JP2003064584A - Leather-like sheet - Google Patents

Abstract

(57) [Summary] [Problem] A leather-like sheet excellent in texture such as coloring property, flexibility, surface appearance and fulfillment, and durability such as dyeing fastness and light resistance. A leather-like sheet in which a resin is provided inside a fibrous base material and which is dyed with a disperse dye, wherein the following conditions (I), (II), and (I): The continuous phase comprises a component having a glass transition temperature of 20 ° C. or lower, and the dispersed phase has a single-layer structure comprising a component having a glass transition temperature of 60 ° C. or higher, or glass. A multilayer structure having at least one layer of a component having a transition temperature of 60 ° C. or higher, (II)
A leather-like sheet that satisfies that the outermost layer in the dispersed phase has a diameter of 150 nm or more among the layers composed of components having a glass transition temperature of 60 ° C or higher.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is directed to color development, flexibility,
The present invention relates to a leather-like sheet excellent in various feelings such as fullness, texture such as surface appearance, dyeing fastness and light resistance.

[0002]

2. Description of the Related Art Conventionally, as a leather-like sheet, a fiber fluff is present on the surface of a base material having a polymeric elastic body provided inside a fibrous base material such as a non-woven fabric, or a resin layer on the surface of the base material. Laminated sheets are known, and leather-like sheets having fiber naps on the surface are particularly preferred as high-grade products because of their excellent texture and appearance. Urethane-based elastic bodies, acrylic-based elastic bodies, etc. are known as polymeric elastic bodies to be applied to the nonwoven fabric, and polyurethane-based elastic bodies are preferably used from the viewpoint of the texture of the leather-like sheet and mechanical properties. ing. As a general method for producing a leather-like sheet in which a polymer elastic material is applied to the inside of a fibrous base material, a fibrous base material such as a non-woven fabric is prepared from a polymer elastic material using an organic solvent such as dimethylformamide as a solvent. Although a method of manufacturing by impregnating and solidifying a solution or the like is used, a manufacturing method using an organic solvent is not preferable from the viewpoint of environment, safety and the like. In consideration of these points, various methods of manufacturing a leather-like sheet by impregnating an aqueous dispersion of a polymeric elastic material in place of the method using an organic solvent solution of a polymeric elastic material have been proposed.

However, in any method using either an organic solvent solution or an aqueous dispersion of these polymeric elastomers, in a leather-like sheet having fiber naps on the surface, the dyeability of the impregnated polymeric elastomers and fibers is improved. Due to the difference in color unevenness is likely to be noticeable. In particular, in a leather-like sheet using a polyester fiber which can be dyed with a disperse dye which does not contain a heavy metal and which is environmentally preferable, and which is excellent in light resistance and heat resistance, which is preferably used in automobile applications and the like, The color unevenness of the surface appearance was remarkable.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to achieve the elimination of color unevenness, which has been difficult in the past, in a leather-like sheet dyed with a disperse dye, and to further improve dyeing fastness, flexibility and fullness. Another object of the present invention is to provide a leather-like sheet having an excellent surface feel.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, a leather-like sheet using a resin having a specific morphology as a resin to be provided inside a fibrous base material. It was found that the above-mentioned object can be achieved.

That is, the present invention relates to a leather-like sheet. That is, the present invention is a leather-like sheet in which a resin is provided inside a fibrous base material and which is dyed with a disperse dye, and which has the following conditions (I) and (II):
(I) The resin is composed of a continuous phase and a dispersed phase, the continuous phase comprises a component having a glass transition temperature of 20 ° C. or lower, and the dispersed phase comprises a component having a glass transition temperature of 60 ° C. or higher. It has a structure or a multi-layer structure having at least one layer having a glass transition temperature of 60 ° C. or higher, and (II) the layer having the glass transition temperature of 60 ° C. or higher is the most dispersed layer. Outer layer diameter is 150 nm
It is a leather-like sheet characterized by satisfying the above. The present invention is also the method for producing the above-mentioned leather-like sheet.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below. The fibrous base material used in the present invention may be one having a suitable thickness and a sense of fulfillment and having a soft texture, and various fibrous materials conventionally used for the production of leather-like sheets can be used. A non-woven fabric can be used, and a non-woven fabric is preferable because it gives a natural leather-like texture and physical properties.
The fibers forming these fibrous base materials may be ordinary natural fibers, semi-synthetic fibers, or synthetic fibers,
Ultrafine synthetic fibers or ultrafine synthetic fibers are preferred. Among them, a multi-component fiber composed of a plurality of polymers and having a laminated or sea-island cross-sectional shape in the cross-section of the fibers is preferable. Laminated multi-component fiber, by peeling the laminated portion, by removing the mono-component polymer is laminated, in the case of sea-island multi-component fiber, the sea component polymer By removing them, ultrafine fibers are obtained. Especially in the case of fibers that are made ultrafine by peeling off the laminated part, it is necessary to use organic solvents for extraction such as trichlene and toluene that are harmful to the human body, as in the conventional method of producing ultrafine fibers by extracting sea components. It is excellent in terms of environment and safety, and even when removing one component of the laminated layer to remove the sea component of the ultrafine or sea-island-like fibers, the removal is water or an aqueous solution. When it is possible to do so, it is not necessary to use an organic solvent, and it is excellent in terms of environment and safety.

At least one of such multi-component synthetic fibers is not removed by water or an aqueous solution.
A structure in which more than one kind of polymer substance is laminated, or a structure in which a sea component composed of a polymer substance removable by water or an aqueous solution and an island component of a polymer substance not removed by water or an aqueous solution are preferable is preferable.

Polymer materials which are not removed by water or an aqueous solution include nylon 6, nylon 11 and nylon 1.
2, nylon 46, nylon 66, nylon 96 (nonamethylenediamine and / or 2-methyl-1,8-
Nylon consisting of octane diamine and adipic acid), nylon 910 (nonamethylene diamine and / or 2)
-Methyl-1,8-octanediamine and sebacic acid nylon), Nylon 912 (nonamethylenediamine and / or 2-methyl-1,8-octanediamine and dodecanedioic acid nylon), nylon 6/1
2 (copolymer of caprolactam and laurolactam), nylon 6T (nylon consisting of hexamethylenediamine and terephthalic acid), nylon 9T (nonamethylenediamine and / or consisting of 2-methyl-1,8-octanediamine and terephthalic acid) Polyamides such as nylon) and polyamide block copolymers (polyamide elastomer); polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypentamethylene terephthalate, polyhexamethylene terephthalate and other polyalkylene terephthalates, polyethylene naphthalate, polypropylene naphthalate,
Polyesters such as polybutylene naphthalate, polypentamethylene naphthalate, polyhexamethylene naphthalate, polyester block copolymer (polyester elastomer); polyolefins such as polyethylene, polypropylene, polymethylpentene, ethylene-α-olefin copolymer Polystyrenes, polystyrene-based polymers represented by polystyrene-based block copolymers (polystyrene elastomers); polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate copolymers saponification Examples thereof include polymethacrylates, polymethacrylic acid esters, polyurethane elastomers, etc., and can be arbitrarily selected according to the application and required performance.

The polymer substance which can be removed with water or an aqueous solution is a polymer substance which can be dissolved or removed by decomposition with water or an aqueous solution such as an alkaline aqueous solution or an acidic aqueous solution under conditions such as heating and pressurization. Examples of such polymer substances include modified polyesters obtained by copolymerizing a compound containing polyethylene glycol and / or a sulfonic acid alkali metal salt, polyvinyl alcohol, polyvinyl alcohol-based copolymers, polyethylene oxide and the like.

The multi-component fiber preferably used in the present invention is a dye in which at least one component contains no heavy metal,
That is, it is necessary to be able to dye with a disperse dye which is preferable from the environmental viewpoint. Fibers made of a polymer having a low glass transition temperature are dyed with a disperse dye, but the dye may drop off in the reduction washing step after dyeing, or the dyeing fastness may be poor. Also in the multi-component fiber of the present invention, the glass transition temperature of at least one polymer substance which is not removed by water or an aqueous solution is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher. Is desirable. Furthermore, for polymeric substances that are not removed by water or aqueous solutions,
It is also possible to impart dyeability by blending a polymer substance having a glass transition temperature of 60 ° C. or higher, such as polymethylmethacrylate, polystyrene, or polyethylene terephthalate. The fibrous base material constituting the leather-like sheet of the present invention (the fibrous base material after the ultra-thinning in the case where the fibers are ultrafine synthetic fibers) is preferable in that it has a leather-like fullness and flexibility. The apparent density is 0.1 to 0.5 g / cm ³ , and the thickness is preferably 0.3 to 5.0 mm.

