JP6039992B2 - Water-dispersible polyurethane resin composition, sheet-like material, and method for producing sheet-like material - Google Patents

Description

  The present invention relates to a water-dispersed polyurethane resin composition, a sheet-like material, and a method for producing a sheet-like material.

  More specifically, especially in the production of environment-friendly leather-like sheets that do not use organic solvents in the production process, sandpaper is less clogged in the raising process, productivity is good, and flexible texture The present invention relates to a water-dispersed polyurethane resin composition that achieves both realization of wrinkles and good wrinkle recovery property that does not cause wrinkles, a sheet-like material using the same, and a method for producing the sheet-like material.

  A leather-like sheet-like product mainly composed of a fibrous base material and polyurethane has excellent characteristics not found in natural leather, and is widely used in various applications. In particular, sheet-like materials using a polyester-based fibrous base material are excellent in light resistance, and therefore their use has been expanded year by year for clothing, chair upholstery, and automobile interior materials.

  In producing such a sheet-like product, after impregnating a fibrous base material with an organic solvent solution of polyurethane, the fibrous base material impregnated with the organic solvent solution of polyurethane is treated with water which is a non-solvent of polyurethane. Alternatively, a combination of steps of dipping in an aqueous organic solvent solution and wet coagulating polyurethane is generally employed.

  A water-miscible organic solvent such as N, N-dimethylformamide is used as the organic solvent that is a solvent for such polyurethane. However, since organic solvents are generally highly harmful to the human body and the environment, a method that does not use organic solvents is strongly demanded in the production of sheet-like materials.

  As a specific solution, for example, a method in which polyurethane is dry-coagulated using water-dispersed polyurethane in which polyurethane is dispersed in water instead of conventional organic solvent type polyurethane has been studied. However, the sheet-like material provided by impregnating the fiber base material with water-dispersible polyurethane, compared with the sheet-like material provided by impregnating the conventional organic solvent type polyurethane, There was a problem in that wrinkles remained easily and wrinkle recovery was not good.

  Specifically, when a fibrous base material is impregnated with water-dispersed polyurethane and dry-solidified, a migration phenomenon occurs and the polyurethane is unevenly distributed in the fibrous base material, so that the texture becomes hard.

  In the case of a conventional organic solvent type polyurethane, since the polyurethane is coagulated by a wet coagulation method generally immersed in water after impregnating the fibrous base material, the polyurethane is made porous by replacing the organic solvent with water. The structure is such that polyurethane does not strongly grip the entangled portions of the fibers of the fibrous base material, and the texture of the sheet-like material becomes flexible. On the other hand, in the case of water-dispersed polyurethane, the solidification of the polyurethane after impregnating the fibrous base material is generally based on a dry coagulation method by drying by heating. By strongly grasping the entangled portion of the fiber of the fibrous base material, the texture of the sheet-like material becomes hard.

  Therefore, in the method using water-dispersed polyurethane, various studies and proposals as described below have been made regarding softening of the texture.

  In the method using water-dispersed polyurethane, a method has been proposed in which migration is suppressed by adding an inorganic salt as a heat-sensitive coagulant to the water-dispersed polyurethane and eliminating the fluidity of the water-dispersed polyurethane by heating (patent) Reference 1).

  However, in the proposal of Patent Document 1, since the polyurethane has not been sufficiently studied for strongly gripping the entangled portion of the fiber of the fibrous base material, the texture of the sheet-like material is the flexibility of the polyurethane itself. It will be strongly influenced. For this reason, it is conceivable to apply a flexible polyurethane having low crystallinity in order to develop a flexible texture in the sheet-like material. However, in that case, the abrasion resistance of the sheet-like material is deteriorated, and further, sandpaper used for grinding and raising is easily clogged to obtain a good napped quality. Further, the productivity of the raising process is poor. In addition, when flexible polyurethane is applied, there is a problem that wrinkles are difficult to recover when wrinkles occur in the sheet-like material.

  Regarding the method of weakening the gripping force of the fiber entanglement point of polyurethane, the method of applying the flexible water-dispersed polyurethane described below, or the porous structure obtained by wet coagulation of organic solvent type polyurethane with water-dispersible polyurethane A method of obtaining has been proposed.

That is, as a method of applying a flexible water-dispersible polyurethane, a water-dispersible polyurethane to be applied to a fibrous base material is a heat-sensitive gelling film having a thickness of 100 μm obtained by drying at a temperature of 50 ° C. The elastic modulus at a temperature of 90 ° C. is 2.0 × 10 ^{7 to} 5.0 × 10 ⁸ dyn / cm ² , the elastic modulus at 160 ° C. is 1.0 × 10 ⁷ dyn / cm ² or more, and the temperature of α dispersion (Tα ) Is proposed to use a polyurethane having a temperature of −30 ° C. or less (Patent Document 2). With this proposal, a sheet-like material having a soft texture is obtained. However, when flexible polyurethane is used as in this proposal, the wear resistance of the sheet-like material is deteriorated and further ground and raised. Since sandpaper or the like used for processing is easily clogged, it is difficult to obtain a good napped quality, and productivity is also inferior. Moreover, when wrinkles are generated in the sheet-like material, there is a problem that wrinkles are difficult to recover.

  In addition, as a technique for obtaining a porous structure such as an organic solvent type wet-coagulated polyurethane using water-dispersed polyurethane, the structure of the polyurethane in the fibrous base material is obtained by adding an associative thickener to the water-dispersed polyurethane. Has been proposed to have a porous structure (Patent Document 3). In this proposal, since the polyurethane has a porous structure, the bonding area between the fiber and the polyurethane is reduced, and the gripping force at the entanglement point of the fiber is weakened. However, when an associative thickener is added to a water-dispersible polyurethane, the sheet impregnated with the polyurethane is sticky due to the associative thickener, so a cleaning process for the associative thickener is required. Productivity is low. Furthermore, the associative thickener is dissolved in the water-dispersible polyurethane, and the pores of the polyurethane structure are generated in the existing part of the associative thickener, so the pore diameter cannot be increased. A clear sheet-like texture softening effect cannot be obtained.

  In addition, a coating sheet has been proposed in which a foam stabilizer is added to water-dispersible polyurethane, mechanically foamed, and coated (Patent Document 4). In this proposal, a polyurethane film having a porous structure can be obtained by coating the surface of a fibrous base material with a mechanically foamed water-dispersible polyurethane, but the fibrous base material is impregnated with the foamed water-dispersible polyurethane. When applied, the foam disappears during impregnation, so that the polyurethane cannot have a porous structure inside the fibrous base material.

  Furthermore, a proposal has been made to use a heat-expandable water-dispersible polyurethane together with a heat-expandable plastic microballoon (Patent Document 5). In the proposal of Patent Document 5, the migration of the water-dispersed polyurethane in the sheet-like material is suppressed, and the texture of the sheet-like material is softened by making the water-dispersible polyurethane a porous structure with a thermally expandable microballoon. It has become. However, the polyurethane specifically disclosed in this proposal is only a flexible polyurethane having polybutylene adipate diol and polyoxyethylene propylene random copolymer glycol as a polyol component, and other polyurethane compositions are not disclosed. Absent. When flexible polyurethane is applied, the texture of the sheet-like material becomes soft, but the abrasion resistance of the sheet-like material, wrinkle recovery property when wrinkles occur, and sandpaper when ground and brushed Productivity was inferior, such as clogging.

JP-A-7-229071 JP 2000-17582 A JP 2000-297211 A JP 2002-69858 A JP-A-1-104634

  In the prior art, when producing a sheet-like material in a process that does not use an organic solvent, the sheet-like material having good productivity in the raising process and having both a soft texture and a wrinkle recovery property, and the same are produced. No water-dispersible polyurethane resin composition has been obtained so far.

  An object of the present invention is to provide a water-dispersed polyurethane resin composition that achieves both a soft texture and good wrinkle recovery properties that do not cause wrinkles, a sheet-like product using the same, and a method for producing the sheet-like product. is there.

The water-dispersed polyurethane resin composition of the present invention that achieves the above-described object has the following configuration (1).
(1) A water-dispersible polyurethane resin, a microballoon, and a film- forming silicone , and a dry membrane formed from the water-dispersible polyurethane resin has a 100% modulus of 2 to 8 MPa, and the water-dispersible polyurethane A water-dispersed polyurethane resin composition, wherein the dry film formed from a resin has a glass transition temperature of -25 ° C to 0 ° C.

In addition, the water-dispersed polyurethane resin composition of the present invention preferably has any one of the following (2) to (3).
(2) The water-dispersible polyurethane resin composition as described in (1) above, wherein the water-dispersible polyurethane resin has a hydrophilic group.
(3) The water-dispersed polyurethane resin composition according to the above (1) or (2), wherein the expansion start temperature T1 (° C.) of the microballoon has a relationship represented by the following formula (a).
40 ≦ T1 ≦ 150 (a) formula

Moreover, the sheet-like material of the present invention that achieves the above-described object has the following configuration (4).
(4) A sheet-like material containing polyurethane inside a fibrous base material comprising ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm, wherein the polyurethane is any of the above (1) to (3) A sheet-like product comprising the water-dispersible polyurethane resin composition according to any one of the above.

