TW202129118A - Sheet-like article and method for producing same - Google Patents

Abstract

The object of the present invention is to provide a sheet-like article that has a soft hand and excellent light resistance and a method for producing the same. In order to achieve the above-mentioned object, the sheet-like article of the present invention has the following constitution. that is: A sheet-like article, which is a sheet-like article containing a polymer elastomer in a fibrous base material, wherein the fibrous base material contains ultrafine fibers with an average single fiber diameter of 0.1 μm or more and 10 μm or less, and the polymer elastomer has a hydrophilic base , And containing polyether glycol as a constituent, having N-urea bonds and/or isourea bonds in the polymer elastomer, the sheet meets the following conditions 1 and 2; Condition 1: The stiffness in the longitudinal direction specified by the specific specifications is 40mm or more and 140mm or less, Condition 2: After the light resistance test measured under the conditions specified in the specific specifications, the abrasion loss after 20,000 times of the Martindale abrasion test specified in JIS L 1096:2005 is 25 mg or less.

Description

Flake and its manufacturing method

The present invention relates to a sheet-like article and a manufacturing method thereof, and particularly relates to a sheet-like article having excellent flexibility and light resistance and a manufacturing method thereof.

The sheet-like material, which mainly contains fibrous base material such as non-woven fabric and polyurethane, has excellent characteristics that natural leather does not have, and is widely used in various applications such as artificial leather. In particular, sheet-like articles using polyester-based fibrous substrates have excellent light resistance and are becoming more widely used in clothing, chair veneers, automobile interior materials, and the like.

When manufacturing such a sheet, it is generally used to impregnate the fibrous base material with an organic solvent solution of polyurethane, and then immerse the resulting fibrous base material in water or water that is not a solvent of polyurethane. A combination of the steps of wet solidification of polyurethane in an aqueous organic solvent solution. At this time, as the organic solvent of the polyurethane solvent, water-miscible organic solvents such as N,N-dimethylformamide are used, but in general, organic solvents are highly harmful to the environment, so In the manufacture of flakes, it is strongly required not to use organic solvents.

As a specific solution, instead of the conventional organic solvent-based polyurethane, the method of using a water-dispersed polyurethane in which a polyurethane resin is dispersed in water is reviewed, but generally speaking The sheet-like article coagulated by using water-dispersed polyurethane has a problem that the hand feel is easy to harden.

As one of the main reasons, there is a difference in the solidification method of the two. That is, the organic solvent is suitable for polyurethane coagulation, which is a so-called wet coagulation method in which water is used to replace the polyurethane molecules dissolved in the organic solvent with the solvent to coagulate. Looking at the acid ester film, a porous film with low density is formed. Therefore, it is considered that when polyurethane is impregnated into the fibrous base material and coagulated, the area where the fiber and the polyurethane are bonded is also reduced, and it becomes a soft sheet.

On the other hand, the water-dispersed polyurethane system is mainly heated to disintegrate the hydrated state of the water-dispersed polyurethane dispersion, so that the polyurethane emulsions are coagulated and solidified. The so-called moist heat coagulation method is the mainstream, and the resulting polyurethane film has a high-density non-porous film structure. Therefore, it is considered that the adhesion between the fibrous base material and the polyurethane becomes dense, and the entangled part of the fiber is strongly grasped, so that the hand feel becomes hard.

So far, in order to use water-dispersed polyurethane to obtain soft-touch sheet-like objects, for example, it has been proposed to add a tackifier to a solution containing water-dispersed polyurethane and use hot water A method of treating the fibrous substrate impregnated with the solution to reduce the polyurethane coating film covering the fibrous substrate to obtain a soft touch (Patent Document 1).

As a coagulation method that also uses hot water treatment, it has been proposed to apply a curing treatment after dyeing to prevent the deterioration of physical properties due to polyurethane swelling during dyeing, and to obtain a sheet with excellent moisture and heat resistance. Method (Patent Document 2), or using water-dispersed polyurethane containing hindered amine compounds, to obtain sheet-like objects with excellent lightfastness and flexibility, such as light yellowing resistance, lightfastness fastness, etc. (Patent Document 3).

In addition, there is a proposal to adjust the gelation temperature of the water-dispersible polyurethane by dissolving and mixing inorganic salts in the nonionic water-dispersible polyurethane that is forcedly emulsified. The gelation temperature is a method for obtaining a soft touch by suppressing the phenomenon that the particles of the polymer emulsion dispersed in water are concentrated on the surface layer of the sheet with the movement of the water, the so-called migration phenomenon (Patent Document 4).

Furthermore, there is a proposal to impregnate a sheet-like substance with water-dispersed polyurethane added with polysaccharides, and heat and dry it at a two-stage temperature to make the polymer elastomer porous and soften the hand. Method (Patent Document 5). In this method, in the first stage of drying, polysaccharides are used to capture water to completely coagulate the polymer elastomer, and in the second stage of drying, the polymer elastomer is completely coagulated to make high The water trapped by the polysaccharide contained in the molecular elastomer evaporates, and the part where the water trapped by the polysaccharide exists becomes voids, forming a porous structure.

Alternatively, there is a proposal for a method of applying a crosslinking agent ‧ to the sheet after coagulation of the water-dispersed polyurethane, and heating it to react, and maintaining the texture before the addition of the crosslinking agent (Patent Document 6). In this method, regardless of the coagulation method of the polyurethane, the water-dispersed polyurethane can be reacted with the cross-linking agent to maintain a state close to the original polyurethane agglomerated structure . [Prior Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2015/129602 Patent Document 2: Japanese Patent Application Publication No. 2017-172074 Patent Document 3: Japanese Patent Laid-Open No. 2000-265052 Patent Document 4: Japanese Patent Laid-Open No. 6-316877 Patent Document 5: Japanese Patent Application Publication No. 2019-112742 Patent Document 6: International Publication No. 2016/052189

[The problem to be solved by the invention]

However, when the sheet is used outdoors for automobile interior materials, the ultraviolet rays contained in the sunlight decompose the polyurethane that grabs the fibers in the sheet, and the sheet deteriorates. The subject.

Generally, the water-dispersed polyurethane is obtained by the reaction of a polymer polyol with an organic polyisocyanate and a chain extender, and exhibits various properties depending on the composition of the polymer polyol. As representative polymer polyols, there are two types of polyether polyols and polycarbonate polyols. However, the use of polyether-based polyurethane-applied sheet-like materials, although it can be more than polycarbonate It is suitable for the soft hand of polyurethane, but it has poor light resistance. In order to have a soft touch and light fastness, it is necessary to use polyether-based applicable polyurethane to improve light fastness so as to withstand practical use.

In the methods disclosed in Patent Documents 1 to 3, although the hardness of the hand feeling can be improved by hot water coagulation, and a soft hand feeling can be obtained to a certain extent, the polyurethane does not fully function as a binder and is abrasion resistant. Insufficient sex change. In the method disclosed in Patent Document 2, since the dye is heated at a high temperature after dyeing, the dye may be sublimated, and therefore the color may fade in actual use, and the light resistance may become insufficient. In addition, in the method disclosed in Patent Document 3, although the light resistance is improved by the inclusion of a hindered amine compound, the physical properties of the film are reduced due to the inclusion of the compound in the polymer polyol, and the fiber grip is weak, and the sheet-like material The wear resistance is insufficient. Also, regarding flexibility, it cannot be said to be sufficient.

Furthermore, in the method disclosed in Patent Document 4, although a soft hand can be achieved by inhibiting migration, since the polyurethane resin is not three-dimensionally cross-linked, the fibers cannot be sufficiently grasped and the wear resistance Consumption and light resistance become insufficient.

On the other hand, in the method disclosed in Patent Document 5, a porous structure can be obtained through two-stage drying, but the migration phenomenon cannot be completely suppressed, and the hand feel is insufficient. In addition, since the polyurethane resin is not three-dimensionally crosslinked, the fibers cannot be sufficiently grasped, and the abrasion resistance and light resistance are insufficient.

Alternatively, in the method disclosed in Patent Document 6, although the crosslinking agent is impregnated after the polyurethane is solidified, the reaction between the polyurethane and the crosslinking agent does not proceed too much, so that the polycarbonate cannot be sufficiently formed. The three-dimensional structure caused by the urethane and the cross-linking agent, abrasion resistance and light resistance become insufficient.

Therefore, the object of the present invention is to provide a sheet-like article and a method of manufacturing the same in view of the background of the above-mentioned prior art. [Means to solve the problem]

In order to achieve the above objective, the inventors have repeatedly reviewed and found that: in the coagulation of a polymer elastomer containing polyether glycol as a constituent, and a specific amount of an inorganic salt containing a monovalent cation and a crosslinking agent By adjusting the drying temperature, not only can the sheet be manufactured by caring about the environment, but also a sheet with superior hand feeling and light resistance can be obtained compared with the conventional sheet, which is an invention.