In the leather-like sheet of the present invention, the resin is composed of a continuous phase and a dispersed phase in the above-mentioned fibrous base material, and the continuous phase comprises components having a glass transition temperature of 20 ° C. or lower. The dispersed phase has a single layer structure composed of components having a glass transition temperature of 60 ° C. or higher, or has a glass transition temperature of 6
Of the layers having a glass transition temperature of 60 ° C. or more, the outermost layer in the dispersed phase has a diameter of 150 n.
It is necessary that a resin having m or more is added, and it is preferable that the resin forms a three-dimensional network structure in the fibrous base material. Further, at least the continuous phase is composed of a component having a glass transition temperature of 0 ° C. or lower, and the dispersed phase is composed of a component having a glass transition temperature of 70 to 120 ° C. or a component having a glass transition temperature of 70 to 120 ° C. Of the layers having a multi-layer structure having one layer and having a glass transition temperature of 70 to 120 ° C., the outermost layer in the dispersed phase preferably has a diameter of 180 to 500 nm. More preferably, the glass transition temperature of the continuous phase of the impregnated resin is −20 ° C. or lower, and the dispersed phase has a monolayer structure composed of components having a glass transition temperature of 80 to 110 ° C. or a glass transition temperature of 80 to 110 ° C. The outermost layer in the dispersed phase has a diameter of 200 to 400 nm, which is a multilayer structure having at least a single-layer structure of components and has a glass transition temperature of 80 to 110 ° C. When the glass transition temperature of the resin continuous phase exceeds 20 ° C, the leather-like sheet has low flexibility and poor texture. Further, when the resin does not have a dispersed phase containing a layer having a glass transition temperature of 60 ° C. or higher, the dye in the resin falls off in the reduction washing step after dyeing with the disperse dye, and the amount of the dye retained is significantly reduced. Therefore, the color developability of the resin is lowered, and the color unevenness on the surface becomes noticeable. Also, loosening the reducing conditions to prevent the dye from falling off improves the color unevenness, but the dyeing fastness is poor,
Contamination occurs due to dye migration. Further, even when the resin has a dispersed phase including a layer having a glass transition temperature of 60 ° C. or higher, the diameter of the outermost layer in the dispersed phase is 15
If it is less than 0 nm, the dye retention is poor and the color development is insufficient.

The glass transition temperature of each layer is determined by synthesizing a polymer having the same composition separately and measuring by DSC (differential scanning calorimeter).
Although it can be obtained by performing measurement with a TMA (thermo-mechanical measuring device) or the like, the value obtained by calculation by the following equation (1) may be used. The glass transition temperature of the homopolymer from each monomer component can be found in "Polymer Data Handbook (Basic Edition)" published by Baifukan Co., John Wiley & Sons, I
Published by nc. "Polymer HandBook Third
The values described in publications such as “prints” can be used. 1 / Tg _t = w ₁ / Tg ₁ + w ₂ / Tg ₂ + ... + w _i / Tg _i (1) (where Tg _t is the glass transition temperature of the polymer, w ₁ , ...
.., w _i : weight fraction of each monomer component of the polymer, Tg
₁ , ..., Tg _i : glass transition temperature of homopolymer from each monomer component of the polymer)

The proportion of the resin of the continuous phase in the resin impregnated into the fibrous base material is 20 to 95% by weight, which is more excellent in flexibility, color developability and dyeing fastness of the leather-like sheet. Therefore, it is more preferably 25 to 90% by weight, further preferably 30 to 80% by weight.

Further, the impregnating resin is composed mainly of a polymer of an ethylenically unsaturated monomer and, if necessary, a polyurethane resin, the texture of a leather-like sheet,
It is preferable because it has excellent physical properties and the leather-like sheet is easily manufactured. As the ethylenically unsaturated monomer that can be used, any of those conventionally used as a monofunctional ethylenically unsaturated monomer and a bifunctional or more polyfunctional ethylenically unsaturated monomer can be used. Examples of the monofunctional ethylenically unsaturated monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth)
Isobornyl acrylate, benzyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (Meth) acrylic acid 2-
(Meth) acrylic acid derivatives such as hydroxyethyl and 2-hydroxypropyl (meth) acrylate; styrene,
Aromatic vinyl compounds such as α-methylstyrene and p-methylstyrene; acrylamides such as (meth) acrylamide, diacetone (meth) acrylamide, N- [3- (dimethylamino) propyl] (meth) acrylamide; maleic acid, Fumaric acid, itaconic acid and their derivatives; Heterocyclic vinyl compounds such as vinylpyrrolidone; Vinyl compounds such as vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinylamide;
Examples include α-olefins typified by ethylene and propylene, and one or more of these can be used. Among these, the proportion of the (meth) acrylic acid derivative is preferably 60% by weight or more, and more preferably 70% by weight or more, since the light resistance, durability and texture of the leather-like sheet are further excellent. More preferably 80% by weight or more.

Examples of the bifunctional or more polyfunctional ethylenically unsaturated monomer that can be used together with the above-mentioned monofunctional ethylenically unsaturated monomer include, for example, ethylene glycol di (meth) acrylate and triethylene glycol di (meth). Acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (Meta)
Di (meth) acrylates such as acrylate, dimethyloltricyclodecanedi (meth) acrylate, glycerin di (meth) acrylate; tri-represented by trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc. Tetra (meth) acrylates represented by (meth) acrylates, pentaerythritol tetra (meth) acrylate, etc .; Polyfunctional aromatic vinyl compounds represented by divinylbenzene, trivinylbenzene, etc .; Allyl (meth) acrylate , 2 or more different ethylenically unsaturated bond-containing compounds represented by vinyl (meth) acrylate and the like; 2: 1 addition reaction product of 2-hydroxy-3-phenoxypropyl acrylate and hexamethylene diisocyanate, Pentaerythritol triacrylate and hexamethylene diisocyanate 2: 1 adduct, 2 of glycerol dimethacrylate and tolylene diisocyanate: molecular weight, such as 1 addition reaction product of 1500
The following urethane acrylates may be mentioned, and one or more of them may be used.

The proportion of the polyfunctional ethylenically unsaturated monomer in the total ethylenically unsaturated monomer is preferably 20% by weight or less, more preferably 0.1 to 15% by weight, and 0.5 to 20% by weight. It is more preferably 10% by weight. When the amount of the polyfunctional ethylenically unsaturated monomer exceeds 20% by weight, the production stability of the polymer of the ethylenically unsaturated monomer decreases, and the mechanical properties of the leather-like sheet obtained by excessive crosslinking of the resin Or the fluidity of the resin is lowered, so that the surface feel tends to be rough, which is not preferable.

Further, in order to further improve the light resistance of the leather-like sheet, as a part of the ethylenically unsaturated monomer, a hindered amino group having a light stabilizing effect and //
It is also possible to copolymerize an ethylenically unsaturated monomer having an ultraviolet absorbing group. Examples of the ethylenically unsaturated monomer having a hindered amino group and / or an ultraviolet absorbing group include 4- (meth) acryloyloxy-
2,2,6,6-Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloylamino-
Ethylenically unsaturated monomers having a hindered amino group such as 2,2,6,6-tetramethylpiperidine and 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 2- "2'-hydroxy-5'
(Meth) acryloyloxyethylphenyl "-2H-
Benzotriazole, 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4
Examples thereof include ethylenically unsaturated monomers having a benzotriazole group and a benzophenone group such as-(meth) acryloyloxyethylbenzophenone.

As the polyurethane resin which can be used in the present invention, known polyurethanes can be used. For example, a polyurethane resin obtained by using a polymer polyol, an organic polyisocyanate and a chain extender as main raw materials is used. be able to. As the polymer polyol, any of known polymer polyols can be used, and examples thereof include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and poly (methyltetramethylene glycol); polybutylene adipate diol, Polybutylene sebacate diol, polyhexamethylene adipate diol, poly (3-methyl-1,5-pentylene
Polyester polyols such as adipate) diol, poly (3-methyl-1,5-pentylene sebacate) diol, polycaprolactone diol, poly <β-methyl-δ-valerolactone>diol; polyhexamethylene carbonate diol, poly ( 3-methyl-1,5-
Polycarbonate polyols represented by pentylene carbonate) diol and the like; polyester carbonate polyols, etc.
One kind or two or more kinds can be used.

As the organic polyisocyanate that can be used in the present invention, any of the organic polyisocyanates that have been conventionally used in the production of ordinary polyurethane resins can be used. For example, hexamethylene diisocyanate, isophorone diisocyanate, 4,4 '. -Dicyclohexylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '
-Diphenylmethane diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,
Examples thereof include 5-naphthylene diisocyanate, and of these, one kind or two or more kinds can be used.