Moreover, the manufacturing method of the sheet-like material of this invention which achieves the objective mentioned above has the following structure ( 5 ).
( 5 ) A fibrous base material comprising fibers having an average single fiber diameter of 10 to 40 μm is impregnated with an aqueous dispersion of the water-dispersible polyurethane resin composition according to any one of (1) to (3) above. Then, after the wet heat treatment, the polyurethane is solidified by dry heat treatment.

  According to the present invention, in a sheet-like material manufactured using a water-dispersed polyurethane resin composition in consideration of the environment in which no organic solvent is used in the manufacturing process, there is little clogging due to sandpaper in the raising process, and productivity is low. A sheet-like material having good softness that can be used practically as a garment and a good wrinkle recovery property that does not wrinkle when folded after folding and a manufacturing method thereof are obtained.

  Moreover, according to this invention, the water dispersion-type polyurethane resin composition used optimally for manufacture of this sheet-like material is obtained.

  The sheet-like material of the present invention is a sheet-like material comprising a coagulated product of a water-dispersible polyurethane resin composition inside a fibrous base material comprising ultrafine fibers having an average single fiber diameter of 0.3 to 7 μm. is there.

  Examples of fibers constituting the fibrous base material include polyethylene terephthalate, polybutylene terephthalate, polyester such as polytrimethylene terephthalate or polylactic acid, polyamide such as 6-nylon and 66-nylon, polyacryl, polyethylene, polypropylene, and thermoplastic cellulose. A fiber made of a thermoplastic resin that can be melt-spun such as can be used. Among these, polyester fibers are preferably used from the viewpoint of strength, dimensional stability, and light resistance.

  The fibrous base material may be configured by mixing fibers of different materials.

  The cross-sectional shape of the fibers constituting the fibrous base material may be a round cross section, but may be a polygonal shape such as an ellipse, a flat shape, or a triangle, or a modified cross section such as a sector shape or a cross shape.

  In the present invention, it is important that the average single fiber diameter of the fibers constituting the fibrous base material is 0.3 to 7 μm. By setting the average single fiber diameter to 7 μm or less, more preferably 6 μm or less, and even more preferably 5 μm or less, it is possible to obtain a sheet-like product having excellent flexibility and napping quality. On the other hand, by setting the average single fiber diameter to 0.3 μm or more, more preferably 0.7 μm or more, and even more preferably 1 μm or more, the bundle-like fibers at the time of napping such as coloring after dyeing or grinding with sandpaper are used. Excellent dispersibility and ease of judgment.

  As the form of the fibrous base material composed of ultrafine fibers, woven fabric, knitted fabric, non-woven fabric, and the like can be employed. Especially, since the surface quality of the sheet-like thing at the time of surface raising treatment is favorable, a nonwoven fabric is used preferably.

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

  The fiber length of the short fiber in the short fiber nonwoven fabric is preferably 25 to 90 mm. By setting the fiber length to 25 mm or more, a sheet-like material having excellent abrasion resistance can be obtained by entanglement. In addition, when the fiber length is 90 mm or less, it is possible to obtain a sheet-like product having a better texture and quality.

  When the fibrous base material made of ultrafine fibers is a non-woven fabric, the non-woven fabric preferably has a structure in which a bundle of fibers (fiber bundle) is entangled. When the fibers are intertwined in a bundle state, the strength of the sheet-like material is improved. As will be described later, the nonwoven fabric of this aspect can be obtained by expressing the ultrafine fibers after entanglement of the ultrafine fiber-expressing fibers in advance.

  When the ultrafine fiber or the fiber bundle thereof constitutes a nonwoven fabric, a woven fabric or a knitted fabric may be inserted for the purpose of improving the strength. The average single fiber diameter of the fibers constituting the woven or knitted fabric is preferably about 0.3 to 15 μm.

If the basis weight of the fibrous base material is too low, physical properties such as tensile strength and tear strength of the sheet-like material will be weak, and if it is too high, the texture of the sheet-like material will be hard, so 50 to 2000 g / m ² is preferable. .

  Further, if the thickness of the fibrous base material is too thin, physical properties such as tensile strength and tear strength of the sheet-like material are weakened, and if it is too thick, the texture of the sheet-like material becomes hard, so 0.1 to 5 mm preferable.

In the present invention, it is important that the water-dispersible polyurethane resin composition contains a water-dispersible polyurethane resin, a microballoon, and a film-forming silicone .

  The water-dispersed polyurethane resin is obtained by reacting a polyol, an organic polyisocyanate, and a chain extender.

  Examples of the polyol include a polymer diol. As such a polymer diol, for example, a polycarbonate diol, a polyester diol, a polyether diol, a silicone diol, and a fluorine diol can be suitably employed, and a copolymer obtained by combining these can also be used. Good. From the viewpoint of hydrolysis resistance, polycarbonate diols and polyether diols are preferably used. From the viewpoints of light resistance and heat resistance, polycarbonate and polyester diols are preferably used. From the viewpoint of the balance of hydrolysis resistance, heat resistance, and light resistance, polycarbonate diols and polyester diols are more preferable, and polycarbonate diols are particularly preferable.

  The polycarbonate-based diol can be produced by a transesterification reaction between an alkylene glycol and a carbonate ester or a reaction between phosgene or chloroformate ester and an alkylene glycol.

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

  A commercially available product can be used as the polycarbonate diol, and for example, ETERNACOLL UH series (manufactured by Ube Industries), C2090 (manufactured by Kuraray Co., Ltd.) and the like are used.

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

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

  Polybasic acids include, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydro One kind or two or more kinds selected from isophthalic acid can be mentioned.

  Examples of the polyether diol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol (PTMEG), and copolymerized diols obtained by combining them.

  Commercially available products can be used as the polyether-based diol, and specific examples include TERATHANE series (polytetramethylene ether glycol, manufactured by INVISTA).

  The number average molecular weight of the polymer diol is preferably 500 to 4000. By setting the number average molecular weight to 500 or more, more preferably 1000 or more, it is possible to prevent the texture from becoming hard. Moreover, the intensity | strength as a polyurethane is maintainable by making a number average molecular weight into 4000 or less, More preferably, 3000 or less.

  As the diol, in addition to the polymer diol, the above-described low molecular weight polyol can be used in combination with the polymer diol. As such a low molecular weight polyol, ethylene glycol is preferable.

  Examples of the organic polyisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, alicyclic diisocyanates such as dicyclohexylmethane diisocyanate and isophorone diisocyanate, and aromatic diisocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate. Or may be used in combination. Among these, alicyclic diisocyanates are preferably used from the viewpoint of light resistance.

  As the chain extender, for example, an amine chain extender such as ethylenediamine, 1,6-hexamethylenediamine or methylenebisaniline, for example, a diol chain extender such as ethylene glycol, water or the like can be used. . Moreover, the polyamine obtained by making polyisocyanate and water react can also be used as a chain extender. Furthermore, examples of the amine chain extender include alkoxysilyl group-containing amine chain extenders.

  The alkoxysilyl group-containing amine chain extender is a compound containing at least two active hydrogen groups and an alkoxysilyl group in one molecule. Specifically, for example, N-β (aminoethyl) -γ -Aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, γ- (2-aminoethyl) aminopropyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropyldiethoxysilane, N, N′-bis [ a- (trimethoxysilyl) propyl] ethylenediamine and the like.

  As the chain extender, an amine chain extender and water are preferable.

  Chain extenders can be used alone or in combination. Preferably, an amine chain extender and water are used in combination.

  A cross-linking agent may be used in combination with the water-dispersed polyurethane resin for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like. The cross-linking agent may be an external cross-linking agent added as a third component to the water-dispersible polyurethane resin, or may be an internal cross-linking agent that introduces a reactive site that becomes a cross-linked structure in advance in the molecular structure of the water-dispersible polyurethane resin. . It is preferable to use an internal cross-linking agent from the viewpoint that the cross-linking points can be formed more uniformly in the molecular structure of the water-dispersible polyurethane resin and the reduction in flexibility can be reduced.

  As the crosslinking agent, compounds having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group, and the like can be suitably used. However, when crosslinking proceeds excessively, the water-dispersed polyurethane resin tends to harden and the texture of the sheet-like material tends to harden, so that a crosslinking agent having a silanol group is preferably used in terms of the balance between reactivity and flexibility. It is done. When silanol groups are introduced into the molecular structure of a water-dispersible polyurethane resin as an internal cross-linking agent, the water-dispersed polyurethane resin impregnated and solidified in the inner space of the nonwoven fabric has a cross-linked structure due to siloxane bonds. Durability such as hydrolysis resistance of the water-dispersed polyurethane resin can be drastically improved while maintaining the texture of the product.