That is, the present invention intends to solve the aforementioned problems. The sheet of the present invention is a sheet containing a polymer elastomer in a fibrous base material, wherein the fibrous base material includes an average single fiber diameter of 0.1 μm or more and 10 μm or less The ultra-fine fiber of the polymer elastomer has a hydrophilic group, and contains polyether glycol as a constituent component, and has an N-urea bond and/or an isourea bond in the interior of the polymer elastomer. The sheet satisfies the following Condition 1 and Condition 2; Condition 1: The stiffness in the longitudinal direction specified by Method A (45° Cantilever Method) described in JIS L 1096:2010 "Test Methods for Grey Fabrics and Knitted Fabrics" is 40mm or more and 140mm or less ^{, Condition 2: After the light fastness test measured under the condition of 110MJ/m 2 in the} light fastness measuring method of JIS L 0843:2006, the light fastness test is followed by the Martindale abrasion test 2 specified in JIS L 1096:2005 The abrasion loss of ten thousand times is less than 25mg. According to a preferable aspect of the sheet-like article of the present invention, in the sheet-like article before the light resistance test, the abrasion loss after 20,000 times of the Martindale abrasion test specified in JIS L 1096:2010 is 20 mg or less.

According to a preferred aspect of the sheet-like article of the present invention, the aforementioned polymer elastomer is contained in an amount of 10% by mass or more.

According to a preferred aspect of the sheet of the present invention, in the aforementioned sheet, the following condition 3 is further satisfied; Condition 3: Place the napped surface of the aforementioned sheet on a hot plate heated to 150°C, and the retention of the L value when pressed with a pressing load of 2.5 kPa for 10 seconds is 90% or more and 100% or less. The method of manufacturing a sheet of the present invention is a method of manufacturing a sheet including the following steps (1) to (4) in sequence. (1) A polymer elastomer impregnation step, which involves impregnating a fibrous substrate containing ultra-fine fiber-exposed fibers with an aqueous dispersion containing a polymer elastomer, an inorganic salt containing monovalent cations, and a crosslinking agent, followed by 120 The step of impregnating the polymer elastomer with heat treatment at a temperature above 180°C, the polymer elastomer has a hydrophilic group and contains polyether glycol as a constituent, and the aqueous dispersion contains monovalent cations 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 aforementioned polymer elastomer; (2) The ultra-fine fiber unfolding step, which is an alkali treatment of the aforementioned ultra-fine fiber unfolding fiber to unfold the ultra-fine fiber; (3) The drying step, which is heat treatment at a temperature above 120°C and below 180°C; (4) Raising step, which is to raise at least one side of the unfluffed sheet to form fluff on the surface. According to a preferred aspect of the method of manufacturing a sheet of the present invention, after the aforementioned drying step, it includes a dyeing step of dyeing the unfluffed sheet or the sheet.

According to a preferred aspect of the method for manufacturing a sheet of the present invention, the aforementioned monovalent cation-containing inorganic salt is sodium chloride and/or sodium sulfate.

According to a preferred aspect of the method for manufacturing a sheet-like article of the present invention, the aforementioned crosslinking agent is a carbodiimide-based crosslinking agent. [Effects of Invention]

According to the present invention, it is possible to obtain a sheet-like article that has both a soft hand and excellent light resistance.

[Form to implement the invention]

The sheet-like article of the present invention is a sheet-like article containing a polymer elastomer in a fibrous base material, wherein the fibrous base material contains ultrafine fibers with an average single fiber diameter of 0.1 μm or more and 10 μm or less, and the polymer elastomer has a hydrophilic base. , And containing polyether glycol as a constituent, having N-urea bonds and/or isourea bonds in the polymer elastomer, the sheet satisfies the following conditions 1 and 2; Condition 1: JIS L 1096: The stiffness in the longitudinal direction specified by Method A (45° cantilever method) described in 2010 "Test Methods for Grey Fabrics of Woven Fabrics and Knitted Fabrics" is 40mm or more and 140mm or less. Condition 2: Light fastness in JIS L 0843: 2006 Determination of the amount of xenon arc of the light resistance test was measured after the 110MJ / m ² conditions to JIS L 1096: Martindale abrasion test under 2005 20,000 followed by abrasion of 25mg or less weight loss.

The constituent elements are described in detail below, but the present invention is not limited at all by the scope of the following description as long as it does not exceed the spirit.

[Ultra-fine fiber] As resins that can be used for the ultrafine fibers used in the present invention, from the viewpoint of excellent durability, especially mechanical strength, heat resistance, and light resistance, for example, polyester resins or polyamide resins can be cited. Specific examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate. The polyester resin can be obtained from, for example, dicarboxylic acid and/or its ester-forming derivative and 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, and diphenyl-4,4' -Dicarboxylic acid and its ester-forming derivatives, etc. Furthermore, the ester-forming derivatives referred to in the present invention are lower alkyl esters of dicarboxylic acids, acid anhydrides, and chlorinated compounds. Specifically, methyl, ethyl, and hydroxyethyl are preferably used. As the dicarboxylic acid and/or its ester-forming derivative used in the present invention, a more preferable aspect is terephthalic acid and/or its dimethyl ester.

As the diol used for the polyester resin, ethylene glycol, 1,3-propanediol, 1,4-butanediol, cyclohexanedimethanol, etc. may be mentioned, and among them, ethylene glycol is preferably used.

As the resin used for ultrafine fibers, when polyamide resins are used, polyamide 6, polyamide 66, polyamide 56, polyamide 610, polyamide 11, polyamide 12, copolymerized polyamide can be used Amide and so on.

The resin used for ultrafine fibers may contain inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, and antibacterial agents for various purposes.

In addition, the resin used for the ultrafine fibers preferably contains components derived from biomass resources.

Regarding the bio-resource-derived component when polyester resin is used as the resin used in the ultrafine fiber, the bio-resource-derived component can be used as its constituent dicarboxylic acid or its ester-forming derivative. It is possible to use components derived from biomass resources as the diol, but from the viewpoint of reducing environmental load, it is preferable to use both of the dicarboxylic acid or its ester-forming derivative and the diol. Ingredients.

As far as the components derived from biomass resources are used when polyamide resin is used as the resin for ultrafine fibers, it is more suitable to use polyamide resins from the viewpoint of economically obtaining raw materials derived from biomass resources or the physical properties of fibers. Amide 56, polyamide 610, polyamide 11.

As the cross-sectional shape of the ultrafine fiber, either a circular cross-section or a special-shaped cross-section can be adopted. Specific examples of the profiled cross-section include polygonal shapes such as elliptical, flat, and triangular shapes, fan shapes, and cross shapes.

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. Since the average single fiber diameter of the ultrafine fibers is 10 μm or less, preferably 7 μm or less, and more preferably 5 μm or less, the sheet-like material can be made softer. In addition, the quality of fluff can be improved. On the other hand, since the average single fiber diameter of the ultra-fine fibers is 0.1 μm or more, preferably 0.3 μm or more, and more preferably 0.7 μm or more, it can be a sheet with excellent color development after dyeing. . In addition, it is possible to improve the ease of dispersing and dividing the ultrafine fibers in bundles when performing fluff treatment by polishing.

The average single fiber diameter mentioned in the present invention is measured by the following method. That is: (1) The cross section of the sheet-like article cut in the thickness direction is observed with a scanning electron microscope (SEM). (2) Measure the fiber diameter of any 50 ultra-fine fibers in the observation plane in three directions in each ultra-fine fiber section. However, when using ultra-fine fibers with a profiled cross-section, first measure the cross-sectional area of the single fiber, and calculate the diameter of the circle that forms the cross-sectional area using the following formula. The diameter thus obtained is regarded as the single fiber diameter of the single fiber.・Single fiber diameter (μm)=(4×(single fiber cross-sectional area (μm ² ))/π) ^1/2 Two digits are rounded off.

[Fibrous base material] The fibrous substrate used in the present invention contains the aforementioned ultrafine fibers. Moreover, in the fibrous base material, very fine fibers of different raw materials are allowed to be mixed.

As a specific form of the fibrous base material, a nonwoven fabric in which the aforementioned ultrafine fibers are entangled, or a nonwoven fabric in which fiber bundles of ultrafine fibers are entangled can be used. Among them, from the standpoint of the strength and feel of the sheet-like material, it is preferable to use a nonwoven fabric in which fiber bundles of ultrafine fibers are entangled. From the viewpoint of softness and hand feeling, it is particularly preferable to use a non-woven fabric in which the ultrafine fibers constituting the fiber bundle of the ultrafine fibers are appropriately spaced from each other and have voids. In this way, a non-woven fabric formed by entangled fiber bundles of ultrafine fibers can be obtained by, for example, entanglement of ultrafine fiber unfolding fibers in advance, and then unfolding ultrafine fibers. In addition, a non-woven fabric in which the ultra-fine fibers constituting the fiber bundle of the ultra-fine fibers are appropriately spaced from each other with voids can be obtained, for example, by using sea-island-type composite fibers, which can be made into islands by removing sea components. Become a gap between.

As the aforementioned non-woven fabric, either short-fiber non-woven fabric or long-fiber non-woven fabric may be used, but from the viewpoint of the feel and quality of the sheet, it is more preferable to use short-fiber non-woven fabric.

When the short fiber nonwoven 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. Since the fiber length is 25 mm or more, more preferably 35 mm or more, and particularly preferably 40 mm or more, it becomes easy to obtain a sheet-like article having excellent abrasion resistance due to entanglement. In addition, since the fiber length is set to 90 mm or less, more preferably 80 mm or less, and particularly preferably 70 mm or less, a sheet-like article with better texture and quality can be obtained.

In the present invention, when a non-woven fabric is used as a fibrous base material, for the purpose of improving strength, etc., a woven fabric or knitted fabric may be inserted into the non-woven fabric, or may be laminated or attached to the back. The average single fiber diameter of the fibers constituting the woven fabric or knitted fabric is more preferably 0.3 μm or more and 10 μm or less because damage during needle sticking can be suppressed and the strength can be maintained.