The chain extender component that can be used in the present invention is
Any of the chain extenders conventionally used in the production of ordinary polyurethane can be used, but a low molecular weight compound having a molecular weight of 300 or less and having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule is used. Is preferred. For example, diamines such as hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, phenylenediamine, tolylenediamine, xylenediamine, adipic acid dihydrazide, and isophthalic acid dihydrazide. Ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis- (β-hydroxyethyl) terephthalate , Diols such as xylylene glycol; triols such as trimethylolpropane; pentaols such as pentaerythritol; aminoethyl alcohol And amino alcohols represented by aminopropyl alcohol and the like, and one or more of them can be used.
In addition, during the chain elongation reaction, monoamines such as ethylamine, n-propylamine, i-propylamine, n-butylamine, i-butylamine, t-butylamine, cyclohexylamine, etc. together with the chain extender; 4-aminobutanoic acid, 6- Carboxyl group-containing monoamine compounds such as aminohexanoic acid, aminocyclohexanecarboxylic acid and aminobenzoic acid; monools such as methanol, ethanol, propanol and butanol may be used in combination.

Further, as a raw material for the polyurethane resin,
2,2-bis (hydroxymethyl) propionic acid, 2,
A carboxyl group-containing diol such as 2-bis (hydroxymethyl) butanoic acid or 2,2-bis (hydroxymethyl) valeric acid may be used in combination to introduce the carboxyl group into the polyurethane resin.

The method for producing the leather-like sheet of the present invention is not particularly limited, and it can be obtained by impregnating a fibrous base material with an aqueous dispersion of a resin or an organic solvent solution, coagulating and drying. Among these, the method using an aqueous resin dispersion is preferable because an organic solvent harmful to the environment and the human body is not used. In particular, as a production method, the inside of the fibrous base material has a single layer structure (A) consisting of a component having a glass transition temperature of 60 ° C. or more and a diameter of 150 nm or more in terms of an active ingredient, or a glass transition temperature of Resin aqueous dispersion (a) 10 to 100 parts by weight, (B) other resin aqueous dispersion or aqueous solution consisting of particles having a multilayer structure having at least one layer having a diameter of 150 nm or more and having a component of 60 ° C. or more (B) 0 to 90 parts by weight, (C) 0 to 20 parts by weight of a curing agent (c) and a resin that constitutes the resin aqueous dispersion (a), or the other resin aqueous dispersion or aqueous solution. An aqueous resin composition in which a component having a glass transition temperature of 20 ° C. or lower is present in one or both of the resins constituting (b) to give a component having a glass transition temperature of 20 ° C. or lower and glass. Transition temperature is 60
It contains at least a component of ℃ or more and has a glass transition temperature of 20
At least a part of the components having a glass transition temperature of 60 ° C or less forms a continuous phase, a layer having a glass transition temperature of 60 ° C or more and a diameter of 150 nm or more is attached to a resin inside the fiber substrate, and dyed with a disperse dye. Is important to do.

The aqueous resin dispersion (a) is particularly preferably an aqueous dispersion (a1) of a polymer obtained by emulsion polymerization of ethylenically unsaturated monomers. Also,
Other aqueous resin dispersions or aqueous solutions (b) described above
Are (i) an aqueous dispersion (b1) of a polymer obtained by emulsion polymerization of an ethylenically unsaturated monomer, (ii) an aqueous dispersion or aqueous solution (b2) of a polyurethane resin, and (iii) a polyurethane resin. Particularly preferred is at least one selected from the aqueous dispersion liquid (b3) of the composite resin obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of the aqueous dispersion liquid or aqueous solution.

The aqueous dispersions (a1 and b1) of the polymer obtained by emulsion-polymerizing the ethylenically unsaturated monomer that can be used in the present invention are the above-mentioned ethylenically unsaturated monomers which are emulsion-polymerized in water. It was obtained by this. The polymerization conditions at this time are not particularly limited, and the polymerization can be carried out in the same manner as the conventionally known emulsion polymerization of ethylenically unsaturated monomers, but the emulsion polymerization is generally performed at a temperature of 0 to 90 ° C. under an inert gas atmosphere. It is preferable to carry out from the viewpoint of polymerization stability and the like.

Examples of the polymerization initiator usable for the polymerization of ethylenically unsaturated monomers include benzoyl peroxide, lauroyl peroxide, dicumyl peroxide,
Oil-soluble peroxides such as di-t-butyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and diisopropylbenzene hydroperoxide;
Oil-soluble azo compounds such as 2'-azobisisobutyronitrile and 2,2'-azobis- (2,4-dimethylvaleronitrile); water-soluble such as hydrogen peroxide, potassium persulfate, sodium persulfate and ammonium persulfate Water-soluble azo compounds represented by azobiscyanovaleric acid, 2,2'-azobis- (2-amidinopropane) dihydrochloride and the like, and one or two of them can be mentioned. The above can be used. Further, together with the above-mentioned polymerization initiator, reducing agents such as ferrous sulfate, copper sulfate, Rongalit (sodium formaldehyde sulfoxylate), sodium thiosulfate, and sodium ascorbate, and sodium pyrophosphate, ethylenediaminetetraacetic acid if necessary. A redox initiator system combined with a chelating agent typified by a salt may be used.

Surfactants may be used to emulsify the polymer of ethylenically unsaturated monomers in water. As the surfactant that can be used, for example, sodium lauryl sulfate,
Anionic surfactants such as ammonium lauryl sulfate, sodium polyoxyethylene tridecyl ether acetate, sodium dodecylbenzene sulfonate, sodium alkyl diphenyl ether disulfonate, sodium dioctyl sulfosuccinate; polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether , Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene-polyoxypropylene block copolymer, and other nonionic surfactants. It is also possible to use a surfactant containing an ethylenically unsaturated group, a so-called reactive surfactant.

The polyurethane resin aqueous dispersion (b2) that can be used in the present invention may be any of those prepared by emulsifying and dispersing the above-mentioned polyurethane resin in water. It can be used and is not particularly limited. For example, (1) a hydrophobic terminal isocyanate prepolymer obtained from a high molecular weight polyol and an organic polyisocyanate is emulsified and dispersed in water by high mechanical shearing force in the presence of an emulsifier, and / or after being emulsified and dispersed. Prepolymer forced emulsification method to increase the molecular weight with a chain extender such as polyamine
It is possible to use a prepolymer mixing method in which a hydrophilic terminal isocyanate prepolymer having a carboxyl group introduced therein is self-emulsified in water and / or at the same time it is self-emulsified and then polymerized with a chain extender such as polyamine. As the emulsifier, an aqueous dispersion (a) of a polymer obtained by emulsion-polymerizing an ethylenically unsaturated monomer
The emulsifiers mentioned as examples of the emulsifiers which can be used for 1) and b1) can be used. Further, the terminal isocyanate prepolymer may be diluted with an organic solvent such as acetone, 2-butanone, toluene, ethyl acetate, tetrahydrofuran, dimethylformamide or the like in order to facilitate emulsification and dispersion. Further, part or all of the chain extender may be reacted before emulsifying the polyurethane.

The aqueous dispersion (b3) of the composite resin which can be used in the present invention is obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of an aqueous dispersion of polyurethane resin. As the polyurethane resin aqueous dispersion used at this time, the same polyurethane resin aqueous dispersion (b2) as described above can be used. At that time, the polyurethane prepolymer may be prepared by diluting the polyurethane prepolymer with an ethylenically unsaturated monomer having a (meth) acrylic acid derivative as a main component instead of an organic solvent such as 2-butanone. Further, it is preferable to use a polyurethane resin containing an ethylenically unsaturated group because coarse phase separation between the polyurethane resin and the acrylic resin in the composite resin does not easily occur and the physical properties of the leather-like sheet are further improved. Introduction of an ethylenically unsaturated group into polyurethane is carried out by using 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
Allyl alcohol, ethylene glycol diglycidyl ether and (meth) acrylic acid 1: 2 adduct, 1,6-
This is achieved by using a hydroxyl group-containing ethylenically unsaturated monomer such as a 1: 2 adduct of hexanediol diglycidyl ether and (meth) acrylic acid as a polyurethane raw material. On the other hand, as the ethylenically unsaturated monomer that is emulsion polymerized in the presence of the polyurethane resin aqueous dispersion,
What was illustrated as a manufacturing raw material of the aqueous dispersion liquid (a1 and b1) of the polymer obtained by emulsion-polymerizing an ethylenically unsaturated monomer can be used.