  In order to obtain a water-dispersed polyurethane resin, for example, a one-shot method, a prepolymer method, or the like is used, and a prepolymer method is preferably used.

  In the prepolymer method, for example, an isocyanate group-terminated prepolymer is obtained by reacting a polyol with an organic polyisocyanate. A solvent and a catalyst may be used as appropriate.

  Next, if necessary, an emulsifier (external emulsifier) is added, and then an appropriate solvent is added and blended. Then, water is added to disperse the isocyanate group-terminated prepolymer in water. Alternatively, an isocyanate group-terminated prepolymer may be added to water and dispersed in water.

  Examples of the external emulsifier include nonionic emulsifiers such as ether emulsifiers such as polyoxyethylene distyrenated phenyl ether. Such external emulsifiers usually have a cloud point, specifically a cloud point of 35-100 ° C, and further a cloud point of 50-90 ° C. Moreover, the HLB value of an external emulsifier is 7-20, for example.

  Thereafter, a chain extender is added to cause a chain extension reaction. The chain extender can be divided and blended.

  Thereafter, the solvent is distilled off.

  As a result, the water-dispersed polyurethane resin is obtained as a water-dispersed polyurethane liquid in which the water-dispersed polyurethane resin is dispersed in water.

  The water-dispersed polyurethane resin preferably has a hydrophilic group in the molecular structure. By having a hydrophilic group in the molecular structure, the dispersion / stability of the water-dispersible polyurethane resin can be improved.

  Examples of hydrophilic groups include cationic hydrophilic groups such as quaternary amine salts, anionic hydrophilic groups such as sulfonates and carboxylates, nonionic hydrophilic groups such as polyethylene glycol, and cationic hydrophilic groups. Any hydrophilic group of a combination of a group and a nonionic hydrophilic group and a combination of an anionic hydrophilic group and a nonionic hydrophilic group can be employed.

  Among these, nonionic hydrophilic groups that are free from fear of yellowing due to light and harmful effects due to a neutralizing agent are particularly preferably used.

  That is, in the case of an anionic hydrophilic group, a neutralizing agent is required. For example, the neutralizing agent is a tertiary amine such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine, and dimethylethanolamine. In this case, amine is generated and volatilized by heat generated during film formation and drying, and is released outside the system. For this reason, in order to suppress the release of air and the deterioration of the working environment, it is essential to introduce a device for recovering volatile amines.

  In addition, when the amine does not volatilize by heating and remains in the final product sheet, it may be discharged to the environment when the product is incinerated. On the other hand, in the case of a nonionic hydrophilic group, since a neutralizing agent is not used, there is no need to introduce an amine recovery device, and there is no fear of remaining amine in the sheet. In addition, when the neutralizing agent is an alkali metal such as sodium hydroxide, potassium hydroxide or calcium hydroxide, or a hydroxide of an alkaline earth metal, it becomes alkaline when the polyurethane (water-dispersed polyurethane) part gets wet with water. However, in the case of a nonionic hydrophilic group, since a neutralizing agent is not used, there is no need to worry about degradation of the water-dispersed polyurethane due to hydrolysis.

  Specific examples of the hydrophilic group include a polyoxyalkylene group such as a polyoxyethylene group.

  The water-dispersible polyurethane resin having hydrophilicity is obtained, for example, by a reaction of a polyoxyethylene chain-containing diol containing a polyoxyethylene chain (polyoxyalkylene group), an organic polyisocyanate, a polyol, and a chain extender.

  Specifically, the water-dispersible polyurethane resin having hydrophilicity is obtained by the prepolymer method using the above raw materials.

  Examples of the polyoxyethylene chain-containing diol include those disclosed in JP 2010-150398 A. A commercially available product can be used as the polyoxyethylene chain-containing diol, and specifically, DHD1000S (manufactured by Mitsui Chemicals) or the like is used.

  In addition, the content rate in the water dispersion type polyurethane resin of a polyoxyethylene chain becomes like this. Preferably it is 3-50 mass%, More preferably, it is 5-25 mass%.

  Further, as the diol, for example, a diol other than the above-described polyoxyethylene chain-containing diol may be contained. Specifically, as the polyol, for example, a polyoxyethylene chain-containing diol and a polycarbonate diol (copolymerized polycarbonate) A combination of a polyoxyethylene chain-containing polyether diol and a polymer diol such as a combination of a polyoxyethylene chain-containing diol and a polytetramethylene ether glycol. Furthermore, combined use of polyoxyethylene chain-containing polyether diol, polymer diol, and low molecular weight polyol (specifically, ethylene glycol) can also be mentioned.

  Then, an isocyanate group terminal prepolymer is obtained by mixing a polyol and an appropriate solvent, and then blending an organic polyisocyanate and an appropriate urethanization catalyst, followed by urethanation reaction.

  Subsequently, an appropriate solvent is added and blended, and then water is added to disperse the isocyanate group-terminated prepolymer in water. In the aqueous dispersion of the isocyanate group-terminated prepolymer, it is not necessary to add an external emulsifier, and the emulsion is self-emulsified because it contains polyoxyethylene chains in the molecule.

  Thereafter, in the same manner as described above, a chain extender is added to cause a chain extension reaction.

  Thereafter, the solvent is distilled off.

  As a result, a water-dispersed polyurethane liquid is obtained.

  The 100% modulus of the dry film formed from the water-dispersed polyurethane resin is 2 to 8 MPa. The 100% modulus of the dry film is an index representing the hardness of the polyurethane. By using the water-dispersed polyurethane resin within the range of the 100% modulus of the dry film, the fiber binding force in the sheet is strongly increased. In addition, good wear resistance and good wrinkle recovery can be obtained.

  On the other hand, when the 100% modulus exceeds the above upper limit, the texture of the sheet-like material is hard, and the sheet-like material almost retains its form after folding, and the wrinkle recovery property is also lowered.

  On the other hand, if the 100% modulus is less than the above lower limit, the wrinkle recovery property is lowered.

  Further, by using such a water-dispersible polyurethane resin and making the structure of the polyurethane in the sheet-like material porous by a microballoon described later, the texture can be softened structurally even with a hard polyurethane. .

  In addition, by using hard polyurethane, it shows good grindability in the napping process with sandpaper, etc., obtains an elegant appearance with napped hair, and further suppresses clogging of sandpaper to obtain good productivity. it can. The 100% modulus of the water-dispersed polyurethane dry film is preferably 2 to 6 MPa, and the texture and abrasion resistance of the sheet-like material are further improved by being in this range. The 100% modulus of the water-dispersible polyurethane dry membrane is the ratio of the hard segment structure caused by isocyanate and chain extender in the molecular structure of the water-dispersible polyurethane resin, the type of diol and organic isocyanate, and the amount of crosslinking agent used. Can be adjusted.

  The 100% modulus of the dry film is a value measured as a tensile strength in a tensile test, which will be described in detail in the following examples.

  It is important that the glass transition temperature of the dry film formed from the water-dispersed polyurethane resin is -25 ° C to 0 ° C. Similar to the 100% modulus of the polyurethane dry film described above, the glass transition temperature of polyurethane is also an index representing the hardness of the polyurethane, and by using a water-dispersed polyurethane resin with a glass transition temperature of the dry film within this range. In addition, the binding force of the fiber in the sheet-like material is strong, and good abrasion resistance is exhibited, and good wrinkle recovery property can be obtained. Further, by using such a water-dispersible polyurethane resin and making the structure of the polyurethane in the sheet-like material porous by a microballoon described later, the texture can be softened structurally even with a hard polyurethane. .

  In addition, by using a water-dispersed polyurethane resin with a hard dry film, it exhibits good grindability in the napping process with sandpaper, etc., gives an elegant appearance with napped hair, and further suppresses clogging with sandpaper Productivity can be obtained. The glass transition temperature of the dry film is preferably −25 ° C. to −10 ° C. Within this range, the texture and wear resistance of the sheet-like material become better.

  Specifically, if the glass transition temperature of the dry film is less than the lower limit described above, the wrinkle recoverability of the sheet-like material is lowered.

  On the other hand, when the glass transition temperature of the dry film exceeds the above upper limit, the texture of the sheet-like material is hard and the wrinkle recovery property is also lowered.

  The glass transition temperature of the dry film is adjusted by the ratio of hard segment structure due to isocyanate and chain extender in the molecular structure of the water-dispersed polyurethane resin, the type of diol and organic diisocyanate, and the amount of crosslinking agent used. can do.

  The glass transition temperature of the dry film is a value measured as a peak value of tan δ in the dynamic viscoelasticity test, which will be described in detail in Examples.

  In the present invention, the microballoon is preferably encapsulated and encapsulated in an organic compound having a specific boiling point as a swelling agent with a thermoplastic resin as a shell, preferably 5 to 300 μm, more preferably 10 A micro hollow sphere having a size of ˜25 μm. The microballoon is one in which the outer shell of the thermoplastic resin is softened by heating, and the encapsulated organic compound is gasified and expanded, and normally expands to a volume of about 50 to 100 times.