As the fibers constituting the aforementioned woven fabrics and knitted fabrics, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polylactic acid, or 6- Synthetic fibers such as polyamides such as nylon or 66-nylon, regenerated fibers such as cellulose polymers, and natural fibers such as cotton or hemp.

[Polymer Elastomer] In the sheet-like article of the present invention, examples of polymer elastomers include water-dispersed polysiloxane resins, water-dispersed acrylic resins, water-dispersed urethane resins, or their copolymers. Among them, water-dispersible polyurethane resins are more suitable from the viewpoint of hand feeling.

As the water-dispersed polyurethane resin, it is preferable to use a resin obtained by the reaction of 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. In addition, 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 easy to prevent the texture from becoming hard. In addition, by setting the number average molecular weight to 5,000 or less, more preferably 4,000 or less, the strength of polyurethane as a binder can be easily maintained. Hereinafter, a case where a water-dispersed polyurethane resin is used as the polymer elastomer will be described.

(1) Each reaction component of water-dispersed polyurethane resin First, the reaction components of the water-dispersed polyurethane resin will be explained.

(1-1) Polymer polyol In the sheet-like article of the present invention, the aforementioned polymer elastomer contains polyether glycol as a constituent component. The content of the polyether glycol in the polymer polyol is preferably 50% by mass or more of the entire polymer polyol, more preferably 70% by mass or more, and particularly preferably 90% by mass or more. Specific examples of polyether glycols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and copolymerized polyether glycols in which these are combined. In addition, in this specification, the term "contained as a constituent" means to be contained as a monomer component and an oligomer component constituting the polymer elastomer. Polyether glycol has a high degree of freedom of ether bond, low glass transition temperature, and weak cohesion, so it is easy to obtain polyurethane with excellent flexibility.

(1-2) Organic Diisocyanate The organic diisocyanate used in the present invention includes an aromatic diisocyanate with a carbon number (except the carbon in the NCO group, the same below) of 6 to 20, and aliphatic diisocyanate with a carbon number of 2 to 18, and a carbon number of Alicyclic diisocyanates with 4 or more and 15 or less, aromatic aliphatic diisocyanates with 8 or more and 15 or less carbon atoms, modification of these diisocyanates (carbodiimide modification, urethane modification , Uretdione modified body, etc.) and a mixture of two or more of these.

Specific examples of the aforementioned aromatic diisocyanates having 6 or more and 20 or less carbon atoms include 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/2,6-methylene diisocyanate Phenyl diisocyanate, 2,4'- and/or 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4,4'-diisocyanatobiphenyl, 3,3'-di Methyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1,5-naphthylene diisocyanate, etc. .

Specific examples of the aforementioned aliphatic diisocyanate having a carbon number of 2 or more and 18 or less include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2 , 2,4-Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylhexanoate, bis(2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

Specific examples of the aforementioned alicyclic diisocyanate having a carbon number of 4 or more and 15 or less include isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, cyclohexyl diisocyanate, and methyl isocyanate. Cyclohexyl diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexylene-1,2-dicarboxylate, 2,5- and/or 2,6-norbornane diisocyanate, etc.

Specific examples of the aforementioned aromatic aliphatic diisocyanates having 8 to 15 carbon atoms include meta and/or p-xylylene diisocyanate, α,α,α',α'-tetramethylxylylene Base diisocyanate and so on.

Among these, the preferred organic diisocyanate is an alicyclic diisocyanate. In addition, a particularly preferred diisocyanate is dicyclohexylmethane-4,4'-diisocyanate.

(1-3) Chain extender As the chain extender used in the present invention, water, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and Low-molecular-weight diols such as neopentyl glycol, etc., alicyclic diols such as 1,4-bis(hydroxymethyl)cyclohexane, etc., and 1,4-bis(hydroxyethyl)benzene, etc. Aromatic diols, aliphatic diamines such as ethylenediamine, alicyclic diamines such as isophorone diamine, and aromatic diamines such as 4,4-diaminodiphenylmethane Amines, aromatic aliphatic diamines such as xylene diamine, alkanolamines such as ethanolamine, hydrazine, dihydrazine such as dihydrazine adipate, and mixtures of two or more of these .

Among these, preferred chain extenders are water, low-molecular-weight glycols, and aromatic diamines, especially water, ethylene glycol, 1,4-butanediol, and 4,4'-diamine. Diphenylmethane and a mixture of two or more of these.

(2) Additives for water-dispersed polyurethane resin In the present invention, it is important to add an inorganic salt containing a monovalent cation to a solution containing a water-dispersed polyurethane for the reason described later. In addition, if necessary, coloring agents such as titanium oxide, ultraviolet absorbers (diphenyl ketone series, benzotriazole series, etc.) or antioxidants [4,4-butylene-bis(3-methyl -6-1-butylphenol) and other hindered phenols; triphenyl phosphite, trichloroethyl phosphite and other organic phosphites, etc.] various stabilizers, inorganic fillers (calcium carbonate, etc.), etc.

(3) The composition of water-dispersed polyurethane resin In the water-dispersible polyurethane used in the present invention, as a component for making the polyurethane contain a hydrophilic group, for example, a hydrophilic group-containing active hydrogen component can be cited. Examples of the active hydrogen component containing a hydrophilic group include a compound containing a nonionic group and/or an anionic group and/or a cationic group and an active hydrogen.

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

Examples of compounds having an anionic group and active hydrogen include carboxyl-containing compounds such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid. The compounds and their derivatives, or 1,3-phenylenediamine-4,6-disulfonic acid, 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid, etc. containing sulfonic acid Radical compounds and their derivatives, and the salts of these compounds neutralized by neutralizing agents.

Examples of compounds containing cationic groups and active hydrogen include tertiary amino group-containing compounds such as 3-dimethylaminopropanol, N-methyldiethanolamine, N-propyldiethanolamine, and others. derivative.

The aforementioned active hydrogen component containing a hydrophilic group can also be used in the form of a salt neutralized by a neutralizing agent.

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

In the present invention, the so-called hydrophilic group in the polymer elastomer is a group having active hydrogen. Specific examples of the hydrophilic group include a hydroxyl group, a carboxyl group, a sulfonic acid group, and an amino group.

In the present invention, there is an N-urea bond and/or an isourea bond in the polymer elastomer. Here, the phrase "have an N-urea bond and/or an isourea bond in the polymer elastomer" means that the polymer elastomer has an N-urea bond and/or an isourea bond. When a water-dispersed polyurethane resin is used as the polymer elastomer, the N-urea bond and/or isourea bond system can be used, for example, the aforementioned hydroxyl group and/or the hydrophilic group-containing active hydrogen component. Or the carboxyl group is formed by reacting with the carbodiimide-based crosslinking agent. As a result, in the molecule of the polymer elastomer, a three-dimensional cross-linked structure formed by N-urea bonds and/or isourea bonds with excellent physical properties such as light resistance, heat resistance, and abrasion resistance, and flexibility, is provided , It can significantly improve physical properties such as abrasion resistance while maintaining the flexibility of the sheet.

Moreover, the presence of the above-mentioned N-urea group or isourea group in the polymer elastomer can be used for mapping processing such as time-of-flight secondary ion mass analysis (TOF-SIMS analysis) for the cross section of the sheet. (As an analysis device, for example, "TOF. SIMS 5" manufactured by ION-TOF) or infrared spectroscopy (as an analysis device, for example, "FT/IR 4000 series" manufactured by JASCO Corporation).

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

The number average molecular weight of the aforementioned polymer elastomer can be determined by gel permeation chromatography, for example, measured under the following conditions. ・Machine: HLC-8220 manufactured by Tosoh Corporation ・String: Tosoh TSKgel α-M ・Solvent: N,N-dimethylformamide (DMF) ・Temperature: 40℃ ・Calibration: Polystyrene The polymer elastomer used in the present invention, from the viewpoint of moderately grasping the fibers in the sheet, and preferably having fluff on at least one side of the sheet, the preferred aspect is that it is present in the fibers The interior of the base material.

[Flakes] The important thing for the sheet of the present invention is that the stiffness in the longitudinal direction specified by the A method (45° cantilever method) described in JIS L 1096:2010 "Test Methods for Grey Fabrics of Woven Fabrics and Knitted Fabrics" is 40 mm or more and 140 mm or less . Since the stiffness is set in the above range, it can have moderate flexibility and resilience. Regarding the stiffness, from the viewpoint of obtaining a resilient sheet-like article, it is preferably 50 mm or more, more preferably 55 mm or greater, and from the viewpoint of obtaining a flexible sheet-like article, it is preferably 120 mm or less , More preferably 110mm or less.

The so-called longitudinal direction in the sheet-like article of the present invention refers to the direction in which the sheet-like article is raised. As a method of searching for the direction of the raising treatment, it can be suitably used in accordance with the composition of the sheet, such as visual confirmation when a finger is swiped, or SEM photography. That is, the direction in which the fluff fibers can lie down or stand up when they are swiped by a finger is the longitudinal direction. In addition, on the surface of the sheet that was swiped with a finger by SEM photography, the direction of the lying down fluff fibers is the vertical direction. On the other hand, the so-called lateral direction in the sheet-like article of the present invention refers to the direction perpendicular to the longitudinal direction as the lateral direction.