It is preferable that the aqueous resin composition used in the present invention has a cross-linking curability since it can withstand dyeing at high temperature. The impartation of the crosslinking curability is easily achieved by adding the curing agent (c) to the aqueous resin dispersion. The curing agent (c) that can be used has two or more functional groups in the molecule capable of reacting with the functional groups of the resin that constitutes the resin aqueous dispersion (a) and / or the resin aqueous dispersion or the aqueous solution (b). It is a water-soluble or water-dispersible compound contained. Examples of the combination of the functional group of the resin and the functional group of the curing agent (c) include a carboxyl group and an oxazoline group, a carboxyl group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and a cyclocarbonate group, a carboxyl group and an aziridine group, Examples include a combination of a carbonyl group and a hydrazide group. Among these,
The pot life of the aqueous resin composition is excellent, the production of the resin aqueous dispersion is easy, and since the resulting leather-like sheet has excellent texture and physical properties, a resin having a carboxyl group and an oxazoline group or a carbodiimide group are used. The combination of curing agents that they have is preferred. Examples of the curing agent having an oxazoline group include "Epocros K-2010E" and "Epocros K-2020" manufactured by Nippon Shokubai Co., Ltd.
E "," Epocros WS-500 "and the like. Examples of the curing agent having a carbodiimide group include" Carbodilite E-01 "manufactured by Nisshinbo Co., Ltd.,
"Carbodilite E-02", "Carbodilite V-0"
2 ”and the like. The amount of the curing agent (c) applied was such that the effective component of the curing agent (C) was 0.10 with respect to the total amount of the resin component of the resin aqueous dispersion (a) and the resin component of the resin aqueous dispersion (b). It is preferably 1 to 20% by weight, more preferably 0.5 to 15% by weight, and further preferably 1.0 to 10% by weight.
If the amount is less than 0.1% by weight, mechanical properties may be deteriorated by dyeing treatment at high temperature if the crosslinking in the resin is insufficient, and if it exceeds 20% by weight, the texture tends to be deteriorated. is there.

The concentration of the active ingredient of the aqueous resin composition used in the present invention is preferably 20% by weight or more, more preferably 25% by weight or more, and further preferably 30% by weight or more. If the concentration of the active ingredient is less than 20% by weight, there is a limit to the amount of the aqueous resin composition (A) that can be absorbed into the fibrous base material, so the amount of resin applied tends to be insufficient, and If the operation of drying after impregnation in order to increase the applied amount is repeated many times, the cost increases, which is not preferable.

The water-based resin composition used in the present invention can be used as long as it does not impair the properties of the leather-like sheet obtained.
Penetrants, defoamers, thickeners, extenders, curing accelerators, antioxidants, ultraviolet absorbers, fluorescent agents, fungicides, polyvinyl alcohol, water-soluble polymer compounds such as carboxymethyl cellulose, dyes, pigments, etc. May be appropriately contained.

The method for producing the leather-like sheet of the present invention is not particularly limited, but it is preferably obtained by combining the following steps. That is, it is obtained by sequentially performing the following steps (a) to (d). (A) a step of preparing fibers, (b) a step of producing a fibrous base material composed of the fibers, preferably a entangled nonwoven fabric, (c)
When the fiber is an ultrafine fiber-forming fiber, a step of separating and exfoliating or removing at least one component of the fiber by dissolution or decomposition to generate an ultrafine fiber, (2) a step of dyeing with a disperse dye, and the above step It is necessary to include the following step (e) between (b) and (c) or between (c) and (ii). (E) a step of applying the resin composition to the cloth by impregnating and solidifying the aqueous resin composition, and
If necessary, the following steps (f) and (g) may be added prior to impregnation with the aqueous resin composition, or the following step (h) may be added before or after the above step (d). Good. (F) a step of shrinking the cloth, (g) a step of temporarily fixing the cloth with a water-soluble sizing agent, (h) a step of forming naps of ultrafine fibers on at least one surface

The aqueous resin composition may be uniformly impregnated and applied to the entire fibrous base material, or may be applied to the surface of the fibrous base material so that the fibrous base material migrates to the surface and has a gradient in the thickness direction. Coagulation is 5
It is possible to adopt a method of heat-coagulating by heat treatment in a drying device of 0 to 200 ° C, or dry coagulation, or heat treatment at 50 to 200 ° C, hot water treatment at 70 to 100 ° C, and steam treatment at 100 to 200 ° C. . After impregnating the aqueous resin composition, coagulating and drying, the impregnated resin and the fiber may be adhered to each other or a space may be formed between the impregnated resin and the fiber. The amount of impregnated resin applied is
The solid content of the impregnated resin is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, still more preferably 30 to 120 parts by weight, based on 100 parts by weight of the fibrous base material. . When the amount of the impregnated resin is less than 10 parts by weight, the obtained sheet tends to have insufficient solidity, and when it exceeds 200 parts by weight, the flexibility of the obtained sheet tends to be impaired. The obtained leather-like sheet is dyed with a known disperse dye, and in the case of a fibrous base material that needs to be made into ultrafine fibers, the leather-like sheet made into ultrafine fibers can be obtained by the method described above. It is also possible to make a suede-like leather-like sheet by subjecting at least one surface of the obtained leather-like sheet to a raising process by a known raising method, for example, sandpaper, needle cloth or the like.
The thickness of the obtained suede-like leather-like sheet is 0.
3 to 3.0 mm has an apparent density of 0.2 to 0.8
g / cm ³ is preferable from the viewpoint of leather-like texture.

The leather-like sheet of the present invention has excellent dyeing fastness and color developability and is excellent in texture. As a suede type, not only for clothing but also for clothing, interiors, shoes, car seats, Suitable for bags, bags, various gloves, sports goods such as gloves.

[0036]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[Lightfastness] A fade tester (UV long life fade meter FAL-5H / B / BL manufactured by Suga Test Instruments Co., Ltd.
The surface of the leather-like sheet was subjected to light irradiation with an ultraviolet carbon arc lamp (63 ° C.) for 160 hours, and the degree of discoloration was determined using a gray scale for discoloration (JIS L 0804). It should be noted that the smaller this value is, the more the color is significantly faded.

[Sublimation fastness] JIS on the leather-like sheet surface
Attached white cloth nylon specified by L 0803 (No. 8)
And apply pressure evenly so that the load is 300 g / cm ^2, and leave it for 24 hours in an atmosphere of 40 ° C. and 90% relative humidity to determine the degree of migration of the dye to the nylon white cloth by staining with gray scale (JIS Issue determination was performed using L 0805). It should be noted that the smaller this value is, the more significantly the nylon white cloth is contaminated.

[Outer Diameter of Each Layer of Resin-Dispersed Particles] A part of the emulsion was withdrawn after the polymerization of each layer and measured by a dynamic light scattering method using "ELS-800" manufactured by Otsuka Electronics Co., Ltd. The average particle size of the particles in emulsion was determined by the analysis described in "Colloid Science Vol. IV, Colloid Science Experimental Method", page 103, issued by Tokyo Kagaku Dojinsha, and this was taken as the outer diameter of each layer.

Table 1 shows the abbreviations of the compounds used in the following Reference Examples, Examples and Comparative Examples.

[0041]

[Table 1]

<< Production of Fibrous Base Material >> [Reference Example 1] PET and nylon 6 were melt extruded by separate extruders, respectively, and the PET / nylon 6 weight ratio was 70.
After measuring each with a gear pump to become / 30,
It is supplied into a spinning pack, discharged at a spinneret temperature of 290 ° C., wound at a speed of 500 m / min, and then stretched to obtain a multi-layer splittable fiber in which PET and nylon 6 having a single yarn fineness of 3.0 decitex are alternately laminated. It was On the cut surface of the obtained split fiber, PET (6 layer portion) and nylon 6 (5 layer portion) were alternately arranged in 11 layers. After the drawing, mechanical crimping was applied and then cut into 51 mm to obtain staple fibers. The staple fiber thus obtained was processed into a web through a card and a cross wrapper. Next, needle punching with a punch number of 1600 punches / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was dipped in a bath containing hot water at 90 ° C. to shrink the nonwoven fabric. Shrinkage rate [(length of nonwoven fabric after shrinkage / length of nonwoven fabric before shrinkage) × 10
0] was 16% in the vertical direction and 17% in the horizontal direction.
Then, the contracted nonwoven fabric is dried to give an apparent density of 0.17.
A fibrous base material composed of ultrafine fiber-forming fibers having a laminated cross-sectional shape of 0 g / cm ³ was obtained (hereinafter referred to as nonwoven fabric (A)).