  In the present invention, the structure of polyurethane (coagulated product) is made porous by incorporating a microballoon in the water-dispersible polyurethane resin composition.

  That is, the main object of the present invention is to achieve both a soft texture and good wrinkle recovery in a sheet-like material, but in order to develop good wrinkle recovery, it is essential to apply a hard polyurethane. On the other hand, the texture becomes stiff. Therefore, in order to soften the texture, the polyurethane film structure is made porous so as to structurally soften the hard polyurethane, thereby obtaining both good wrinkle recovery and flexible texture. Furthermore, a sheet-like material having an elegant appearance having napped hairs can be obtained by incorporating a microballoon into the water-dispersible polyurethane resin composition.

  The shell of the microballoon is made of a thermoplastic resin. As the thermoplastic resin, for example, an acrylic polymer such as an acrylonitrile copolymer or a vinylidene chloride / acrylonitrile copolymer, polyurethane, or the like can be used.

  A typical example of the microballoon is one in which the thermoplastic resin is used as a shell and isobutane is encapsulated and encapsulated. However, since there are various grades in the form of fine powder or water-containing cake with different expansion start temperature T1 (° C.) and maximum expansion point depending on the polymer type, shell thickness and balloon diameter, etc. It is preferable to select appropriately according to the relationship between the solidification temperature T2 (° C.) and the treatment bath temperature with water or steam.

  It is preferable to use a microballoon having an expansion start temperature T1 (° C.) of 40 to 150 ° C. By using a material that satisfies this relationship, the microballoons are contained in the polyurethane in an expanded state, and a clear porous structure can be formed in the polyurethane. On the other hand, if the expansion start temperature T1 (° C.) of the microballoon is too low, it expands during storage at room temperature, and the dispersibility in the polyurethane water dispersion decreases, so the expansion start temperature T1 (° C.) of the microballoon is 40-150 degreeC is preferable, More preferably, it is 40-120 degreeC, Furthermore, More preferably, it is 45-100 degreeC, Most preferably, it is 50-80 degreeC. As such a microballoon, for example, those marketed as “Matsumoto Microsphere” series manufactured by Matsumoto Yushi Seiyaku Co., Ltd. or “Expancel” series manufactured by Expancel can be adopted. In general, the expansion start temperature T1 (° C.) of the microballoon may have a certain range as described in Examples described later. In such a case, in the present invention, One of the boundary values of the range may be in the range of 40 to 150 ° C. described above.

  The content of the microballoon contained in the water-dispersible polyurethane resin composition is preferably 0.1 to 10% by mass with respect to the mass of the water-dispersible polyurethane resin. If the content of the microballoon is too small, the polyurethane cannot be made into a porous structure, so the texture of the sheet-like material cannot be softened. If the content is too large, the texture of the sheet-like material becomes hard due to the hardness of the microballoon itself. The content of the microballoon is more preferably 0.5 to 5% by mass.

The water-dispersible polyurethane resin composition according to the present invention, it contains silicone. When the water-dispersible polyurethane resin composition contains silicone, the frictional force between the polyurethane structured with microballoons and the fibers of the fibrous base material is reduced, and the texture of the sheet-like material is made more flexible. Because it can.

  In addition, when adding the microballoon to the water-dispersible polyurethane resin composition, the dispersibility of the microballoon can be improved by adding silicone to the water-dispersible polyurethane liquid. The silicone content is preferably 0.1 to 10% by mass relative to the mass of the solid content of the water-dispersible polyurethane liquid (water-dispersible polyurethane resin). If the silicone content is too small, the softening effect of the sheet-like material will be insufficient, and if it is too much, the force with which the polyurethane grips the fibers in the sheet-like material will be weakened, and the wear resistance will be reduced. More preferably, it is 0.5-8 mass%.

Silicones, Ru film-forming silicone der.

  “Film-forming silicone” is a silicone that becomes a three-dimensional cross-linked structure by heating and cannot be redispersed in water. After the film-forming silicone is applied, Even if there are external factors such as water handling such as washing, dyeing and washing of the sheet and friction, the silicone does not fall from the sheet, and the flexibility of the sheet can be maintained. Further, after impregnating a fibrous base material with an aqueous dispersion of a water-dispersible polyurethane resin composition containing a film-forming silicone aqueous dispersion, the sheet is treated with hot water and / or an alkaline aqueous solution to make the fibers extremely fine. In the case of forming, the flexibility of the sheet-like material can be maintained due to the film-forming property of silicone.

  In the present invention, "the film-forming silicone remains in the sheet-like material even after the fiber ultrafine treatment" is a comparison between the measured value and the theoretical calculation value of the mass of the sheet-like material after the ultrafine treatment, The difference is within 30%.

  The water-dispersed polyurethane resin composition has various additives such as pigments such as carbon black, phosphorus-based, halogen-based, silicone-based or inorganic flame retardants, phenol-based, sulfur-based or phosphorus-based antioxidants. UV absorbers such as benzotriazoles, benzophenones, salicylates, cyanoacrylates or oxalic anilides, light stabilizers such as hindered amines and benzoates, hydrolysis stabilizers such as polycarbodiimides, plastics Agent, antistatic agent, surfactant, foaming agent, softener, water repellent, coagulation regulator, dye, preservative, antibacterial agent, deodorant, filler such as cellulose particles, or inorganic such as silica or titanium oxide It may contain particles or the like.

  The mass ratio of the solid content of the water-dispersed polyurethane resin composition to the sheet-like material is preferably 10 to 80% by mass. By setting the ratio of the solid content of the water-dispersed polyurethane resin composition to 10% by mass or more, more preferably 15% by mass or more, it is possible to obtain the strength of the sheet-like material and prevent the fibers from dropping off. Moreover, by setting the ratio of the solid content of the water-dispersible polyurethane resin composition to 80% by mass or less, more preferably 70% by mass or less, it is possible to prevent the texture from becoming hard and to obtain good napped quality.

  Next, the manufacturing method of the sheet-like material concerning this invention is described.

  In the method for producing a sheet-like material, a fibrous base material is impregnated with an aqueous dispersion of a water-dispersed polyurethane resin composition. That is, polyurethane is imparted to the fibrous base material.

  As a means for forming the ultrafine fiber of the fibrous base material, it is preferable to use an ultrafine fiber expression type fiber. By using the ultrafine fiber expression type fiber, a form in which the fiber bundles are entangled can be stably obtained.

  It is important that the average single fiber diameter of the ultrafine fiber expression type fiber is 10 to 40 μm. By setting the average single fiber diameter to 40 μm or less, more preferably 35 μm or less, and even more preferably 30 μm or less, an excellent flexible sheet can be obtained. Further, the nonwoven fabric of the fibrous base material can be obtained by a method such as needle punching, water jet punching, etc., but the average single fiber diameter is not too large, the fiber entanglement efficiency is good, and the physical properties are good. It becomes a quality base material. On the other hand, by setting the average single fiber diameter to 10 μm or more, more preferably 12 μm or more, and even more preferably 15 μm or more, physical properties such as strength of the fibrous base material can be maintained, and the water dispersion of the water-dispersed polyurethane resin composition can be maintained. The process passability in the step of impregnating the liquid is improved.

  As ultrafine fiber expression type fiber, two-component thermoplastic resins with different solvent solubility are used as sea component and island component, and the sea component is dissolved and removed using solvent etc. to make island component as ultrafine fiber. Alternatively, a two-component thermoplastic resin may be alternately disposed in a radial or multilayer manner on the fiber cross section, and a peelable composite fiber that is split into ultrafine fibers by separating and separating each component may be employed. Among them, the sea-island type fiber can be preferably used also from the viewpoint of flexibility and texture of the sheet-like material because it can provide an appropriate gap between the island components, that is, between the ultrafine fibers, by removing the sea component.

  For the sea-island type fiber, a sea-island type composite fiber base is used, and the sea-island type composite fiber, in which two components of the sea component and the island component are arranged and spun together, and the two components of the sea component and the island component are mixed and spun. There are mixed spinning fibers. Sea-island type composite fibers are preferably used from the viewpoint that ultrafine fibers having a uniform fineness can be obtained, and that a sufficiently long ultrafine fiber is obtained and contributes to the strength of the sheet-like material.

  As the sea component of the sea-island fiber, polyethylene, polypropylene, polystyrene, copolymer polyester obtained by copolymerizing sodium sulfoisophthalic acid, polyethylene glycol, or the like, polylactic acid, or polyvinyl alcohol can be used. Of these, copolyester or polylactic acid copolymerized with alkali-degradable sodium sulfoisophthalic acid or polyethylene glycol that can be decomposed without using an organic solvent, and polyvinyl alcohol that can remove sea components with hot water are preferably used. It is done.

