification of 99% and a degree of polymerization of 1400, and heated and dried at a temperature of 140 ° C. for 10 minutes to obtain a fibrous substrate. A PVA-imparting sheet having a PVA adhering amount of 30 parts by mass with respect to 100 parts by mass of fibers of the non-woven fabric for use was obtained.

The obtained PVA-imparting sheet was immersed in an aqueous solution of sodium hydroxide having a concentration of 8 g / L heated to a temperature of 95 ° C. and treated for 30 minutes to remove the sea component of the sea-island type composite fiber. PVA-imparted ultrafine fiber non-woven fabric) was obtained.

To 100 parts by mass of the polymer elastic body, 15 parts by mass of sodium chloride (described as "NaCl" in Table 1) was added as a heat-sensitive coagulant, 3 parts by mass of a carbodiimide-based cross-linking agent was added, and the whole was solidified by water. The mass was adjusted to a mass%, and an aqueous dispersion containing a polymer elastic body was obtained. The thermal solidification temperature was 68 ° C. The obtained non-woven fabric A for a fibrous base material was immersed in the aqueous dispersion and then dried with hot air at a temperature of 160 ° C. for 20 minutes to form a sheet-like material in 100% by mass of the sheet-like material. A polymer elastic body-imparting sheet having a thickness of 2.05 mm, to which the polymer elastic body was added so that the polymer elastic body was 38% by mass, was obtained.

The obtained polymer elastic body-imparting sheet was immersed in water heated to 95 ° C. for 10 minutes, and dried in a dryer at 120 ° C. for 30 minutes to obtain a sheet from which the applied PVA had been removed. ..

(Dyeing / finishing)
This was done in the same manner as in Example 1. The hardness and softness of the obtained sheet-like material was 90 mm, the wear loss before the light resistance test was 11 mg, and the wear loss after the light resistance test was 26 mg, and the light resistance was inferior. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 91%, the heat resistance was excellent, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was 1.2% by mass.

[Comparative Example 10]
(Non-woven fabric)
As in Example 6, the non-woven fabric B for a fibrous base material was used as the non-woven fabric.

(Giving a polymer elastic body)
A non-woven fabric with a polymer elastic body was obtained in the same manner as in Example 6 except that the heating temperature was changed.

(Ultrafine fiber expression treatment)
The procedure was the same as in Example 6 except that the drying temperature was changed.

(Dyeing / finishing)
This was done in the same manner as in Example 6. The obtained sheet-like material had a rigidity of 85 mm, a wear loss before the light resistance test was 21 mg, and a wear loss after the light resistance test was 31 mg, and the light resistance and the wear resistance were inferior. In addition, N-acylurea bond and isourea bond were present inside the polymer elastic body. Further, the L value retention rate was 85%, the heat resistance was not sufficient, and the amount of monovalent cation-containing inorganic salt inside the polymer elastic body was less than the lower limit of detection.

Note that "PU" in Table 2 represents polyurethane.

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

Claims

A sheet-like material containing a polymer elastic body in a fibrous base material, the fibrous base material is composed of ultrafine fibers having an average single fiber diameter of 0.1 μm or more and 10 μm or less, and the polymer elastic body has a hydrophilic group. A sheet-like material containing a polyether diol as a constituent component, having an N-acylurea bond and / or an isourea bond inside the polymer elastic body, and satisfying the following conditions 1 and 2.
Condition 1: JIS L 1096: 2010 The longitudinal stiffness specified by method A (45 ° cantilever method) described in "Fabric test method for woven fabrics and knitted fabrics" is 40 mm or more and 140 mm or less Condition 2: JIS L 0843: 2006 The amount of xenon arc in the light fastness measurement method is 110 MJ / m. The wear loss in the Martindale wear test 20,000 times specified by JIS L 1096: 2005 after the light resistance test measured under 2 conditions is 25 mg or less.
The sheet-like material according to claim 1, wherein the wear loss in the Martindale wear test 20,000 times specified in JIS L 1096: 2010 is 20 mg or less in the sheet-like material before the light resistance test.
The sheet-like material according to claim 1 or 2, which contains 10% by mass or more of the polymer elastic body.
The sheet-like material according to any one of claims 1 to 3, further satisfying the following condition 3 in the sheet-like material.
Condition 3: The retention rate of the L value when the raised surface of the sheet-like material is placed on a hot plate heated to 150 ° C. and pressed for 10 seconds with a pressing load of 2.5 kPa is 90% or more and 100% or less.
A method for producing a sheet-like material, which comprises the following steps (1) to (4) in this order.
(1) A fibrous base material made of ultrafine fiber-expressing fibers is impregnated with an aqueous dispersion containing a polymer elastic body, a monovalent cation-containing inorganic salt, and a cross-linking agent, and then at 120 ° C. or higher and 180 ° C. or lower. A polymer elastic body impregnation step in which heat treatment is performed at a temperature, wherein the polymer elastic body has a hydrophilic group, contains a polyether diol as a constituent component, and contains monovalent cations in the aqueous dispersion. Polymer elastic body impregnation step in which the content of the inorganic salt is 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polymer elastic body (2) The ultrafine fiber-expressing fiber is alkali-treated and the ultrafine fiber is treated. (3) Heat treatment at a temperature of 120 ° C. or higher and 180 ° C. or lower, drying step (4) Raising at least one surface of the unraised sheet-like material to form naps on the surface. Process
The method for producing a sheet-like material according to claim 5, further comprising a dyeing step of dyeing the unbrushed sheet-like material or the sheet-like material after the drying step.
The method for producing a sheet-like product according to claim 5 or 6, wherein the monovalent cation-containing inorganic salt is sodium chloride and / or sodium sulfate.
The method for producing a sheet-like product according to any one of claims 5 to 7, wherein the cross-linking agent is a carbodiimide-based cross-linking agent.