In addition, it is important for the sheet-like article of the present invention to use the Martin generation specified in JIS L 1096:2005 after the light resistance test measured under the condition of ^{110MJ/m 2 in the xenon arc test method of JIS L 0843:2006 light fastness measurement method.} The abrasion loss of 20,000 times in the Er abrasion test is less than 25 mg. Since the abrasion loss after the light resistance test is set to the above range, even if it is used for a long period of time in a harsh environment such as exposure to sunlight, the deterioration of the polymer elastomer can be suppressed, and the appearance of the sheet can be maintained. From the viewpoint of suppressing the deterioration of the appearance of the sheet-like article, the abrasion loss is preferably 23 mg or less, and more preferably 20 mg or less.

The sheet-like article of the present invention is a sheet-like article before the light resistance test, and the abrasion loss of 20,000 times of the Martindale abrasion test specified in JIS L 1096:2010 is preferably 20 mg or less. Since the abrasion loss before the light resistance test is set to the above range, it is easy to suppress hair loss or appearance deterioration during actual use. From the viewpoint of more suppressing lint during actual use, the abrasion loss is preferably 18 mg or less, and more preferably 15 mg or less.

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

The sheet-like article of the present invention preferably further satisfies the following condition 3. Condition 3: The raised surface of the sheet is placed on a hot plate heated to 150°C, and the L value retention rate when pressed with a pressing load of 2.5 kPa for 10 seconds (hereinafter sometimes simply referred to as the L value retention rate) It is above 90% and below 100%.

Among them, since the retention rate of the L value is 90% or more, more preferably 92% or more, and particularly preferably 95% or more, the sheet has high heat resistance.

Furthermore, the "raised surface of the sheet-like article" in the present invention refers to the surface of the sheet-like article after raising it. In addition, the so-called L value refers to the L value defined by the Commission International on Illumination (CIE). However, the L value retention rate in the present invention means that the ratio of lightness changes under heating and pressing conditions is small, which means that The sheet with a dark color before heating and pressing is an indicator of how bright the sheet does not become bright after heating and pressing.

Furthermore, in the present invention, the L value retention rate refers to the value measured and calculated by the following procedure. (1) The cut piece 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) With the raised side of the test piece facing down, place the test piece on a hot plate heated to 150°C (for example, "CHP-250DN" manufactured by AS ONE Co., Ltd.). (3) Place the indenter adjusted so that the pressing load becomes 2.5 kPa on the test piece, and hold it for 10 seconds. (4) The indenter on the test piece was removed, and the L value of the raised surface of the test piece was measured with the aforementioned color difference meter. (5) Calculate the L value retention rate by the following formula.

L value retention rate (%)=((1) measured L value)/((4) measured L value)×100 In order to make the stiffness, the abrasion loss before and after the light resistance test, and the retention of the L value fall within the above ranges, for example, the sheet can be produced through the polymer elastomer impregnation step, the ultrafine fiber development step, and the drying step described later. . After impregnating the polymer elastomer, by going through the ultra-fine fiber development step, the gap between the ultra-fine fiber and the polymer elastomer can be formed, and a soft hand feeling can be easily obtained. In addition, for example, in the drying step, heat treatment (aging treatment) at a temperature above 120°C and below 180°C can agglomerate the particles of the polymer elastomer, which can easily improve light resistance, abrasion resistance, and heat resistance. . Furthermore, since the heat-sensitive coagulation temperature of the aqueous dispersion is set in the range described later, it is possible to suppress the partial presence (migration) of the polyurethane on the surface of the sheet-like object due to the evaporation of water, and it is possible to increase the retention rate of the L value.

[Method of manufacturing flakes] Next, the method of manufacturing the sheet of the present invention is described.

The manufacturing method of the sheet-like article of the present invention includes the following steps (1) to (4) in sequence. (1) A polymer elastomer impregnation step, which involves impregnating a fibrous substrate containing ultra-fine fiber-exposed fibers with an aqueous dispersion containing a polymer elastomer, an inorganic salt containing monovalent cations, and a crosslinking agent, followed by 120 The step of impregnating the polymer elastomer with heat treatment at a temperature above 180°C, the polymer elastomer has a hydrophilic group and contains polyether glycol as a constituent, and the aqueous dispersion contains monovalent cations 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 aforementioned polymer elastomer; (2) The ultra-fine fiber unfolding step, which is an alkali treatment of the aforementioned ultra-fine fiber unfolding fiber to unfold the ultra-fine fiber; (3) The drying step, which is heat treatment at a temperature above 120°C and below 180°C; (4) Raising step, which is to raise at least one side of the unfluffed sheet to form fluff on the surface.

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

In the present invention, as a means for obtaining ultra-fine fibers, it is preferable to use ultra-fine fiber development type fibers. After pre-entangled ultra-fine fiber unfolding fibers to form a non-woven fabric, the ultra-fine fiber bundles are entangled to obtain a non-woven fabric by performing ultra-fine fiber.

As an ultra-fine fiber-expression type fiber, a thermoplastic resin of two components (two or three components when the island fiber is a core-sheath composite fiber) with different solvent solubility is used as the sea component and the island component, and the aforementioned components are dissolved and removed by using a solvent, etc. The sea component uses the island-in-the-sea composite fiber with the island component as the ultra-fine fiber. When the sea component is removed, a moderate gap can be provided between the island components, that is, between the ultra-fine fibers inside the fiber bundle. It is better from the viewpoint of surface quality.

As a sea-island composite fiber, a sea-island composite spinneret is used to alternately arrange the two components of the sea component and the island component (the island fiber is a core-sheath composite fiber when it is a three-component) and spin it using a polymer alternating arrangement. The method is preferable from the viewpoint of obtaining ultrafine fibers having a uniform single fiber diameter.

As the sea component of the island-in-the-sea composite fiber, polyethylene, polypropylene, polystyrene, copolymerized polyester with sodium sulfoisophthalic acid or polyethylene glycol, and polylactic acid can be used. From the standpoints of yarn properties and easy dissolution properties, polystyrene and copolymerized polyester are preferably used.

It is preferable to dissolve and remove the sea component after the application of the polymer elastomer. As 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. If the mass ratio of the sea component is 10% by mass or more, the island component is likely to be sufficiently ultrafine. In addition, if the mass ratio of the sea component is 80 mass or less, the productivity is improved because the ratio of the eluted component is small. The mass ratio of the sea component to the island component is more preferably the sea component: the island component = the range of 20:80 to 70:30.

In addition, the fiber entangled body is preferably in the form of a non-woven fabric. Both short-fiber non-woven fabrics or long-fiber non-woven fabrics can be used as described above. However, if it is a short-fiber non-woven fabric, the fibers facing the thickness direction of the fibrous base material are higher than the long-fiber non-woven fabric. Many, the surface of the fibrous base material at the time of fluffing can obtain a high density, so it is better.

When a short fiber nonwoven fabric is used as a fiber entangled body, it is preferable to apply a crimping process to the obtained ultra-fine fiber unfolding fiber and cut into a specified length to obtain raw cotton. Well-known methods can be used for crimping and cutting.

Next, the obtained raw cotton is made into a fiber web by a cross-layer or the like, and the short fiber non-woven fabric is obtained by entanglement. As a method of entanglement of the fiber web to obtain a short-fiber nonwoven fabric, needle punching treatment, water jet piercing treatment, etc. can be used.

Furthermore, the obtained short-fiber non-woven fabric and woven fabric can be laminated and then entangled and integrated. In the entanglement integration of short fiber non-woven fabric and woven fabric, the woven fabric can be sandwiched between the single-sided or two-area layer of the short fiber non-woven fabric, or the woven fabric between multiple short fiber non-woven nets, and then processed by needle tying. , Water jet puncture treatment, etc., to entangle the fibers of the short fiber non-woven fabric and the woven fabric.

The apparent density of the short-fiber non-woven fabric containing composite fibers (extremely fine fiber development type fibers) after needle punching treatment or water jet puncturing treatment is preferably 0.15 g/cm ³ or more and 0.45 g/cm ³ or less. By setting the apparent density to preferably 0.15 g/cm ³ or more, the fibrous base material can obtain sufficient morphological stability and dimensional stability. On the other hand, by setting the apparent density to 0.45 g/cm ³ or less, it is possible to maintain a sufficient space for providing the polymer elastomer.

From the viewpoint of densification, the non-woven fabric obtained in this way is preferably shrunk by dry heat, moist heat, or both, to further increase the density. In addition, the non-woven fabric may be compressed in the thickness direction by a calendering process or the like.

The method for producing a sheet of the present invention includes (1) a polymer elastomer impregnation step, which impregnates a fibrous base material containing ultra-fine fiber unfolding fibers with an inorganic polymer containing elastomer and monovalent cations. An aqueous dispersion of salt and a crosslinking agent, followed by a polymer elastomer impregnation step of heat treatment at a temperature above 120°C and below 180°C. The polymer elastomer has a hydrophilic group and contains polyether glycol as a constituent Ingredients: 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 elastomer.

In the method for producing a sheet-like article of the present invention, a polymer elastomer having a hydrophilic group and containing polyether glycol as a constituent is provided to a fibrous base material. The application of the polymer elastomer when the nonwoven fabric is used as the fibrous base material can be applied to either a nonwoven fabric containing composite fibers or a nonwoven fabric made of ultrafine fibers.