  The sea removal treatment (treatment for removing sea components) when using sea-island fibers may be performed before or after application of polyurethane to the fibrous base material. If the sea removal treatment is performed before the polyurethane is applied, the polyurethane is in close contact with the ultrafine fibers so that the ultrafine fibers can be strongly gripped, so that the wear resistance of the sheet-like material is improved. On the other hand, when sea removal treatment is performed after polyurethane is applied, voids are generated between the polyurethane and the ultrafine fibers due to the sea component being desealed, and the structure is such that the ultrafine fibers are not directly held by the polyurethane. The texture becomes flexible.

  It is important that the average single fiber diameter of the ultrafine fibers obtained by sea removal treatment (treatment for removing sea components) is 0.3 to 7 μm. By setting the average single fiber diameter to 7 μm or less, more preferably 6 μm or less, and even more preferably 5 μm or less, it is possible to obtain a sheet-like product having excellent flexibility and napping quality. On the other hand, by setting the average single fiber diameter to 0.3 μm or more, more preferably 0.7 μm or more, and even more preferably 1 μm or more, the bundle-like fibers at the time of napping such as coloring after dyeing or grinding with sandpaper are used. Excellent dispersibility and ease of judgment.

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

  In the nonwoven fabric used as the fibrous base material, needle punching or water jet punching can be employed as a method for entanglement of fibers or fiber bundles.

  The aqueous dispersion resin composition is prepared, for example, by blending an aqueous dispersion polyurethane liquid in which an aqueous dispersion polyurethane resin composition is dispersed in water with a microballoon. The microballoon can be blended in a water-dispersed polyurethane liquid prepared in advance, or can be blended in a water-dispersed polyurethane liquid being prepared.

  In the water-dispersible polyurethane liquid, the water-dispersible polyurethane resin is dispersed and stabilized in water. In addition, as described above, the water-dispersible polyurethane resin includes a forced emulsification-type polyurethane resin that is forcibly dispersed and stabilized using an emulsifier (external emulsifier), a hydrophilic group in the molecular structure, and the emulsifier It is classified as a self-emulsifying polyurethane resin that can be dispersed and stabilized in water even if it does not exist. Any water-dispersible polyurethane liquid may be used, but a self-emulsifying polyurethane resin is preferably used in that it does not contain an emulsifier. When a forced emulsification type polyurethane containing an emulsifier is used, the emulsifier causes a sticky surface on the surface of the sheet-like material, and a cleaning process is required, resulting in an increase in processing steps and an increase in cost. In addition, due to the presence of the emulsifier, the water resistance of the dry film containing the water-dispersed polyurethane resin that has been converted into a film is lowered, and therefore, in the dyeing of a sheet-like material to which polyurethane has been added, the polyurethane tends to drop into the dyeing solution. It is in.

  The concentration of the water-dispersible polyurethane resin (content of the water-dispersible polyurethane resin relative to the water-dispersible polyurethane liquid) is 5% by mass to 50% by mass from the viewpoint of storage stability of the water-dispersible polyurethane liquid. Preferably, it is 10 mass%-40 mass%.

  Further, the water-dispersed polyurethane liquid contains a water-soluble organic solvent (for example, a ketone solvent such as acetone) in an amount of 40% by mass or less based on the water-dispersed polyurethane liquid in order to improve storage stability and film-forming property. However, the content of the organic solvent is preferably 1% by mass or less from the viewpoint of the preservation of the film forming environment.

  Moreover, as a water dispersion type polyurethane liquid, what has a heat-sensitive coagulation property is preferable. By using a water-dispersed polyurethane liquid having heat-sensitive coagulation properties, polyurethane can be uniformly applied in the thickness direction of the fibrous base material. The heat-sensitive coagulation property refers to the property that, when the water-dispersed polyurethane liquid is heated, the fluidity of the water-dispersible polyurethane liquid decreases and reaches a certain temperature (heat-sensitive coagulation temperature T2 (° C.)). . In the production of a sheet-like material, after applying a water-dispersible polyurethane liquid to a fibrous base material, the fibrous base material is solidified by dry heat coagulation, wet heat coagulation, wet coagulation, or a combination thereof, and dried. Polyurethane (coagulated product) is added to.

  As a method of coagulating a water-dispersible polyurethane liquid that does not exhibit heat-sensitive coagulation, dry coagulation is practical in industrial production, but in that case, the water-dispersible polyurethane resin concentrates on the surface layer of the fibrous base material. A migration phenomenon occurs, and the texture of the sheet-like material tends to harden.

  The heat-sensitive coagulation temperature T2 (° C.) of the water-dispersed polyurethane liquid is preferably 40 ° C. to 90 ° C. By setting the heat-sensitive coagulation temperature T2 (° C.) to 40 ° C. or higher, the stability of the water-dispersed polyurethane liquid during storage is improved, and adhesion of the water-dispersed polyurethane to the machine during operation can be suppressed. . Moreover, the migration phenomenon of the water-dispersed polyurethane in the fibrous base material can be suppressed by setting the thermal coagulation temperature T2 (° C.) to 90 ° C. or less. The thermal coagulation temperature T2 (° C.) is more preferably 50 ° C. to 80 ° C.

  The expansion start temperature T1 (° C.) of the microballoon is at least equal to or lower than the thermal coagulation temperature T2 (° C.) of the water-dispersed polyurethane liquid, so that the microballoon is contained in the polyurethane in an expanded state. Thus, since a clear porous structure of polyurethane can be obtained, a heat-sensitive coagulant may be appropriately added to the water-dispersed polyurethane resin composition liquid in order to achieve the heat-sensitive coagulation temperature T2 (° C.) as described above. . Examples of the heat-sensitive coagulant include inorganic salts such as sodium sulfate, magnesium sulfate, calcium sulfate, and calcium chloride, sodium persulfate, potassium persulfate, ammonium persulfate (APS), azobisisobutyronitrile, and benzoyl peroxide. These radical reaction initiators.

  The blending ratio of the heat-sensitive coagulant is, for example, 0.1 to 10% by mass, preferably 0.5 to 5% by mass with respect to the water-dispersed polyurethane resin (solid content).

  In the method for producing a sheet-like material, since the 100% modulus of the dry film formed from the water-dispersed polyurethane resin constituting the water-dispersed polyurethane liquid applied to the fibrous base material is 2 to 8 MPa, Recoverability can be obtained.

  Further, by using such water-dispersed polyurethane and making the polyurethane structure in the sheet-like material porous with a microballoon, the texture can be softened structurally even with hard polyurethane. Also, by using hard polyurethane, it shows good grindability in the napping process with sandpaper, etc., obtains an elegant appearance with napping, and further suppresses clogging with sandpaper to obtain good productivity it can.

  In addition, since the glass transition temperature of the dry film formed from the water-dispersed polyurethane resin is -25 ° C to 0 ° C, it exhibits good wear resistance and good wrinkle recovery properties. be able to.

Water-dispersible polyurethane solution, it contains a silicone aqueous dispersion. By containing the silicone aqueous dispersion, the frictional force between the polyurethane having a micro-balloon structure and the fibers of the fibrous base material can be reduced, and the texture of the sheet-like material can be made more flexible. In addition, when the microballoon is added to the water-dispersible polyurethane liquid, the dispersibility of the microballoon can be improved by adding the silicone water dispersion to the water-dispersible polyurethane liquid. The silicone water dispersion content of the water-dispersed polyurethane liquid is preferably 0.1 to 10% by mass as the solid content of the silicone with respect to the mass of the water-dispersible polyurethane resin. If the content is too small, the effect of softening the sheet becomes insufficient. If the content is too large, the force with which the polyurethane grips the fibers is weakened in the sheet-like material and the wear resistance is lowered. % By mass.

  The viscosity of the water-dispersed polyurethane liquid is preferably 1 to 900 mPa · s under measurement conditions at a temperature of 25 ° C. By setting the viscosity to 900 mPa · s or less, more preferably 500 mPa · s or less, the water-dispersed polyurethane liquid can be penetrated into the fibrous base material. On the other hand, by setting the viscosity to 1 mPa · s or more, more preferably 5 mPa · s or more, the water-dispersed polyurethane resin composition can be efficiently solidified.

  A water-dispersed polyurethane resin composition can be coagulated by impregnating and applying a water-dispersible polyurethane liquid to a fibrous base material, and dry heat coagulation, wet heat coagulation, wet coagulation, or a combination thereof.

  The wet heat coagulation temperature is set to be equal to or higher than the heat sensitive coagulation temperature T2 (° C.) of the water-dispersed polyurethane, and is preferably 40 to 200 ° C. By setting the wet heat solidification temperature to 40 ° C. or higher, more preferably 80 ° C. or higher, the time to solidification of the water-dispersed polyurethane resin composition can be shortened to further suppress the migration phenomenon. On the other hand, by setting the wet heat coagulation temperature to 200 ° C. or lower, more preferably 160 ° C. or lower, thermal degradation of the water-dispersed polyurethane resin composition can be prevented.