[Reference Example 2] PET was used as an island component, and alkali-soluble PET was used as a sea component, melt-extruded by separate extruders, and weighed by a gear pump so that the weight ratio of PET / alkali-soluble PET was 60/40. After that, it is supplied into the spinning pack, the fiber shape is regulated by the spinneret,
It was discharged at a spinneret temperature of 290 ° C., wound at a speed of 500 m / min, and then stretched to obtain sea-island fibers having a single yarn fineness of 3.0 decitex. The cut surface obtained by cutting the obtained sea-island fiber is
It was a sea-island shape with 25 islands. After the drawing, mechanical crimping was applied and then cut into 51 mm to obtain staple fibers. The staple fiber thus obtained was processed into a web through a card and a cross wrapper. Next, the number of punches is 120
Needle punching of 0 punch / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was dipped in a bath containing hot water at 90 ° C. to shrink the nonwoven fabric. Shrinkage rate [(length of nonwoven fabric after shrinkage / length of nonwoven fabric before shrinkage) x
100] was 20% in the vertical direction and 21% in the horizontal direction. Thereafter, the contracted nonwoven fabric is dried to give an apparent density of 0.
A fibrous base material composed of ultrafine fiber-forming fibers having a sea-island cross-sectional shape of 180 g / cm ³ was obtained (hereinafter referred to as nonwoven fabric (B)).

[Reference Example 3] IPA-modified PET as an island component, ethylene copolymerized PVA as a sea component, and IPA-modified P
ET and ethylene copolymerized PVA are melt-extruded by separate extruders, and IPA-modified PET and ethylene copolymerized PVA are melt-extruded.
Was weighed with a gear pump so that the weight ratio was 60/40, then fed into the spinning pack, the fiber shape was regulated by the spinneret part, and the fiber was discharged at a spinneret temperature of 260 ° C. at a speed of 500 m /
Rolled up in minutes. After spinning, drawing was performed to obtain sea-island fibers having a single yarn fineness of 3.0 decitex. The cut surface obtained by cutting the obtained sea-island fiber had a sea-island shape with 25 islands.
After the drawing, mechanical crimping was applied and then cut into 51 mm to obtain staple fibers. The staple fiber thus obtained was processed into a web through a card and a cross wrapper. Next, needle punching with a punch number of 1200 punches / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was dipped in a bath containing hot water at 90 ° C. to shrink the nonwoven fabric. The shrinkage ratio [(length of nonwoven fabric after shrinkage / length of nonwoven fabric before shrinkage) × 100] was 18% in the vertical direction and 17% in the horizontal direction. Then, the contracted nonwoven fabric was dried to obtain a fibrous base material composed of ultrafine fiber-forming fibers having an apparent density of 0.174 g / cm ^{3 and} a sea-island cross-sectional shape (hereinafter referred to as a nonwoven fabric (C)). .

<< Production of Acrylic Resin Aqueous Dispersion >> [Reference Example 4] (1) Initial charging: SS-H was added to a flask equipped with a cooling tube.
0.18 g, sodium carbonate 0.18 g and distilled water 3
After 41 g was weighed and heated to 80 ° C., the inside of the system was sufficiently replaced with nitrogen.

(2) Emulsion polymerization: Next, 17.6 g of MMA
And 0.36 g of HDDA and stirred for 20 minutes, then K
An aqueous solution containing 0.05 g of PS and 1.6 g of distilled water was added, and the mixture was kept at 80 ° C. for 40 minutes (glass transition temperature of this layer was 104 ° C., outer diameter of layer was 110 nm).
Then, an aqueous solution containing 0.23 g of KPS and 7.0 g of distilled water was added, and 5 minutes after that, BA153.1 was added.
g, HDDA 1.55g, ALMA 0.16g and S
The DOSS (0.77 g) was added dropwise from the dropping funnel into the flask over 120 minutes, and the mixture was heated to 80 ° C. for 3 minutes after completion of the dropping.
Hold for 0 minutes (The glass transition temperature of this layer is -53 ° C.
Is). Then, 0.06 g of KPS and distilled water 2.
An aqueous solution consisting of 0 g was added, and after 5 minutes, MMA
42.7g, HDDA0.43g, ALMA0.09
g, and a mixed solution of 0.22 g of SDOSS were dropped into the flask from the dropping funnel over 50 minutes, and after the dropping, the temperature was maintained at 80 ° C. for 30 minutes (the glass transition temperature of this layer was 104 ° C., and the outer diameter of the layer was Is 250 nm). Furthermore, an aqueous solution consisting of 0.22 g of KPS and 6.5 g of distilled water was added, and 5 minutes later, 136.8 g of BA and M
A mixture of 7.2 g of AA and 0.72 g of SDOSS,
Dropping from the dropping funnel into the flask over 100 minutes,
After the completion of the dropping, the temperature was kept at 80 ° C. for 60 minutes to complete the polymerization (the glass transition temperature of this layer is −48 ° C.). Next, 4.5 g of N, N-dimethylethanolamine, 4.2 g of sodium hydrogen carbonate, 7.2 g of EM, 1.8 g of SS-H.
And a mixed solution of 64.0 g of distilled water were added to obtain an acrylic resin aqueous dispersion having a resin solid content concentration of 45% by weight (hereinafter referred to as acrylic). It should be noted that the polymerization proceeds without generating new particles during the seed polymerization, and the particle size distribution of acrylic is monodisperse.

Reference Example 5 (1) Initial charging: SS-H was placed in a flask equipped with a cooling tube.
0.18 g, sodium carbonate 0.18 g and distilled water 3
After weighing 34 g and raising the temperature to 80 ° C., the system was thoroughly replaced with nitrogen.

(2) Emulsion polymerization: Next, 17.6 g of St and 0.36 g of HDDA were added and after stirring for 20 minutes, KP
An aqueous solution containing 0.05 g of S and 1.6 g of distilled water was added, and the mixture was kept at 80 ° C. for 40 minutes (glass transition temperature of this layer was 99 ° C., outer diameter of layer was 110 nm). Then, an aqueous solution containing 0.32 g of KPS and 9.8 g of distilled water was added, and after 5 minutes, 212.3 g of EA and H were added.
DDA 3.24g, ALMA 0.43g and SDOS
The mixed solution of S1.08 g was dropped into the flask from the dropping funnel over 160 minutes, and after the dropping was finished, the mixture was kept at 80 ° C. for 30 minutes (the glass transition temperature of this layer is −23 ° C.). After that, 0.05 g of KPS and 1.6 g of distilled water
5 minutes later, MMA2 was added.
7.0g, EA8.64g, HDDA0.29g, AL
A mixed solution of 0.07 g of MA and 0.18 g of SDOSS was dropped into the flask from the dropping funnel over 40 minutes, and after completion of the dropping, the mixture was kept at 80 ° C. for 30 minutes (glass transition temperature of this layer was 63 ° C. The outer diameter is 270 nm). Furthermore, 0.14 g of KPS and 4.1 g of distilled water
5 minutes later, BA81.
A mixed liquid of 9 g, 8.1 g of MAA and 0.45 g of SDOSS was dropped into the flask from the dropping funnel over 70 minutes, and after completion of the dropping, the mixture was kept at 80 ° C. for 60 minutes to complete the polymerization (glass transition temperature of this layer). Is -42 ° C).
Next, 5.0 g of N, N-dimethylethanolamine, 4.7 g of sodium hydrogen carbonate, 7.2 g of EM, SS-H.
A mixed solution of 1.8 g and 70 g of distilled water was added to obtain an acrylic resin aqueous dispersion having a resin solid content concentration of 45% by weight (hereinafter referred to as acrylic). It should be noted that the polymerization proceeds without generating new particles during the seed polymerization, and the particle size distribution of acrylic is monodisperse.

Reference Example 6 (1) Initial charging: SS-H was placed in a flask equipped with a cooling tube.
0.18 g, sodium carbonate 0.18 g and distilled water 3
After weighing 49 g and raising the temperature to 80 ° C., the inside of the system was sufficiently replaced with nitrogen.

(2) Emulsion polymerization: Next, 17.6 g of MMA
And 0.36 g of HDDA and stirred for 20 minutes, then K
An aqueous solution containing 0.05 g of PS and 1.6 g of distilled water was added, and the mixture was kept at 80 ° C. for 40 minutes (glass transition temperature of this layer was 104 ° C., outer diameter of layer was 110 nm).
Then, an aqueous solution containing 0.32 g of KPS and 9.8 g of distilled water was added, and after 5 minutes, MMA211.7 was added.
g, HDDA 3.24g, ALMA 1.08g and S
A mixture of DOSS (1.08 g) was added dropwise from the dropping funnel into the flask over 180 minutes, and the mixture was heated to 80 ° C. for 3 minutes after the addition was completed.
Hold for 0 minutes (glass transition temperature of this layer is 104 ° C., outer diameter of layer is 260 nm). Furthermore, KPS
An aqueous solution consisting of 0.19 g and 5.7 g of distilled water was added, and 5 minutes later, 119.7 g of BA and 6.3 of MAA.
g and SDOSS (0.63 g) were added dropwise from the dropping funnel into the flask over 90 minutes.
The polymerization was completed by holding at 0 ° C for 60 minutes (the glass transition temperature of this layer is -48 ° C). Then, a mixed solution of 3.9 g of N, N-dimethylethanolamine, 3.7 g of sodium hydrogen carbonate, 7.2 g of EM, 1.8 g of SS-H and 58 g of distilled water was added to the acrylic system having a resin solid content concentration of 45% by weight. An aqueous resin dispersion was obtained (hereinafter referred to as acrylic). It should be noted that the polymerization proceeds without generating new particles during the seed polymerization, and the particle size distribution of acrylic is monodisperse.