In the method for producing a sheet-like article of the present invention, the polymer elastomer contains polyether glycol as a constituent. The reason is as described in the item (1-1) Polymer Polyol.

In the manufacturing method of the sheet-like article of the present invention, the coagulation after the application of the polymer elastomer is a dry heat coagulation method of heat treatment at a temperature of 120°C or higher and 180°C or lower. In other coagulation methods, such as the hot water coagulation method in which a polymer elastomer is coagulated in hot water, since the polymer elastic system diffuses into the hot water, a part of it falls off, so there is a concern about workability. In addition, in the acid coagulation method in which the polymer elastomer is coagulated by acid, the acid solution remaining in the sheet must be neutralized, which is poor in processing operability. On the other hand, the dry heat coagulation method to which the present invention is applied is a very simple method of heat-treating a sheet impregnated with a polymer elastomer with a hot-air dryer, etc., and there is no concern about the polymer elastomer falling off, which is excellent in processability. The technique.

In the manufacturing method of the sheet-like article of the present invention, the heating temperature in dry heat solidification is 120°C or more and 180°C or less. The heating temperature is more preferably 140°C or higher. This is because the polymer elastomer can be rapidly solidified, and the polymer elastomer is prevented from being biased under the sheet due to its own weight. Furthermore, in the present invention, it is necessary to use a crosslinking agent together, but by setting the temperature as described above, the crosslinking reaction can be sufficiently promoted to form a three-dimensional network structure, and physical properties, light resistance, and heat resistance can be improved. The heating temperature is more preferably 175°C or lower. This is because the thermal degradation of the polymer elastomer can be suppressed.

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

The aqueous dispersion used in the present invention may contain 40% by mass or less of a water-soluble organic solvent in 100% by mass of the aqueous dispersion in order to improve storage stability or film-forming properties. However, from the point of view of the preservation of the film-forming environment, etc. In view of this, the content of the organic solvent is preferably 1% by mass or less.

In the method for producing a sheet-like article of the present invention, an inorganic salt containing a monovalent cation is contained in the aqueous dispersion. By containing the monovalent cation-containing inorganic salt, heat-sensitive coagulability can be imparted to the aqueous dispersion. In the present invention, the heat-sensitive coagulability refers to the property that when the water dispersion reaches a certain temperature (heat-sensitive coagulation temperature), the fluidity of the water dispersion decreases and solidification proceeds.

In the manufacturing method of the sheet-like article of the present invention, after the aqueous dispersion is applied to the fibrous base material, it is heated at a temperature of 120°C or higher and 180°C or lower to coagulate by dry heat, thereby imparting the polymer elastomer To fibrous substrate.

When the polymer elastomer does not have heat-sensitive coagulation properties, the migration of the polymer elastic system to the surface of the sheet occurs along with the evaporation of water. Furthermore, as the moisture evaporates, the polymer elastomer solidifies in a state of being biased around the fiber, so the polymer elastomer covers the fiber periphery and becomes a structure that strongly restricts its movement. Therefore, the feel of the flakes is significantly hardened.

The thermal coagulation temperature of the aqueous dispersion is preferably 55°C or more and 80°C or less. In order to improve the stability of the aqueous dispersion during storage and to prevent the adhesion of the polymer elastomer to the machine during handling, etc., it is more preferable to make the heat-sensitive temperature 60°C or higher. It can inhibit the migration phenomenon of the polymer elastomer to the surface layer of the fibrous base material. Furthermore, by coagulating the polymer elastomer before the water evaporates from the fibrous base material, it can be formed similar to the wet solvent-based polymer elastomer. The structure obtained by the type coagulation can also form a structure in which the polymer elastomer does not strongly restrain the fibers. Since good flexibility and resilience can be achieved, it is more preferable to make the thermal coagulation temperature less than 70°C.

In the present invention, it is important to use a monovalent cation-containing inorganic salt among the inorganic salts used as the heat-sensitive coagulant. The aforementioned monovalent cation-containing inorganic salt is preferably sodium chloride and/or sodium sulfate. In the conventional technique, as the heat-sensitive coagulant, inorganic salts with divalent cations such as magnesium sulfate or calcium chloride can be suitably used. However, even small additions of these inorganic salts greatly affect the stability of the aqueous dispersion, so Depending on the type of polymer elastomer, it is difficult to tightly control the heat-sensitive gelation temperature for the adjustment of the amount of addition, and there are problems such as gelation during the adjustment of the aqueous dispersion or the storage. On the other hand, inorganic salts containing monovalent cations with a small ion valence have little effect on the stability of the aqueous dispersion, and the stability of the aqueous dispersion can be ensured by adjusting the addition amount, and at the same time, the thermal coagulation temperature can be tightly controlled .

Furthermore, 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 elastomer. Since the content is set to 10 parts by mass or more, the ionic system present in a large amount in the aqueous dispersion uniformly acts on the polymer elastomer particles, and the coagulation can be completed quickly at a specific thermal coagulation temperature. Thereby, in the coagulation of the polymer elastomer in a state where a large amount of water is contained in the fibrous base material as described above, a more significant effect can be obtained. As a result, a structure very similar to that obtained by wet solidification of a solvent-based polymer elastomer can be formed, and a good flexibility and resilience can be achieved. Furthermore, since the addition amount is set to the above, the inorganic salt becomes an inhibitor of the fusion of the polymer elastomer particles, and it is also possible to suppress the hardening of the polymer elastomer due to the continuous film formation. On the other hand, since the content is set to 50 parts by mass or less, a suitable continuous film structure of the polymer elastomer can be left, and the decrease in physical properties can be suppressed. In addition, the stability of the aqueous dispersion can also be maintained.

In the manufacturing method of the sheet-like article of the present invention, it is important to include a crosslinking agent in the aqueous dispersion. By introducing the three-dimensional mesh structure into the polymer elastomer with a crosslinking agent, physical properties such as abrasion resistance can be improved. Furthermore, by combining with the aforementioned monovalent cation-containing inorganic salt, the coagulation of the polymer elastomer and the reaction of the polymer elastomer and the crosslinking agent can proceed simultaneously, by forming a dense three-dimensional network structure and controlling fibers The bonding structure softens the sheet, and at the same time can achieve high physical properties, high light resistance, and high heat resistance of the sheet. That is, in order to improve the physical properties, light resistance, and heat resistance of the sheet-like article, it is necessary and indispensable to use a monovalent cation-containing inorganic salt and a crosslinking agent together, and to control the heating temperature for dry heat coagulation.

In view of the excellent light resistance, heat resistance, and abrasion resistance of the polymer elastic system obtained after the reaction, and also good flexibility, the aforementioned crosslinking agent is preferably a carbodiimide-based crosslinking agent.

The manufacturing method of the sheet-like article of the present invention includes (2) the ultrafine fiber unfolding step, which is an alkali treatment of ultrafine fiber unfolding fibers to unfold the ultrafine fibers. By performing alkali treatment after the polymer elastomer is provided, voids caused by the components dissolved by the alkali treatment are formed between the polymer elastomer and the ultrafine fibers. Therefore, the polymer elastomer does not directly grasp the ultrafine fibers and sheet-like objects. The feel is changed and soft.

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

In the ultra-fine fiber development step, devices such as continuous dyeing machine, vibrating washing type sea removing machine, liquid flow dyeing machine, rope dyeing machine, and winding dyeing machine can be used.

After the ultrafine fiber development step, it is preferable to perform a sufficient washing step after the alkali treatment. By going through the washing step, the alkali or the monovalent cation-containing inorganic salt attached to the sheet can not remain in the sheet, and the processing can be performed without affecting the production equipment. In consideration of environmental aspects and safety of the cleaning liquid, it is preferable to use water.

The manufacturing method of the sheet-like article of the present invention includes (3) a drying step, which is heat-treated at a temperature above 120°C and below 180°C. During the ultrafine fiber development step, the bonds of the polymer elastomer will be partially decomposed due to the solvent that dissolves the components other than the ultrafine fibers in the ultrafine fiber development fiber, so it can be cured by drying. The particles of the polymer elastomer aggregate with each other to further improve physical properties such as light resistance, abrasion resistance, and heat resistance.

In the manufacturing method of the sheet-like article of the present invention, the heating temperature of the aging treatment by drying is 120°C or more and 180°C or less. In order to improve the effect of the aging treatment and to improve the physical properties such as light resistance, abrasion resistance, and heat resistance, the temperature is preferably 140°C or higher, and more preferably 150°C or higher. In order to inhibit thermal degradation of the polymer elastomer, it is preferably 175°C or less, more preferably 170°C or less.

The manufacturing method of the sheet-like article of the present invention preferably includes a dyeing step of dyeing the unfluffed sheet-like article or the sheet-like article after the aforementioned drying step. As this dyeing treatment, various methods commonly used in this field can be used. For example, liquid dyeing treatment using an interlace dyeing machine or a liquid stream dyeing machine, a hot melt dyeing treatment using a continuous dyeing machine, etc. can be used. Or by roller printing, screen printing, inkjet printing, sublimation printing and vacuum sublimation printing and dyeing, etc., printing and dyeing on the pile surface, etc. Among them, it is preferable to use a liquid flow dyeing machine from the viewpoint of imparting a kneading effect at the same time as the dyeing of the non-raised sheet or sheet-like material so that the non-raised sheet-like material or the sheet-like material can be softened. In addition, if necessary, various resin finishing processes can be applied after dyeing.