  The wet coagulation temperature is set to be equal to or higher than the thermal coagulation temperature T2 (° C.) of the water-dispersed polyurethane liquid and is preferably 40 to 100 ° C. By setting the temperature of wet coagulation in hot water to 40 ° C. or higher, more preferably 80 ° C. or higher, the time to solidification of the water-dispersed polyurethane liquid can be shortened to further suppress the migration phenomenon.

  The dry coagulation temperature and the drying temperature are preferably 80 to 180 ° C. By setting the dry solidification temperature and the drying temperature to 80 ° C. or higher, more preferably 90 ° C. or higher, the productivity is excellent. On the other hand, thermal degradation of the water-dispersed polyurethane can be prevented by setting the dry coagulation temperature and the drying temperature to 180 ° C. or lower, more preferably 160 ° C. or lower.

  The expansion of the microballoon may be performed in a step of coagulating polyurethane, may be performed in a drying step, or may be performed by a step of performing a heat treatment at a higher temperature after drying.

  After polyurethane is applied, dividing the polyurethane-applied sheet-like material into the sheet thickness direction (cutting so that the thickness is halved) or into several sheets is a preferable aspect with excellent production efficiency.

  Applying an antistatic agent before the raising process described later is a preferable embodiment in order to make it difficult for the grinding powder generated from the sheet-like material to be deposited on the sandpaper by grinding.

  In order to form napping on the surface of the sheet-like material, napping treatment may be performed. The raising treatment can be performed by a method of grinding using sandpaper, roll sander or the like.

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

  The dyeing temperature is preferably 80 to 150 ° C., although it depends on the type of fiber. By setting the dyeing temperature to 80 ° C. or higher, more preferably 110 ° C. or higher, it is possible to efficiently dye the fibers. On the other hand, deterioration of the water-dispersed polyurethane can be prevented by setting the dyeing temperature to 150 ° C. or lower, more preferably 130 ° C. or lower.

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

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

  Sheet materials according to the present invention include furniture, chairs and wall materials, and interior materials, shirts having a very elegant appearance as skin materials such as seats, ceilings, and interiors in vehicle interiors such as automobiles, trains, and aircraft, Jackets, casual shoes, sports shoes, uppers and trims of shoes such as men's shoes or women's shoes, clothing materials, wiping cloths, abrasive cloths or CD curtains used for bags, belts, wallets, etc. It can be suitably used as an industrial material.

  In particular, the soft texture and the good wrinkle recovery property that does not cause wrinkles, which are the effects of the sheet-like material, can be suitably used for apparel applications that strongly require these functions.

EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example demonstrate this invention further in detail, this invention is not limited only to these.
[Synthesis Example A]
To a four-necked flask equipped with a stirrer, thermometer, reflux tube, and nitrogen introduction tube, 71.0 g of DHD1000S (Mitsui Chemicals, polyoxyethylene chain-containing diol), UH200 (Ube Industries, ETERNACOLL UH- 200, polycarbonate diol) 420.0 g and acetone 160.0 g were mixed.

  Next, 109.1 g of 4,4-dicyclohexylmethane diisocyanate (Degussa) and 0.2 g of stannous octylate were added to them and reacted at 55 ° C. to obtain an isocyanate group-terminated prepolymer.

  Next, 240.0 g of acetone was added to the reaction solution and mixed well, then cooled to 30 ° C., and then 1083.5 g of ion-exchanged water was gradually added to disperse the isocyanate group-terminated prepolymer in water. .

  Next, an aqueous amine solution containing 14.5 g of 1,6-hexamethylenediamine and 58.0 water as chain extender 1 was added to chain extend the isocyanate group-terminated prepolymer.

  Thereafter, acetone was distilled off to obtain a water-dispersed polyurethane liquid A having a solid content (water-dispersed polyurethane resin) of 35% by mass.

The formulation of Synthesis Example A is shown in Table 1.
[Synthesis Example B], [Synthesis Example D], [Synthesis Example E] and [Synthesis Example G]
A water-dispersed polyurethane liquid B, D, E, and G were obtained in the same manner as in Synthesis Example A except that the formulation of Table 1 was followed.
[Synthesis Example C] and [Synthesis Example F]
According to the formulation of Table 1, after addition of the chain extender 1, it contains an alkoxysilyl group containing 9.9 g of chain extender 2 (γ- (2-aminoethyl) aminopropyltrimethoxysilane and 39.7 g of water Water-dispersed polyurethane liquids C and F were obtained in the same manner as in Synthesis Example A except that the amine chain extender aqueous solution was added.
[Synthesis Example H]
In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, 495.6 g of UH200 (Ube Industries, ETERNACOLL UH-200, polycarbonate diol) and 160.0 g of acetone were mixed. .

  Next, 104.4 g of 4,4-dicyclohexylmethane diisocyanate (Degussa) and 0.2 g of stannous octylate were added to them and reacted at 55 ° C. to obtain an isocyanate group-terminated prepolymer.

  Next, 60.0 g of Emulgen A60 (manufactured by Kao Corporation, polyoxyethylene distyrenated phenyl ether, external emulsifier, cloud point 61 ° C., HLB 12.8) was added to the reaction solution, and further 240.0 g of acetone was added. After mixing well, the mixture was cooled to 30 ° C., and then 1195.0 g of ion-exchanged water was gradually added to disperse the isocyanate group-terminated prepolymer in water.

  Next, an aqueous amine solution containing 14.5 g of 1,6-hexamethylenediamine and 58.0 water as chain extender 1 was added to chain extend the isocyanate group-terminated prepolymer.

  Thereafter, acetone was distilled off to obtain a water-dispersed polyurethane liquid H having a solid content (water-dispersed polyurethane resin) of 35% by mass.

  The formulation of Synthesis Example H is shown in Table 1.

The raw materials and physical properties in Table 1 will be described in detail below.
-H12MDI: Degussa, 4,4-dicyclohexylmethane diisocyanate-DHD1000S: Mitsui Chemicals, polyoxyethylene chain-containing diol-UH300: Ube Industries, trade name "ETERRNACOLL UH-300", molecular weight 3000, polycarbonate diol・ UH200: Ube Industries, trade name “ETERRNACOLL UH-200”, molecular weight 2000, polycarbonate diol ・ UH100: Ube Industries, trade name “ETERRNACOLL UH-100”, molecular weight 1000, polycarbonate diol ・ UH50: Ube Industries Product name “ETERNACOLL UH-50”, molecular weight 500, polycarbonate diol C2090: Kuraray Co., Ltd., trade name “C2090”, molecular weight 2000, polyhexamethylene Copolymerization of carbonate and 3-methylpentane carbonate Polycarbonate diol Terratan 1000: manufactured by INVISTA, trade name “TERATANE 2000”, molecular weight 2000, polytetramethylene ether glycol A60: trade name “Emulgen A60”, poly Oxyethylene distyrenated phenyl ether, external emulsifier, cloud point 61 ° C., HLB 12.8
KBM603: Shin-Etsu Chemical Co., Ltd., trade name “KBM603”, γ- (2-aminoethyl) aminopropyltrimethoxysilane 100% modulus (MPa): 100 of polyurethane dry film measured by tensile test described later % Modulus (1).
Glass transition temperature Tg (° C.): Glass transition temperature (2) of the dry film measured by a viscoelasticity test described later.

  Hereinafter, an evaluation method of the water-dispersed polyurethane liquid of the synthesis example, the polyurethane formed therefrom, and the water-dispersed polyurethane resin composition containing the water-dispersed polyurethane liquid will be described.

[Method of evaluating polyurethane]
(1) 100% modulus of dry-type membrane A water-dispersed polyurethane liquid containing 30% by mass of solids not containing microballoons is diluted with water and adjusted to 20% by mass, and then it is 5 cm wide × 10 cm long X Put into a polyethylene tray with a depth of 1 cm, air dry at 25 ° C. for 8 hours, and then heat-treat with a hot air dryer at a temperature of 120 ° C. for 2 hours to obtain a polyurethane dry film (coating film) with a thickness of 1 mm. With respect to this dry film, the tensile strength at 100% elongation was measured as 100% modulus in accordance with A method (strip method) described in tensile tester JIS-L1096-8.12.1 (1999).

  Table 1 shows the measurement results for the respective synthesis examples.

(2) Glass transition temperature of dry film The glass transition temperature of the dry film was measured by a viscoelasticity test.

  First, a water-dispersed polyurethane liquid was applied onto a substrate so that the dry thickness was 200 μm, and dried at 200 ° C. for 5 minutes to obtain a polyurethane dry film.

  Thereafter, the dry film is cut into a strip shape having a length of 10.0 cm, a width of 5.0 mm, and a thickness of 2.0 mm, and the dynamic membrane is measured by a dynamic viscoelasticity measuring device (VES-F-III, VISCO-ELASTICSPECTROMETER, Iwamoto Seisakusho). ) And a glass dispersion temperature (Tg) as a peak value of tan δ of the obtained data. Calculated.

  Table 1 shows the measurement results for the respective synthesis examples.