Reference Example 7 (1) Initial charging: SDOSS was added to a flask with a cooling tube.
0.27 g and 560 g of distilled water were weighed out, heated to 80 ° C., and then the system was sufficiently replaced with nitrogen.

(2) Emulsion polymerization: KPS 0.44
g and distilled water 13.1 g were added, and 5 minutes later, 105.8 g of BA and 1.08 of HDDA were added.
g, a mixed solution of 1.08 g of ALMA and 0.43 g of SDOSS was dropped into the flask from the dropping funnel over 90 minutes, and after the dropping was completed, the mixture was kept at 80 ° C. for 60 minutes (the glass transition temperature of this layer is −52 ° C.). ). Then KPS
An aqueous solution consisting of 0.13 g and distilled water 3.9 g was added, and after 5 minutes, 105.8 g of BA, HDDA1.
08g, ALMA 1.08g, and SDOSS 0.4
3 g of the mixed solution was dropped into the flask from the dropping funnel over 90 minutes, and after the completion of dropping, the mixture was kept at 80 ° C for 60 minutes (the glass transition temperature of this layer is -52 ° C). Furthermore, an aqueous solution consisting of 0.07 g of KPS and 2.0 g of distilled water was added, and after 5 minutes, 49.7 g of MMA and H
DDA 0.27g, MAA 4.05g and SDOSS
Add 0.22 g of the mixed solution into the flask from the dropping funnel.
The solution was added dropwise over 0 minutes, and after completion of the addition, the temperature was kept at 80 ° C. for 60 minutes to complete the polymerization (the glass transition temperature of this layer was 11
2 ° C., outer diameter of layer is 180 nm). Then N,
A mixed solution of 2.5 g of N-dimethylethanolamine, 2.4 g of sodium hydrogen carbonate, 5.4 g of EM, 1.4 g of SS-H and 39 g of distilled water was added to give a resin solid content concentration of 3
A 0% by weight acrylic resin aqueous dispersion was obtained (hereinafter referred to as acrylic). It should be noted that the polymerization proceeds without generating new particles during the seed polymerization, and the particle size distribution of acrylic is monodisperse.

Reference Example 8 (1) Initial charging: SS-H was placed in a flask equipped with a cooling tube.
0.18 g, sodium carbonate 0.18 g and distilled water 3
After 41 g was weighed and heated to 80 ° C., the inside of the system was sufficiently replaced with nitrogen.

(2) Emulsion polymerization: Next, 17.6 g of MMA
And 0.36 g of HDDA and stirred for 20 minutes, then K
An aqueous solution containing 0.05 g of PS and 1.6 g of distilled water was added, and the mixture was kept at 80 ° C. for 40 minutes (glass transition temperature of this layer was 104 ° C., outer diameter of layer was 110 nm).
Then, an aqueous solution containing 0.23 g of KPS and 7.0 g of distilled water was added, and 5 minutes after that, BA153.1 was added.
g, HDDA 1.55g, ALMA 0.16g and S
The DOSS (0.77 g) was added dropwise from the dropping funnel into the flask over 120 minutes, and the mixture was heated to 80 ° C. for 3 minutes after completion of the dropping.
Hold for 0 minutes (The glass transition temperature of this layer is -53 ° C.
Is). Then, 0.06 g of KPS and distilled water 2.
An aqueous solution of 0 g was added, and after 5 minutes, EA2
1.4g, MMA21.4g, HDDA0.35g, A
A mixed solution of 0.09 g of LMA and 0.22 g of SDOSS was dropped into the flask from the dropping funnel over 50 minutes, and after the completion of dropping, the mixture was kept at 80 ° C. for 30 minutes (the glass transition temperature of this layer was 28 ° C. The outer diameter is 250 nm). Furthermore, 0.22 g of KPS and 6.5 g of distilled water
5 minutes later, BA13 was added.
6.8 g, MAA 7.2 g and SDOSS 0.72 g
The mixed solution of (1) was dropped into the flask from the dropping funnel over 100 minutes, and after completion of the dropping, the mixture was kept at 80 ° C for 60 minutes to complete the polymerization (the glass transition temperature of this layer is -48 ° C). Then N, N-dimethylethanolamine 4.5
g, sodium hydrogencarbonate 4.2 g, EM 7.2 g, SS
A mixed solution of 1.8 g of H and 64.0 g of distilled water was added to obtain an acrylic resin aqueous dispersion having a resin solid content concentration of 45% by weight (hereinafter referred to as acrylic). It should be noted that the polymerization proceeds without generating new particles during the seed polymerization, and the particle size distribution of acrylic is monodisperse.

Reference Example 9 (1) Initial charging: SS-H was placed in a flask equipped with a cooling tube.
0.18 g, sodium carbonate 0.18 g and distilled water 3
After weighing 39 g and raising the temperature to 80 ° C., the inside of the system was sufficiently replaced with nitrogen.

(2) Emulsion polymerization: Next, BA (17.8 g) and HDDA (0.18 g) were added and stirred for 20 minutes.
An aqueous solution containing 0.05 g of S and 1.6 g of distilled water was added, and the mixture was kept at 80 ° C. for 40 minutes (the glass transition temperature of this layer is −53 ° C.). Then, an aqueous solution consisting of 0.16 g of KPS and 4.9 g of distilled water was added, and 5 minutes later, 106.9 g of BA, 0.97 g of HDDA, ALM.
A mixture of 0.11 g A and 0.54 g SDOSS,
It dripped from the dropping funnel into the flask over 90 minutes, and after the dropping was completed, it was kept at 80 ° C. for 30 minutes (the glass transition temperature of this layer is −53 ° C.). After that, KPS 0.16g
And an aqueous solution consisting of 4.9 g of distilled water was added,
After 10 minutes, BA106.9g, HDDA0.97g, A
A mixed solution of 0.11 g of LMA and 0.54 g of SDOSS was dropped into the flask from the dropping funnel over 90 minutes and kept at 80 ° C for 30 minutes after completion of the dropping (the glass transition temperature of this layer is -53 ° C). . In addition, KPS0.
An aqueous solution consisting of 19 g and 5.7 g of distilled water was added,
5 minutes later, BA119.1g, MAA6.93g
And a mixed solution of 0.63 g of SDOSS was dropped into the flask from the dropping funnel over 90 minutes, and after completion of the dropping, 80
The temperature was kept at 60 ° C. for 60 minutes to complete the polymerization (the glass transition temperature of this layer is −47 ° C.). Next, 4.3 g of N, N-dimethylethanolamine and sodium hydrogen carbonate 4.
1 g, EM 7.2 g, SS-H 1.8 g and distilled water 6
2 g of the mixed solution was added to obtain an acrylic resin aqueous dispersion having a resin solid content concentration of 45% by weight (hereinafter referred to as acrylic). It should be noted that the polymerization proceeds without generating new particles during the seed polymerization, and the particle size distribution of acrylic is monodisperse.

Reference Example 10 (1) Initial charging: SDOSS was added to a flask with a cooling tube.
After 0.27 g and 549 g of distilled water were weighed and heated to 80 ° C., the system was sufficiently replaced with nitrogen.

(2) Emulsion polymerization: KPS 0.41
g and distilled water 12.3 g were added, and 5 minutes later, 99.2 g of MMA and 1.01 of HDDA were added.
g, a mixed solution of 1.01 g of ALMA and 0.41 g of SDOSS was dropped into the flask from the dropping funnel over 90 minutes, and after the dropping was finished, the mixture was kept at 80 ° C. for 60 minutes (the glass transition temperature of this layer is 104 ° C., Layer outer diameter is 130n
m). Then, an aqueous solution consisting of 0.12 g of KPS and 3.7 g of distilled water was added, and after 5 minutes, B
A99.2g, HDDA1.01g, ALMA1.01
g, and a mixed solution of 0.41 g of SDOSS were dropped into the flask over 90 minutes from the dropping funnel, and after the dropping was completed, the mixture was kept at 80 ° C. for 60 minutes (the glass transition temperature of this layer is −52 ° C.). Further, an aqueous solution consisting of 0.08 g of KPS and 2.5 g of distilled water was added, and 5 minutes later, BA62.1 g, MAA 5.4 g and SDOSS were added.
Add 0.27 g of the mixed solution into the flask from the dropping funnel.
The solution was added dropwise over 0 minutes, and after the completion of the addition, the temperature was kept at 80 ° C. for 60 minutes to complete the polymerization (the glass transition temperature of this layer was −4).
4 ° C). Then, N, N-dimethylethanolamine 3.4 g, sodium hydrogen carbonate 3.2 g, EM5.4.
g, SS-H 1.4 g, and distilled water 48 g were added to obtain an acrylic resin aqueous dispersion having a resin solid content concentration of 30% by weight (hereinafter referred to as acrylic). In addition,
Polymerization proceeds without generating new particles during seed polymerization, and the particle size distribution of acrylic is monodisperse.