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

The dye used in the present invention can 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 if it is a polyamide fiber, then Acid dyes or gold-containing dyes can be used, and furthermore, a combination of them can be used. When dyeing with disperse dyes, it can be reduced and washed after dyeing.

It is also preferable to use a dyeing auxiliary when dyeing. By using dyeing auxiliaries, the uniformity and reproducibility of dyeing can be improved. In addition, after dyeing or bathing in the same bath or dyeing, for example, a finishing agent such as a softener such as silicone, an antistatic agent, a water repellent, a flame retardant, a light stabilizer, and an antibacterial agent can be applied.

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

The manufacturing method of the sheet-like article of the present invention does not restrict the dyeing step before and after, including (4) the raising step, which raises at least one side of the unfluffed sheet-like article to form fluff on the surface. The method of forming fluff is not particularly limited, and various methods commonly performed in the field such as sanding by sandpaper or the like can be used. If the pile length is too short, it is difficult to obtain a beautiful appearance, and if it is too long, there is a tendency for haggling to easily occur, so the pile length is preferably set to 0.2 mm or more and 1.0 mm or less.

Moreover, in one aspect of the present invention, polysiloxane or the like may be applied as a slipping agent to the non-raised sheet-like article before the raising treatment. By imparting a slip agent, the fuzzing of the surface polishing can be facilitated, and the surface quality becomes very good, which is better. In addition, an antistatic agent may be added before the raising treatment. With the provision of antistatic agents, it is a preferable aspect that the grinding powder generated from the grinding of the flakes is not easy to accumulate on the sandpaper.

Furthermore, in one aspect of the present invention, style design can be applied to the surface as needed. For example, post-processing such as perforation processing, embossing processing, laser processing, ultrasonic welding (pinsonic) processing, and printing processing can be applied. [Example]

Next, examples are used to explain the sheet of the present invention more specifically, but the present invention is not limited by these examples.

[Evaluation method] (1) Average single fiber diameter of flakes: Using a scanning electron microscope (SEM, VE-7800 manufactured by KEYENCE Co., Ltd.), the cross section of the sheet including fibers perpendicular to the thickness direction was observed at 3000 times, and 50 samples were randomly extracted within a 30μm×30μm field of view. The single fiber diameter is measured in μm units to the first decimal place.

Perform it at 3 places, measure the diameter of a total of 150 single fibers, and calculate the average value to the first decimal place. When fibers with a fiber diameter of more than 50 μm are mixed, the fibers are considered to be incompatible with ultrafine fibers, and are excluded from the measurement of the average fiber diameter. In addition, when the ultrafine fiber has a profiled cross-section, as described above, first, the cross-sectional area of the single fiber is measured, and the diameter when the cross-section is regarded as a circle is calculated, and the diameter of the single fiber is obtained. Calculate the average value using it as the matrix and use it as the average single fiber diameter.

(2) Solidification temperature of water dispersion Put 20 g of the aqueous dispersion containing the polymer elastomer prepared in each of the Examples and Comparative Examples into a test tube with an inner diameter of 12 mm, insert the thermometer so that the tip is below the liquid level, and seal the test tube. In a warm water bath at a temperature of 95°C, the liquid surface of the water dispersion is immersed below the liquid level of the warm water bath. While checking the temperature rise in the test tube with a thermometer, lift the test tube upwards within 5 seconds as appropriate every time to check whether the liquid surface of the aqueous dispersion is shaken. The temperature at which the liquid surface of the aqueous dispersion loses fluidity is regarded as the freezing temperature. This measurement was performed three times for each type of aqueous dispersion, and the average value was calculated.

(3) Evaluation of the flexibility of the sheet: According to the method A (45° cantilever method) described in 8.21.1 of JIS L 1096:2010 "Testing Methods for Grey Fabrics of Woven Fabrics and Knitted Fabrics", 8.21 The test piece is placed on a water platform with an inclined surface at an angle of 45°, the test piece is slid, and the scale when the center point of one end of the test piece is in contact with the inclined surface is read, and the average value of the 5 pieces is obtained.

(4) Evaluation of abrasion of flakes According to JIS L 1096:2010, the abrasion evaluation was performed. The Model 406 manufactured by James H. Heal & Co. was used as the Martindale abrasion tester, and the ABRASTIVE CLOTH SM25 of the same company was used as the standard friction cloth. For the sheet before and after the light resistance test described later, a load of 12 kPa was applied, and the number of times of abrasion was 20,000 times. Using the mass of the flakes before and after abrasion, the abrasion reduction is calculated by the following formula.

Abrasion loss (mg) = mass before abrasion (mg)-mass after abrasion (mg) Moreover, the reduction in wear is the value after rounding the first decimal point as the reduction in wear.

(5) The light fastness test of the sheet is carried out in accordance with JIS L 0843: 2006 light fastness measurement method (B method, 5th exposure method), under the condition of adjusting the measurement time ^{so that the xenon arc irradiation amount becomes 110MJ/m 2} Irradiate.

(6) Identification of bonding types in polymer elastomers For the polymer elastomer separated from the above-mentioned sheet, the FT/IR 4000 series manufactured by JASCO Corporation was used, and the type of bonding was identified by infrared spectroscopy.

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

(8) Determination of the type and content of inorganic salts contained in the flakes: The sheet was immersed in N,N-dimethylformamide overnight, and then heated and dried at 140°C to concentrate the solution in which the polymer elastomer and inorganic salt had been eluted to solidify it. For the obtained solids, distilled water is added to dissolve 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 is measured. In addition, after the solidified polymer elastomer was heated and dried, the mass was measured, and the mass of the inorganic salt compared with the mass of the polymer elastomer was calculated. However, from the point of view of the validity of the numerical value, compared with the polymer elastomer, less than 0.1% by mass is considered to be less than the lower limit of detection.

Regarding the type of inorganic salt, the above-mentioned aqueous solution containing inorganic salt was identified using an ion chromatography device manufactured by DIONEX Corporation "ICS-3000".

[Method for manufacturing non-woven fabric A for fibrous base material] SSIA (5-sulfoisophthalate) 8 mol% copolymerized polyester is used as the sea component, and polyethylene terephthalate is used as the island component. The sea component is 20% by mass and the island component is 80% by mass to obtain a sea-island composite fiber with 16 islands per filament and an average single fiber diameter of 20 μm. The obtained sea-island composite fiber is cut into short fibers with a fiber length of 51mm, and a fiber web is formed by a carding machine and a cross-layer. By needle punching, the production weight per unit area is 700g/m ² and the thickness is 3.0mm. The non-woven fabric. The non-woven fabric thus obtained was immersed in hot water at a temperature of 98°C for 2 minutes to shrink it, and dried at a temperature of 100°C for 5 minutes to form a non-woven fabric A for fibrous base material.

[Method for manufacturing non-woven fabric B for fibrous base material] SSIA (5-sulfoisophthalate) 8 mol% copolymerized polyester is used as the sea component, and polyethylene terephthalate is used as the island component. The sea component was 43% by mass and the island component was 57% by mass. The sea-island composite fiber with 16 islands per filament and an average single fiber diameter of 20 μm was obtained. The obtained sea-island composite fiber is cut into short fibers with a fiber length of 51mm, and a fiber web is formed by a carding machine and a cross-layer. By needle punching, the production weight per unit area is 550g/m ² and the thickness is 2.9mm. The non-woven fabric. The non-woven fabric thus obtained was immersed in hot water at a temperature of 98°C for 2 minutes to shrink it, and dried at a temperature of 100°C for 5 minutes to form a non-woven fabric B for fibrous base material.

[Manufacturing method of polymer elastomer] Polytetramethylene ether glycol with a number average molecular weight (Mn) of 2,000 (referred to as PTMG in the table) is used for the polyol, MDI is used for the isocyanate, and 2,2-dimethylol is used as the hydrophilic group-containing component Propionic acid, made into a prepolymer in toluene solvent. Ethylene glycol and ethylenediamine as chain extenders, polyoxyethylene nonylphenyl ether and water as external emulsifiers were added and stirred. The pressure was reduced to remove toluene, and an aqueous dispersion of the polymer elastomer was obtained.

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

(Addition of polymer elastomer) With respect to 100 parts by mass of polymer elastomer, add 20 parts by mass of sodium sulfate (described as "Na ₂ SO ₄ "in Table 1) as a heat-sensitive coagulant, and add 3 parts by mass of carbon The diimine-based crosslinking agent was prepared with water to a solid content of 12% by mass, and an aqueous dispersion containing a polymer elastomer was obtained. The heat-sensitive solidification temperature is 70°C. The obtained fibrous base material nonwoven fabric A was immersed in the aforementioned aqueous dispersion, and then dried by hot air at a temperature of 160°C for 20 minutes. The polymer elastomer was applied so that the body became 20% by mass, and a non-woven fabric with a thickness of 2.10 mm was obtained.

(Extremely fine fiber display treatment) The obtained non-woven fabric imparted with polymer elastomer was immersed in a sodium hydroxide aqueous solution with 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 composite fiber. Then, the sodium hydroxide aqueous solution adhering to the non-woven fabric was immersed in water to wash for 30 minutes, and dried in a dryer at 160° C. for 30 minutes to obtain a sheet containing ultrafine fibers (a polymer elastomer-provided sheet).

(Dyeing and finishing) The obtained polymer elastomer-imparted sheet after sea removal was cut in half vertically in the thickness direction, and the opposite side of the cut half surface was polished with sandpaper No. 180 ring sandpaper to obtain a fluffy sheet with a thickness of 0.75mm. Flakes.