[Method for evaluating water-dispersed polyurethane liquid]
(3) Thermal coagulation temperature T2 (° C.) of water-dispersed polyurethane liquid
20 g of water-dispersed polyurethane liquid is placed in a test tube with an inner diameter of 12 mm, and a thermometer is inserted so that the tip is below the liquid level. The test tube is then sealed, and water is dispersed in a hot water bath at a temperature of 95 ° C. It was immersed so that the liquid level of the type polyurethane liquid was lower than the liquid level of the warm water bath. While checking the temperature rise in the test tube with a thermometer, the test tube is pulled up for a time within 5 seconds at a time, and shaken to the extent that the liquid surface of the water-dispersed polyurethane liquid can be checked for fluidity. The temperature at which the liquid level of the dispersion type polyurethane liquid lost its fluidity was defined as the thermal coagulation temperature T2 (° C.). This measurement was performed three times for each water-dispersed polyurethane liquid, and the average value was calculated. The results are shown in Table 1.

[Evaluation method of aqueous dispersion of water-dispersed polyurethane resin composition]
(4) Foaming test First, a water-dispersed polyurethane liquid and a microballoon were blended so as to have a blending ratio (solid content ratio) shown in Table 2 below, and then diluted with water to obtain a solid content (water dispersion). An aqueous dispersion of a water-dispersed polyurethane resin composition that is 30% by mass) was prepared.

  Thereafter, the aqueous dispersion (see Table 2 below) is spread on a polypropylene container so that the thickness after drying is 200 μm, exposed to steam (temperature 95 ° C.) for 1 minute, and then heated at 80 ° C. for 10 minutes. Followed by heating at 120 ° C. for 3 minutes. Thereby, the water-dispersed polyurethane resin composition (samples (a) to (c)) was foamed.

  The foam was evaluated according to the following evaluation criteria. The results are shown in Table 2.

(Evaluation criteria)
○: Foamed into a sponge.
(Triangle | delta): Although it foamed, there were few bubbles.
X: Almost no foaming occurred.

(5) Dissolution test After heating the heated samples (a) to (c) obtained by the foaming test of (4) above at 120 ° C. for 1.5 hours, the ratio of 1 g of sample / 45 g of hot water It was immersed for 5 hours in hot water of 80-85 degreeC so that it might become.

  Then, after pulling up the sample from hot water and drying at 120 ° C. for 1.5 hours, the weight loss rate of the sample (mass% = [weight loss of sample before and after immersion / weight of sample before immersion] × 100) is calculated. Calculated. The results are shown in Table 2.

  Next, the evaluation method of the average single fiber diameter of the fibrous base material used in the examples and comparative examples described later, and the texture of the sheet-like material obtained in the examples and comparative examples described later, wrinkle recovery, wear resistance The property evaluation and the appearance quality evaluation method will be described in detail.

[Fiber substrate evaluation method]
(6) Average single fiber diameter The average single fiber diameter was obtained by taking a scanning electron microscope (SEM) photograph of a fibrous base material at a magnification of 2000 times, randomly selecting 100 fibers, measuring the single fiber diameter, and averaging Calculated by calculating the value.

  When the ultrafine fibers constituting the fibrous base material had an irregular cross section, the outer peripheral circular diameter of the irregular cross section was calculated as a single fiber diameter. Also, when the circular cross section and the irregular cross section are mixed, or when the single fiber diameters are greatly different, the number of samplings corresponding to each existing number ratio is selected and calculated to be 100 in total. did. However, in the case where a reinforcing woven fabric or knitted fabric is inserted in addition to the non-woven fabric composed of ultrafine fibers or fiber bundles thereof, the fibers of the reinforcing woven or knitted fabric are measured by measuring the average single fiber diameter of the ultrafine fibers. Excluded from sampling.

[Evaluation method for sheet]
(7) Texture of sheet-like material Five test pieces each having a size of 2 × 15 cm in the vertical direction and the horizontal direction were prepared based on the method A (45 ° cantilever method) described in JIS L1096-8.19.1 (1999). The sample was placed on a horizontal platform having a slope with a temperature of 45 ° C., and the test piece was slid to read the scale when the center point of one end of the test piece was in contact with the slope.
(8) Wrinkle recoverability of sheet-like material Based on the Monsanto method described in JIS L1059-1 (1998), the wrinkle recovery angle of five test pieces was measured using a 10N load device, and The wrinkle recovery property was calculated by the formula of the wrinkle prevention rate, and the average value of 5 sheets was obtained.
(9) Abrasion resistance evaluation of sheet-like material Nylon 6 nylon fiber having a diameter of 0.4 mm cut into a length of 11 mm perpendicular to the longitudinal direction of the fiber was made into 100 bundles, and the bundle was made 110 mm in diameter. 97 in a 6-fold concentric circle (1 in the center, 6 in the 17 mm diameter circle, 13 in the 37 mm diameter circle, 19 in the 55 mm diameter circle, 26 in the 74 mm diameter circle, Using a circular brush (9700 nylon threads) arranged in a circle with a diameter of 90 mm, under a load of 8 pounds (about 3629 g), a rotational speed of 65 rpm, and a number of rotations of 50, a circular sample (45 mm in diameter) ) And the mass change of the samples before and after that was measured, and the average value of the five samples was defined as the weight loss.
(10) Appearance quality of sheet-like material The appearance quality of sheet-like material is as follows by visual and sensory evaluation with 20 people each as an evaluator, 10 adult men and 10 adult women in good health. Five-stage evaluation was performed, and the highest evaluation was defined as appearance quality. Appearance quality was good from grade 3 to grade 5. The results are shown in Table 2.
Grade 5: There was uniform fiber napping, the fiber was well dispersed, and the appearance was good.
Grade 4: Evaluation was between Grade 5 and Grade 3.
Third grade: The dispersion state of the fiber was slightly poor, but there was fiber napping and the appearance was reasonably good.
Second grade: The evaluation was between the third grade and the first grade.
First grade: There was little napping of the fibers, and the dispersion state of the fibers as a whole was very poor, and the appearance was poor.

  Hereinafter, manufacture of a sheet-like object is explained in full detail in an Example and a comparative example.

Example 1
[Manufacture of nonwoven fabric for fibrous base materials]
Using polyethylene terephthalate copolymerized with 8 mol% of sodium 5-sulfoisophthalate as the sea component and polyethylene terephthalate as the island component, the compound ratio of the island component is 36 mass / A sea-island type composite fiber having one filament and an average single fiber diameter of 17 μm was obtained. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to form a staple, a fiber web was formed through a card and a cross wrapper, and a nonwoven fabric was formed by needle punching. This nonwoven fabric was immersed in hot water at a temperature of 97 ° C. for 2 minutes to shrink and dried at a temperature of 140 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersed polyurethane liquid A, 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 100% by mass of the solid content, “Matsumoto Microsphere F-36LV” (swelled by Matsumoto Yushi Seiyaku) as a microballoon Start temperature T1: 75 to 85 ° C. Average mass before balloon expansion 16 μm) 1 part by mass and 5 parts by mass of “BY22-856EX” manufactured by Toray Dow Corning as a film-forming silicone are added, and the whole is solidified with water 10 An aqueous dispersion of an aqueous dispersion type polyurethane resin composition adjusted to mass% was obtained.
[Applying polyurethane]
The nonwoven fabric for fibrous base material is impregnated with an aqueous dispersion of the water-dispersible polyurethane resin composition, treated for 5 minutes in a moist heat atmosphere at a temperature of 100 ° C., and then dried at a temperature of 120 ° C. for 5 minutes. By drying with hot air, a sheet provided with polyurethane was obtained so that the mass of polyurethane (polyurethane containing heat-sensitive coagulant, microballoon and film-forming silicone) was 30% by mass relative to the mass of the island component of the nonwoven fabric.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the polyurethane was immersed in a 10 g / L sodium hydroxide aqueous solution heated to a temperature of 95 ° C. and treated for 30 minutes to obtain a sea removal sheet from which sea components of sea-island fibers were removed. . The average single fiber diameter on the surface of the obtained sea removal sheet was 2 μm. Next, after the surface of the sea-removed sheet was raised by grinding using a 240 mesh endless sandpaper, it was dyed with a disperse dye using a circular dyeing machine and subjected to reduction cleaning to obtain a sheet.

  The obtained sheet-like product had good appearance quality and wear resistance, and had a soft texture and good wrinkle recovery properties.

Example 2
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersed polyurethane liquid B, 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 100% by mass of the solid content, “Matsumoto Microsphere F-36LV” (swelled by Matsumoto Yushi Seiyaku) as a microballoon Start temperature T1: 75 to 85 ° C. 3 parts by mass of average balloon diameter before expansion (16 μm) and 3 parts by mass of “Drypon 600E” manufactured by Nikka Chemical Co., Ltd. as a film-forming silicone are added, and the entire solid content is 10% by mass with water. An aqueous dispersion of the water-dispersed polyurethane resin composition adjusted to was obtained.
[Providing water-dispersed polyurethane]
The nonwoven fabric for fibrous base material is impregnated with an aqueous dispersion of the water-dispersible polyurethane resin composition, and polyurethane (a polyurethane containing a heat-sensitive coagulant, a microballoon, and a film-forming silicone) is used in the same manner as in Example 1. ) Was obtained.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the above polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

  The obtained sheet-like product had good appearance quality and wear resistance, and had a soft texture and good wrinkle recovery properties.