<< Preparation of Aqueous Polyurethane Resin Dispersion >> [Reference Example 11] In a flask, 200 g of polytetramethylene glycol having a number average molecular weight of 2000, 100 g of polyhexamethylene carbonate diol having a number average molecular weight of 2000, and 2,2-diene were prepared. 8.9 g of methylolbutanoic acid,
62.7 g of 2,4-tolylene diisocyanate was weighed out and stirred at 90 ° C. for 2 hours in a dry nitrogen atmosphere to quantitatively react the hydroxyl groups in the system to obtain an isocyanate-terminated prepolymer. After adding 195 g of 2-butanone to this and stirring uniformly, the temperature inside the flask was lowered to 40 ° C., 5.9 g of triethylamine was added, and the mixture was stirred for 10 minutes. Then, sodium lauryl sulfate as an emulsifier 4.
0 g and an aqueous solution of 4.0 g of sodium polyoxyethylene tridecyl ether acetate dissolved in 522 g of distilled water were added to the above prepolymer, and the mixture was stirred with a homomixer for 1 minute to emulsify, and immediately piperazine hexahydrate 13.4.
g, isophoronediamine 7.1 g and diethylenetriamine 1.9 g were added to an aqueous solution in which distilled water 379 g was added, and the mixture was stirred for 1 minute with a homomixer to carry out a chain extension reaction (the glass transition temperature of this polyurethane resin was -38 ° C). And the average particle size is 140 nm). After that, 2-
Butanone was removed by a rotary evaporator to obtain a polyurethane resin aqueous dispersion having a resin solid content concentration of 30% by weight (hereinafter referred to as PU).

<< Production of Composite Resin Aqueous Dispersion >> [Reference Example 12] 480 g of PU obtained in Reference Example 11,
Ferrous sulfate heptahydrate 0.011 g, potassium pyrophosphate 0.32 g, Rongalit (formaldehyde sodium sulfoxylate dihydrate) 0.50 g, ethylenediamine tetraacetic acid disodium salt 0.022 g and distilled water 35 g Was weighed and heated to 40 ° C., and then the system was thoroughly replaced with nitrogen. Next, a mixture of 205.2 g of BA, 4.32 g of glycidyl methacrylate, 6.48 g of HDDA, and 1.08 g of sodium polyoxyethylene tridecyl ether acetate, 0.43 g of cumene hydroperoxide, and sodium polyoxyethylene tridecyl ether acetate 0 The emulsion of 0.22 g and 25 g of distilled water was dropped into the flask from separate dropping funnels over 300 minutes, and after completion of the dropping, the temperature was raised to 50 ° C. and held for 60 minutes to complete the polymerization (this composite resin Has a glass transition temperature of -42 ° C and an average particle size of 190 nm). A composite resin aqueous dispersion having a resin solid content concentration of 45% by weight was obtained (hereinafter referred to as composite).

Example 1 An aqueous resin composition containing 100 parts of the acrylic prepared in Reference Example 4 and 5 parts of an oxazoline-based cross-linking agent (“Epocros K-2010E” manufactured by Nippon Shokubai Co., Ltd.) was obtained in Reference Example 1. Nonwoven fabric (A) 10
0 part was impregnated to give 60 parts of solid content, dried with hot air of 140 ° C., and then pressed with a roller heated to 160 ° C. to smooth the surface and adjust the thickness, A fibrous substrate having a thickness of about 1 mm was obtained. continue,
Kayalo as a disperse dye by a circular jet dyeing machine
n polyester Blue AUL-S (manufactured by Nippon Kayaku Co., Ltd.)
Used at 5% owf, bath ratio 1:30, 130 ° C x 60 minutes (heating from 50 ° C to 130 ° C over 30 minutes, 130 ° C
And hold for 60 minutes). After dyeing, it is reduced and washed with sodium hydroxide 6 g / L and Techlite (manufactured by Tokai Denka Kogyo Co., Ltd.) 6 g / L at 80 ° C. for 60 minutes, and at the same time, the splittable fibers constituting the fibrous substrate are split (extra fine fibers Average fineness: 0.32 decitex), and 1 g of acetic acid
After being neutralized at 60 ° C. for 10 minutes at / L, it was washed with water and dried. Then, the surface was buffed with sandpaper to finish, and a suede-like leather-like sheet having an apparent density of 0.52 g / cm ³ was obtained. This product was excellent in flexibility and fullness, and exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was 4-5, and the sublimation fastness was 4, showing excellent values.

Example 2 Aqueous solution consisting of 20 parts of the acrylic prepared in Reference Example 4, 80 parts of the acrylic prepared in Reference Example 8 and 3 parts of an oxazoline-based cross-linking agent (“Epocros K-2010E” manufactured by Nippon Shokubai Co., Ltd.). Resin composition,
By impregnating 100 parts of the non-woven fabric (B) obtained in Reference Example 2 with 35 parts of solid content, drying with hot air of 140 ° C., and then pressing with a roller heated to 160 ° C. The surface was smoothed and the thickness was adjusted to obtain a fibrous substrate having a thickness of about 1 mm. Then, the fibrous base material is immersed in an aqueous sodium hydroxide solution having a concentration of 40 g / l adjusted to a temperature of 95 ° C., and squeezing with a roller is repeated to decompose and remove the alkali-soluble PET which is a sea component of the sea-island fiber. Was ultrafine (average fineness of ultrafine fiber: 0.089 decitex). Then, after performing dyeing, reduction washing and neutralization treatment with a circular jet dyeing machine in the same manner as in Example 1, the surface is buffed with sandpaper to finish, and the apparent density is 0.46 g / A cm ³ suede-like leather-like sheet was obtained. This product was excellent in flexibility and fullness, and exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was 4 and the sublimation fastness was 4-5, which were excellent values.

[Example 3] An aqueous resin composition comprising 100 parts of the acrylic prepared in Reference Example 5 and 3 parts of an oxazoline-based cross-linking agent ("Epocros K-2010E" manufactured by Nippon Shokubai Co., Ltd.) was obtained in Reference Example 1. Nonwoven fabric (A) 10
Impregnated so that 40 parts of solid content is added to 0 part,
In the same manner as in Example 1, surface smoothing / thickness adjustment, dyeing,
After reduction cleaning, ultrafine fiberization and neutralization treatment, the surface was buffed with sandpaper to finish, and a suede-like leather-like sheet having an apparent density of 0.47 g / cm ³ was obtained. This product was excellent in flexibility and fullness, and exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was 4 and the sublimation fastness was 3-4, which were excellent values.

Example 4 Aqueous solution consisting of 50 parts of the acrylic prepared in Reference Example 6, 50 parts of the acrylic prepared in Reference Example 8 and 5 parts of an oxazoline-based crosslinking agent (“Epocros K-2010E” manufactured by Nippon Shokubai Co., Ltd.). Resin composition,
By impregnating 100 parts of the non-woven fabric (C) obtained in Reference Example 3 with 40 parts of solid content, drying with hot air of 140 ° C., and pressing with a roller heated to 160 ° C. The surface was smoothed and the thickness was adjusted to obtain a fibrous substrate having a thickness of about 1 mm. Subsequently, the fibrous substrate was immersed in hot water at 95 ° C. and squeezing with a roller was repeated to dissolve and remove the ethylene copolymerized PVA, which is the sea component of the sea-island cross-section multi-component fiber, to make the fiber ultrafine (of ultrafine fiber). Average fineness: 0.0
87 decitex). Then, after performing dyeing, reduction washing and neutralization treatment in the same manner as in Example 1 with a circular jet dyeing machine, the surface is buffed with sandpaper to finish, and the apparent density is 0.47 g / A cm ³ suede-like leather-like sheet was obtained. This product was excellent in flexibility and fullness, and exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was 4-5 and the sublimation fastness was 4-5, which were excellent values.