Using a liquid stream dyeing machine, the resulting fluffy sheet was dyed with black dye at a temperature of 120°C. Then, it was dried with a dryer to obtain a sheet with an average single fiber diameter of ultrafine fibers of 4.4 μm. The obtained sheet has a stiffness of 80mm, a wear loss before the light resistance test of 7 mg, and a wear loss after the light resistance test of 9 mg, which has a soft hand and excellent light resistance and abrasion resistance. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 93%, and it has excellent heat resistance. The amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Endowment of polymer elastomer) The heat-sensitive coagulant was changed to sodium chloride (described as "NaCl" in Table 1). In addition, the same procedure as in Example 1 was carried out except that the addition amount of the thermosensitive coagulant, the heating temperature of the hot air, and the amount of the polymer elastomer were changed to obtain a nonwoven fabric to which the polymer elastomer was provided.

(Extremely fine fiber display treatment) Except for changing the drying temperature, the same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. The obtained sheet has a stiffness of 90 mm, a wear loss before the light resistance test is 6 mg, and a wear loss after the light resistance test is 8 mg. It has a soft hand and excellent light resistance and abrasion resistance. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. In addition, the retention rate of the L value is 91%, and it has excellent heat resistance. The amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Endowment of polymer elastomer) Except for changing the addition amount of the thermal coagulant, the heating temperature of the hot air, and the amount of the polymer elastomer, the same procedure as in Example 1 was carried out to obtain a polymer elastomer-provided nonwoven fabric.

(Extremely fine fiber display treatment) Except for changing the drying temperature, the same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. The resulting sheet has a stiffness 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. It has a soft hand and excellent light resistance and abrasion resistance. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 97%, and it has excellent heat resistance. The amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Endowment of polymer elastomer) Except for changing the heating temperature of the hot air and the amount of the polymer elastomer applied, the same procedure as in Example 2 was carried out to obtain a polymer elastomer-provided nonwoven fabric with a thickness of 2.05 mm.

(Extremely fine fiber display treatment) The obtained non-woven fabric imparted with polymer elastomer was immersed in a sodium hydroxide aqueous solution with 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 island-in-the-sea composite fiber. Then, the sodium hydroxide aqueous solution adhering to the non-woven fabric was immersed in water to wash for 30 minutes, and dried in a dryer at 170° C. for 30 minutes to obtain a sheet containing ultrafine fibers (a polymer elastomer-provided sheet).

(Dyeing and finishing) The obtained polymer elastomer-imparted sheet after sea removal was cut in half vertically in the thickness direction, and the opposite side of the cut half surface was polished with sandpaper No. 120 circular sandpaper to obtain a fluffy sheet with a thickness of 0.75 mm Matter.

Using a liquid stream dyeing machine, the resulting fluffy sheet was dyed with black dye at a temperature of 120°C. Then, it was dried with a dryer to obtain a sheet with an average single fiber diameter of ultrafine fibers of 3.0 μm. The obtained sheet has a stiffness of 75mm, a wear loss before the light resistance test of 7 mg, and a wear loss after the light resistance test of 10 mg, which has a soft hand and excellent light resistance and abrasion resistance. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 96%, and it has excellent heat resistance. The amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Endowment of polymer elastomer) Except for changing the addition amount of the heat-sensitive coagulant and the heat-sensitive coagulant, and the amount of the polymer elastomer provided, the same procedure as in Example 1 was carried out to obtain a polymer elastomer-provided nonwoven fabric.

(Extremely fine fiber display treatment) The same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. The resulting sheet has a stiffness 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, which has a soft hand and excellent light resistance and abrasion resistance. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Moreover, the retention rate of the L value is 94%, and it has excellent heat resistance. The amount of the monovalent cation-containing inorganic salt in the polymer elastomer is 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.

(Endowment of polymer elastomer) In the same manner as in Example 4, a nonwoven fabric provided with a polymer elastomer was obtained.

(Extremely fine fiber display treatment) The same procedure as in Example 4 was carried out.

(Dyeing and finishing) Both sides of the obtained polymer elastomer-imparted sheet after sea removal were polished with sandpaper No. 180 ring-shaped sandpaper to obtain a fluffy sheet with a thickness of 1.50 mm.

Using a liquid stream dyeing machine, the resulting fluffy sheet was dyed with black dye at a temperature of 120°C. Then, after drying with a dryer, it was cut in half vertically in the thickness direction to obtain a sheet-like article having an ultrafine fiber with an average single fiber diameter of 3.0 μm.

The resulting sheet has a stiffness of 80mm, a wear loss before the light resistance test of 6mg, and a wear loss after the light resistance test of 9mg, which has a soft hand and excellent light resistance and abrasion resistance. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 96%, and it has excellent heat resistance. The amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Addition of polymer elastomer) With respect to 100 parts by mass of polymer elastomer, add 10 parts by mass of magnesium sulfate (described as "MgSO ₄ "in Table 1) as a heat-sensitive coagulant, and 3 parts by mass of carbon dioxide The amine-based crosslinking agent is prepared with water to a solid content of 12% by mass to obtain an aqueous dispersion containing a polymer elastomer. However, it gels on the surface of the non-woven fabric during processing, and the polymer elastomer cannot be imparted to the Non-woven.

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

(Endowment of polymer elastomer) Except for changing the addition amount of the thermosensitive coagulant, the same procedure as in Example 1 was carried out to obtain a polymer elastomer-imparted nonwoven fabric.

(Extremely fine fiber display treatment) The same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. Since the stiffness of the obtained sheet was greater than 150 mm, it could not be measured, and it had a hard hand feeling. The abrasion loss before the light resistance test was 15 mg, and the abrasion loss after the light resistance test was 25 mg. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value was 87%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was less than the lower limit of detection.

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

(Endowment of polymer elastomer) Except for changing the addition amount of the thermosensitive coagulant, the same procedure as in Example 1 was carried out to obtain a polymer elastomer-imparted nonwoven fabric.

(Extremely fine fiber display treatment) The same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. Since the stiffness of the obtained sheet was greater than 150 mm, it could not be measured, and it had a hard hand feeling. The abrasion loss before the light fastness test was 16 mg, and the abrasion loss after the light fastness test was 28 mg, and the light fastness was at a disadvantage. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value was 89%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was less than the lower limit of detection.

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

(Endowment of polymer elastomer) Except that no crosslinking agent was provided, the same procedure as in Example 2 was carried out to obtain a nonwoven fabric provided with a polymer elastomer.

(Extremely fine fiber display treatment) The same procedure as in Example 2 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. Since the stiffness of the obtained sheet was greater than 150 mm, it could not be measured, and it had a hard hand feeling. The abrasion loss before the light resistance test was 21 mg, and the abrasion loss after the light resistance test was 32 mg. The light resistance and abrasion resistance are at a disadvantage. In addition, there are no N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 88%, the heat resistance is insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Endowment of polymer elastomer) Except for changing the heating temperature, the same procedure as in Example 1 was carried out to obtain a nonwoven fabric provided with a polymer elastomer.

(Extremely fine fiber display treatment) The same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. The resulting sheet-like material had a stiffness of 120 mm, a loss in abrasion before the light resistance test was 13 mg, and a loss in abrasion after the light resistance test was 29 mg, and the light resistance was at a disadvantage. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 88%, the heat resistance is insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Endowment of polymer elastomer) In the same manner as in Example 1, a nonwoven fabric provided with a polymer elastomer was obtained.

(Extremely fine fiber display treatment) Except for changing the drying temperature, the same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. The resulting sheet-like material had a stiffness of 130 mm, a loss in abrasion before the light resistance test was 16 mg, and a loss in abrasion after the light resistance test was 30 mg, and the light resistance was inferior. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 88%, the heat resistance is insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

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

(Endowment of polymer elastomer) With respect to 100 parts by mass of polymer elastomer, 3 parts by mass of carbodiimide-based crosslinking agent is added, and the active ingredient is added so that 1 part by mass relative to 100 parts by mass of polymer elastomer is a non-ionic thickening agent. Agent (guar gum) ["Neosoft G" manufactured by Taiyo Chemical Co., Ltd.], the whole was prepared with water to a solid content of 13% by mass, and an aqueous dispersion containing a polymer elastomer was obtained. The resulting non-woven fabric was immersed in the aforementioned aqueous dispersion, and 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. % Of the polymer elastomer is 20% by mass, and the polymer elastomer is imparted to obtain a nonwoven fabric with a thickness of 2.10 mm.

(Extremely fine fiber display treatment) The same procedure as in Example 1 was carried out.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. The resulting sheet-like material had a stiffness 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 abrasion resistance were inferior. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value was 87%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer was less than the lower limit of detection.

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

(Endowment of polymer elastomer) Except that no crosslinking agent was provided, the same procedure as in Example 2 was carried out to obtain a nonwoven fabric provided with a polymer elastomer.

(Extremely fine fiber display treatment) The obtained non-woven fabric imparted with polymer elastomer was immersed in a sodium hydroxide aqueous solution with 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 composite fiber. Next, the sodium hydroxide aqueous solution adhering to the nonwoven fabric was immersed in water to wash for 30 minutes, and dried in a dryer at 120°C for 30 minutes. Then, water was added to the carbodiimide-based crosslinking agent to impregnate and apply the crosslinking agent to a total solid content of 2% by mass. The sheet was dried in a dryer at 160°C for 30 minutes to obtain ultrafine fibers. Sheets (sheets provided with polymer elastomers).