Example 3
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersed polyurethane liquid C, 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 100% by mass of the solid content, “Matsumoto Microsphere F-36LV” (swelled by Matsumoto Yushi Seiyaku) as a microballoon Start temperature T1: 75 to 85 ° C. Average mass of balloon before expansion (16 μm) 5 parts by mass and 5 parts by mass of “Drypon 600E” manufactured by Nikka Chemical Co., Ltd. as a film-forming silicone are added, and the entire solid content is 10% by mass with water. An aqueous dispersion of the water-dispersed polyurethane resin composition adjusted to was obtained.
[Applying polyurethane]
A sheet in which the above-mentioned nonwoven fabric for a fibrous base material is impregnated with the above water-dispersed polyurethane liquid and polyurethane (a polyurethane containing a heat-sensitive coagulant, a microballoon and a film-forming silicone) is applied in the same manner as in Example 1. Obtained.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the above water-dispersed polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet-like material.

  The obtained sheet-like product had good appearance quality and wear resistance, and had a soft texture and good wrinkle recovery properties.

Example 4
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersed polyurethane liquid H, 3 parts by mass of magnesium sulfate as a heat-sensitive coagulant and “Matsumoto Microsphere F-36LV” manufactured by Matsumoto Yushi Seiyaku as a microballoon (expansion start temperature T1) : 75 to 85 ° C. 5 parts by mass of an average balloon diameter before expansion of 16 μm) and 2 parts by mass of “Drypon 600E” manufactured by Nikka Chemical as a film-forming silicone were added, and the whole was adjusted to a solid content of 10% by mass with water. An aqueous dispersion of an aqueous dispersion type polyurethane resin composition was obtained.
[Applying polyurethane]
A sheet in which the above-mentioned nonwoven fabric for a fibrous base material is impregnated with the above water-dispersed polyurethane liquid and polyurethane (a polyurethane containing a heat-sensitive coagulant, a microballoon and a film-forming silicone) is applied in the same manner as in Example 1. Obtained.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the above water-dispersed polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet-like material.

  The obtained sheet-like product had good appearance quality and wear resistance, and had a soft texture and good wrinkle recovery properties.

Comparative Example 1
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersed polyurethane liquid D, 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 100% by mass of the solid content, “Matsumoto Microsphere F-36LV” (inflated by Matsumoto Yushi Seiyaku) as a microballoon Start temperature T1: 75-85 ° C. 1 part by mass of an average balloon diameter before expansion (16 μm) was added to obtain an aqueous dispersion of a water-dispersed polyurethane resin composition whose total content was adjusted to 10% by mass with water.
[Applying polyurethane]
The above-mentioned nonwoven fabric for a fibrous base material was impregnated with the above water-dispersed polyurethane liquid, and a sheet having a polyurethane (a polyurethane containing a heat-sensitive coagulant and a microballoon) was obtained in the same manner as in Example 1.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the above polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

  In Comparative Example 1, the 100% modulus of the water-dispersed polyurethane was too low at 1 MPa, so that the obtained sheet-like material had a soft texture but low wrinkle recovery.

Comparative Example 2
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersible polyurethane liquid E, 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 100% by mass of the solid content, “Matsumoto Microsphere F-36LV” (swelled by Matsumoto Yushi Seiyaku) as a microballoon Start temperature T1: 75-85 ° C. 1 part by mass of an average balloon diameter before expansion (16 μm) was added to obtain an aqueous dispersion of a water-dispersed polyurethane resin composition whose total content was adjusted to 10% by mass with water.
[Applying polyurethane]
The above-mentioned nonwoven fabric for fibrous base material was impregnated with the above-mentioned water-dispersed polyurethane liquid, and a sheet provided with polyurethane (a polyurethane containing a heat-sensitive coagulant and a microballoon) was obtained in the same manner as in Example 1.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the above polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

  In Comparative Example 2, since the glass transition temperature of the dry film was too low at −45 ° C., the obtained sheet-like material was soft in texture but low in wrinkle recovery.

Comparative Example 3
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
An aqueous dispersion of an aqueous dispersion polyurethane resin composition in which the aqueous dispersion polyurethane liquid A was adjusted to a solid content of 10% by mass with water was obtained.
[Applying polyurethane]
The nonwoven fabric for fibrous base material was impregnated with the aqueous dispersion of the water-dispersible polyurethane resin composition, and a sheet provided with polyurethane was obtained in the same manner as in Example 1.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the above water-dispersed polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet-like material.

  In Comparative Example 3, since the microballoon was not added, the obtained sheet-like material had good wrinkle recovery, but the texture became hard and the appearance quality was poor.

Comparative Example 4
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersed polyurethane liquid F, 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 100 parts by mass of solids as a heat-sensitive coagulant and “Matsumoto Microsphere F-36LV” manufactured by Matsumoto Yushi Seiyaku as a microballoon Start temperature T1: 75 to 85 ° C. 3 parts by mass of an average balloon diameter before expansion (16 μm) was added to obtain an aqueous dispersion of a water-dispersed polyurethane resin composition whose total content was adjusted to 10% by mass with water.
[Applying polyurethane]
The nonwoven fabric for fibrous base material was impregnated with an aqueous dispersion of the water-dispersible polyurethane resin composition, and polyurethane (a polyurethane containing a heat-sensitive coagulant and a microballoon) was applied in the same manner as in Example 1. A sheet was obtained.
(Desealing, raising, dyeing, reducing cleaning)
The sheet provided with the above polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

  In Comparative Example 4, since the 100% modulus of the dry film was too high as 9 MPa, the obtained sheet-like material had a hard texture, and retained almost its form after folding, and the wrinkle recovery property was low. It became a thing.

Comparative Example 5
[Manufacture of nonwoven fabric for fibrous base materials]
The same nonwoven fabric for fibrous base material as that used in Example 1 was used.
[Production of aqueous dispersion of water-dispersed polyurethane resin composition]
In water-dispersed polyurethane G, 2 parts by mass of ammonium persulfate (APS) as a heat-sensitive coagulant and 100 parts by mass of solid content, “Matsumoto Microsphere F-36LV” (inflated by Matsumoto Yushi Seiyaku) as a microballoon Start temperature T1: 75 to 85 ° C. 3 parts by mass of an average balloon diameter before expansion (16 μm) was added to obtain an aqueous dispersion of a water-dispersed polyurethane resin composition whose total content was adjusted to 10% by mass with water.
[Applying polyurethane]
The above-mentioned nonwoven fabric for a fibrous base material was impregnated with the above water-dispersed polyurethane liquid, and a sheet having a polyurethane (a polyurethane containing a heat-sensitive coagulant and a microballoon) was obtained in the same manner as in Example 1.
[Desealing, raising, dyeing, reducing cleaning]
The sheet provided with the above polyurethane was subjected to sea removal, raising, dyeing, and reduction washing in the same manner as in Example 1 to obtain a sheet.

  In Comparative Example 5, since the glass transition temperature of the dry film was too high at 5 ° C., the obtained sheet was hard in texture and wrinkle recoverability was low.

  Table 3 shows the evaluation results of the sheet-like materials obtained in the respective examples and comparative examples.

Claims (5)

A water-dispersible polyurethane resin, a microballoon, and a film- forming silicone are included, and the dry film formed from the water-dispersible polyurethane resin has a 100% modulus of 2 to 8 MPa, and is formed from the water-dispersible polyurethane resin. The water-dispersible polyurethane resin composition, wherein the dry-type film has a glass transition temperature of -25 ° C to 0 ° C.   The water-dispersible polyurethane resin composition according to claim 1, wherein the water-dispersible polyurethane resin has a hydrophilic group. 3. The water-dispersed polyurethane resin composition according to claim 1, wherein an expansion start temperature T <b> 1 (° C.) of the microballoon has a relationship represented by the following formula (a).
40 ≦ T1 ≦ 150 (a) Formula   A sheet-like material containing polyurethane inside a fibrous base material comprising ultrafine fibers having an average single fiber diameter of 0.3 to 7 µm, wherein the polyurethane is a water dispersion according to any one of claims 1 to 3. A sheet-like product comprising a type polyurethane resin composition. A fibrous base material comprising fibers having an average single fiber diameter of 10 to 40 µm is impregnated with an aqueous dispersion of the water-dispersed polyurethane resin composition according to any one of claims 1 to 3, and then heated by wet heat A process for producing a sheet-like product, characterized by solidifying the polyurethane by dry heat treatment after the treatment.