(Dyeing and finishing) The same procedure as in Example 1 was carried out. Since the stiffness of the obtained sheet was greater than 150 mm, it could not be measured, and it had a hard hand feeling. The abrasion loss before the light resistance test was 20 mg, and the abrasion loss after the light resistance test was 30 mg. The light resistance and abrasion resistance are at a disadvantage. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value was 86%, the heat resistance was insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer 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.

(Endowment of polymer elastomer) The non-woven fabric was impregnated with a 10% by mass aqueous solution of PVA (NM-14 manufactured by Nippon Synthetic Chemical Co., Ltd.) with a saponification degree 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 base For the fiber mass of the nonwoven fabric for materials 100 parts by mass, the adhesion amount of PVA is 30 parts by mass of the PVA-provided sheet.

The obtained PVA-imparted sheet was immersed in an 8g/L sodium hydroxide aqueous solution heated to a temperature of 95°C and treated for 30 minutes to obtain a sheet containing ultrafine fibers after removing the sea component of the island-in-the-sea composite fiber ( Extra-fine fiber non-woven fabric endowed with PVA).

With respect to 100 parts by mass of the polymer elastomer, 15 parts by mass of sodium chloride (described as "NaCl" in Table 1) is added as a heat-sensitive coagulant, and 3 parts by mass of a carbodiimide-based crosslinking agent is added. The entire water was prepared to have a solid content of 12% by mass, and an aqueous dispersion containing a polymer elastomer was obtained. The heat-sensitive solidification temperature is 68°C. The obtained fibrous base material nonwoven fabric A was immersed in the aforementioned aqueous dispersion, and then dried by hot air at a temperature of 160°C for 20 minutes. The polymer elastomer was provided so that the body became 38% by mass, and a polymer elastomer-provided sheet having a thickness of 2.05 mm was obtained.

The obtained polymer elastomer-imparted sheet was immersed in water heated to 95° C., treated for 10 minutes, and dried in a dryer at 120° C. for 30 minutes to obtain a sheet from which the imparted PVA was removed.

(Dyeing and finishing) The same procedure as in Example 1 was carried out. The resulting sheet-like material had a stiffness of 90 mm, a loss in abrasion before the light resistance test was 11 mg, and a loss in abrasion after the light resistance test was 26 mg, and the light resistance was at a disadvantage. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 91%, and it has excellent heat resistance. The amount of the monovalent cation-containing inorganic salt in the polymer elastomer is 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.

(Endowment of polymer elastomer) Except for changing the heating temperature, the same procedure as in Example 6 was carried out to obtain a nonwoven fabric provided with a polymer elastomer.

(Extremely fine fiber display treatment) Except for changing the drying temperature, the same procedure as in Example 6 was carried out.

(Dyeing and finishing) The same procedure as in Example 6 was carried out. The resulting sheet-like material had a stiffness of 85 mm, a loss in abrasion before the light resistance test was 21 mg, and a loss in abrasion after the light resistance test was 31 mg, and the light resistance and abrasion resistance were inferior. In addition, there are N-urea bonds and isourea bonds in the polymer elastomer. Furthermore, the retention rate of the L value is 85%, the heat resistance is insufficient, and the amount of the monovalent cation-containing inorganic salt in the polymer elastomer is less than the lower limit of detection.

[Table 1] Water dispersion liquid containing polymer elastomer with hydrophilic group Processing conditions Thermal coagulant Crosslinking agent Polymer elastomer imparting steps Drying step type Addition amount (parts by mass) Heating temperature (℃) Drying temperature (℃) Example 1 Na ₂ SO ₄ 20 Carbodiimide series 160 160 Example 2 NaCl 15 Carbodiimide series 150 155 Example 3 Na ₂ SO ₄ 15 Carbodiimide series 170 170 Example 4 NaCl 15 Carbodiimide series 160 170 Example 5 NaCl 40 Carbodiimide series 160 160 Example 6 NaCl 15 Carbodiimide series 160 170 Comparative example 1 MgSO ₄ 10 Carbodiimide series - - Comparative example 2 Na ₂ SO ₄ 1 Carbodiimide series 160 160 Comparative example 3 Na ₂ SO ₄ 55 Carbodiimide series 160 160 Comparative example 4 NaCl 15 - 150 155 Comparative example 5 Na ₂ SO ₄ 20 Carbodiimide series 110 160 Comparative example 6 Na ₂ SO ₄ 20 Carbodiimide series 160 110 Comparative example 7 - - Carbodiimide series 160 160 Comparative example 8 NaCl 15 - 150 160 Comparative example 9 NaCl 15 Carbodiimide series 160 - Comparative example 10 NaCl 15 Carbodiimide series 110 110

[Table 2] Average single fiber diameter (μm) PU amount (mass%) Whether there is N-glycylurea bond/isourea bond Stiffness (mm) Abrasion loss (mg) L value retention rate (%) Before lightfastness test After light resistance test Example 1 4.4 20 Have 80 7 9 93 Example 2 4.4 30 Have 90 6 8 91 Example 3 4.4 16 Have 55 12 18 97 Example 4 3.0 38 Have 75 7 10 96 Example 5 4.4 32 Have 100 6 8 94 Example 6 3.0 38 Have 80 6 9 96 Comparative example 1 - - - - - - - Comparative example 2 4.4 20 Have ＞ 150 15 25 87 Comparative example 3 4.4 20 Have ＞ 150 16 28 89 Comparative example 4 4.4 30 without ＞ 150 twenty one 32 88 Comparative example 5 4.4 20 Have 120 13 29 88 Comparative example 6 4.4 20 Have 130 16 30 88 Comparative example 7 4.4 20 Have 90 20 33 87 Comparative example 8 4.4 20 without ＞ 150 20 30 86 Comparative example 9 3.0 38 Have 90 11 26 91 Comparative example 10 3.0 38 Have 85 twenty one 31 85

Furthermore, "PU" in Table 2 means polyurethane. [Possibility of Industrial Use]

The sheet material obtained by the present invention can be used as a skin material for furniture, chairs and wall materials, or seats, ceilings and interiors in vehicles such as automobiles, trams and aircrafts, and has a very beautiful appearance. Materials, shirts, jackets, casual shoes, sports shoes, men’s shoes and women’s shoes, shoe uppers, decorations, leather bags, belts, wallets, etc., as well as materials for clothing, wiping cloths, and abrasives used in some of them Industrial materials such as cloth and CD sheath.

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Claims (8)

A sheet-like article, which is a sheet-like article containing a polymer elastomer in a fibrous base material, wherein the fibrous base material contains ultrafine fibers with an average single fiber diameter of 0.1 μm or more and 10 μm or less, and the polymer elastomer has a hydrophilic base , And containing polyether glycol as a constituent, having N-urea bonds and/or isourea bonds in the polymer elastomer, the sheet satisfies the following conditions 1 and 2; Condition 1: JIS L 1096: The stiffness in the longitudinal direction specified by Method A (45° cantilever method) described in 2010 "Test Methods for Grey Fabrics of Woven Fabrics and Knitted Fabrics" is 40mm or more and 140mm or less. Condition 2: Light fastness in JIS L 0843: 2006 The amount of xenon arc measured by the degree of measurement method is 110MJ/m ² after the light resistance test, and the abrasion loss after 20,000 times of the Martindale abrasion test specified in JIS L 1096:2005 is 25 mg or less. As for the sheet of claim 1, among the sheets before the light resistance test, the abrasion loss of 20,000 times of the Martindale abrasion test specified in JIS L 1096:2010 is 20 mg or less. The sheet of claim 1 or 2, which contains 10% by mass or more of the polymer elastomer. Such as the sheet of any one of claims 1 to 3, wherein the sheet further satisfies the following condition 3; Condition 3: The raised surface of the sheet is placed on a hot plate heated to 150°C, and the retention rate of the L value when pressed with a pressing load of 2.5 kPa for 10 seconds is 90% or more and 100% or less. A method for manufacturing a sheet, which sequentially includes the following steps (1) to (4): (1) A polymer elastomer impregnation step, which involves impregnating a fibrous substrate containing ultra-fine fiber-exposed fibers with an aqueous dispersion containing a polymer elastomer, an inorganic salt containing monovalent cations, and a crosslinking agent, followed by 120 The step of impregnating a polymer elastomer that is heat-treated at a temperature above 180°C. The polymer elastomer has a hydrophilic group and contains polyether glycol as a constituent. The aqueous dispersion contains monovalent cations. 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 elastomer; (2) The ultra-fine fiber unfolding step, which is to process the ultra-fine fiber unfolding fiber with alkali to make the ultra-fine fiber unfold; (3) The drying step, which is heat treatment at a temperature above 120°C and below 180°C; (4) Raising step, which is to raise at least one side of the unfluffed sheet to form fluff on the surface. The method for manufacturing a sheet according to claim 5, wherein after the drying step, it includes a dyeing step of dyeing the non-fuzzy sheet or the sheet. According to claim 5 or 6, the method for manufacturing a sheet-like article, wherein the monovalent cation-containing inorganic salt is sodium chloride and/or sodium sulfate. The method for producing a sheet-like article according to any one of claims 5 to 7, wherein the crosslinking agent is a carbodiimide-based crosslinking agent.