Example 5 Aqueous solution consisting of 40 parts of the acrylic prepared in Reference Example 7, 60 parts of the acrylic prepared in Reference Example 9 and 2 parts of a carbodiimide type crosslinking agent ("Carbodilite E-01" manufactured by Nisshinbo Industries Inc.). Resin composition,
100 parts of the non-woven fabric (A) obtained in Reference Example 1 was impregnated with 30 parts of solid content, dried with hot air at 140 ° C., and then smoothed in the same manner as in Example 1. -Suede-like leather-like sheet with an apparent density of 0.44 g / cm ³ after finishing the thickness adjustment, dyeing, reduction washing, ultrafine fiberization and neutralization treatment, and then buffing the surface with sandpaper. Got This product was excellent in flexibility and fullness, and exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was 3-4, and the sublimation fastness was 4, showing excellent values.

Example 6 An aqueous resin composition consisting of 10 parts of the acrylic produced in Reference Example 6 and 90 parts of PU produced in Reference Example 11 was added to 100 parts of the nonwoven fabric (B) obtained in Reference Example 2. After impregnation so as to give 40 parts of solid content and drying with hot air at 140 ° C., surface smoothing / thickness adjustment, ultrafine fiberization, dyeing, reduction washing and neutralization treatment were carried out in the same manner as in Example 2. After that, the surface is buffed with sandpaper to finish, and the apparent density is 0.
A 45 g / cm ³ suede-like leather-like sheet was obtained. This product was excellent in flexibility and fullness, and exhibited a good texture. Also, the surface appearance of this leather-like sheet is good,
The fibers and the impregnated resin were colored to the same extent. The light fastness was No. 4, and the sublimation fastness was No. 4, showing excellent values.

Example 7 Aqueous solution consisting of 30 parts of the acrylic prepared in Reference Example 4, 70 parts of the composite prepared in Reference Example 12 and 2 parts of oxazoline-based cross-linking agent (“Epocros K-2010E” manufactured by Nippon Shokubai Co., Ltd.). 100 parts of the non-woven fabric (A) obtained in Reference Example 1 was impregnated with the resin composition so that 50 parts of the solid content was applied and dried with hot air at 140 ° C. After surface smoothing / thickness adjustment, dyeing, reduction cleaning / ultrafine fiberization and neutralization treatment, the surface is buffed with sandpaper to finish, and the apparent density is 0.51 g / cm ³ suede. A leather-like sheet having a tone was obtained. This one is excellent in flexibility and fulfillment,
It exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was 3-4, and the sublimation fastness was 4, showing excellent values.

Example 8 An aqueous resin composition consisting of 15 parts of the acrylic prepared in Reference Example 6 and 85 parts of the composite produced in Reference Example 12 was added to 100 parts of the nonwoven fabric (C) obtained in Reference Example 3. After impregnation so that 30 parts of solid content is applied and drying with hot air at 140 ° C., surface smoothing / thickness adjustment, ultrafine fiberization, dyeing, reduction washing and neutralization are carried out in the same manner as in Example 4. After the treatment, the surface is buffed with sandpaper to finish, and the apparent density is 0.
A 45 g / cm ³ suede-like leather-like sheet was obtained. This product was excellent in flexibility and fullness, and exhibited a good texture. Also, the surface appearance of this leather-like sheet is good,
The fibers and the impregnated resin were colored to the same extent. The light fastness was 4 and the sublimation fastness was 4-5, which were excellent values.

Comparative Example 1 An aqueous resin composition containing 100 parts of the acrylic prepared in Reference Example 7 and 3 parts of an oxazoline-based cross-linking agent (“Epocros K-2010E” manufactured by Nippon Shokubai Co., Ltd.) was obtained in Reference Example 1. Nonwoven fabric (A) 10
0 part was impregnated so that 40 parts of solid content was applied, and dried with hot air at 140 ° C., then, in the same manner as in Example 1, surface smoothing / thickness adjustment, dyeing, reduction washing / ultrafine fiber After surfaceization and neutralization, the surface is buffed with sandpaper to finish, and the apparent density is 0.48g / c.
to obtain a leather-like sheet of suede m ^3. This one is
The surface appearance was good, and although the fibers and the impregnated resin were colored to the same extent, they were very hard and significantly lacking in flexibility, and the texture was poor. The light fastness was 4-5 and the sublimation fastness was 4-5.

Comparative Example 2 An aqueous resin composition containing 100 parts of the acrylic prepared in Reference Example 8 and 5 parts of an oxazoline-based cross-linking agent (“Epocros K-2010E” manufactured by Nippon Shokubai Co., Ltd.) was obtained in Reference Example 1. Nonwoven fabric (A) 10
0 part was impregnated to give 50 parts of solid content and dried with hot air at 140 ° C., then, in the same manner as in Example 1, surface smoothing / thickness adjustment, dyeing, reduction washing / ultrafine fiber After neutralization and neutralization, the surface is buffed with sandpaper to finish, and the apparent density is 0.50 g / c.
to obtain a leather-like sheet of suede m ^3. Although this product was excellent in flexibility and fullness, the impregnating resin did not develop color, and the color unevenness on the surface was conspicuous. Light fastness is No. 2,
The sublimation fastness was No. 4.

Comparative Example 3 An aqueous resin composition comprising 100 parts of the acrylic prepared in Reference Example 9 and 5 parts of a carbodiimide type crosslinking agent (“Carbodilite E-01” manufactured by Nisshinbo Industries Inc.) was obtained in Reference Example 2. Nonwoven fabric (B) 10
After impregnating 0 part with 60 parts of solid content and drying with hot air at 140 ° C., surface smoothing / thickness adjustment, ultrafine fiberization, dyeing, and reduction were carried out in the same manner as in Example 2. After washing and neutralization, the surface is buffed with sandpaper to finish, and the apparent density is 0.51 g / c.
to obtain a leather-like sheet of suede m ^3. Although this product was excellent in flexibility and fullness, the impregnating resin did not develop color, and the color unevenness on the surface was conspicuous. Light fastness is No. 2,
The sublimation fastness was No. 3-4.

Comparative Example 4 An aqueous resin composition comprising 100 parts of the acrylic prepared in Reference Example 10 and 2 parts of a carbodiimide type crosslinking agent (“Carbodilite E-01” manufactured by Nisshinbo Industries Inc.) was obtained in Reference Example 3. Nonwoven fabric (C) 1
00 parts were impregnated so that 40 parts of solid content was applied and dried with hot air at 140 ° C., and then surface smoothing / thickness adjustment, ultrafine fiberization, dyeing, reduction were carried out in the same manner as in Example 4. After washing and neutralization, the surface is buffed with sandpaper to finish, and the apparent density is 0.48g / c.
to obtain a leather-like sheet of suede m ^3. Although this product was excellent in flexibility and fullness, the impregnating resin did not develop color, and the color unevenness on the surface was conspicuous. Light fastness is 2-3
No. 4, sublimation fastness was No. 4.

Comparative Example 5 A suede-like leather having an apparent density of 0.48 g / cm ³ was obtained in the same manner as in Comparative Example 3 except that the reduction washing and the neutralization treatment were not carried out. Got the sheet. This product was excellent in flexibility and fullness, and exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was No. 4-5, but the sublimation fastness was No. 2, which was inferior.

Comparative Example 6 PU produced in Reference Example 11
100 parts of the non-woven fabric (A) obtained in Reference Example 1 was impregnated so that 40 parts of solid content was applied, and 140 ° C.
After drying with hot air, the surface smoothing / thickness adjustment, dyeing, reduction washing / ultrafine fiberization and neutralization treatment were performed in the same manner as in Example 1, and then the surface was buffed with sandpaper to finish. A suede-like leather-like sheet having an apparent density of 0.47 g / cm ³ was obtained. Although this product was excellent in flexibility and fullness, the impregnating resin did not develop color, and the color unevenness on the surface was conspicuous. Light fastness was No. 2 and sublimation fastness was 3-4.

[Comparative Example 7] A suede-like leather having an apparent density of 0.47 g / cm ³ was obtained in the same manner as in Comparative Example 6 except that the reduction washing and the neutralization treatment were not carried out. Got the sheet. This product was excellent in flexibility and fullness, and exhibited a good texture. The surface appearance of this leather-like sheet was good, and the fibers and the impregnated resin were colored to the same extent. The light fastness was 3-4, but the sublimation fastness was inferior to 1-2.

[Comparative Example 8] The composite produced in Reference Example 12 was impregnated so that 100 parts of the nonwoven fabric (A) obtained in Reference Example 1 would have a solid content of 40 parts, and the temperature was 140 ° C.
After drying with hot air, the surface smoothing / thickness adjustment, dyeing, reduction washing / ultrafine fiberization and neutralization treatment were performed in the same manner as in Example 1, and then the surface was buffed with sandpaper to finish. A suede-like leather-like sheet having an apparent density of 0.46 g / cm ³ was obtained. Although this product was excellent in flexibility and fullness, the impregnating resin did not develop color, and the color unevenness on the surface was conspicuous. Light fastness was 2-3 and sublimation fastness was 4.

From the results of Examples 1-8 and Comparative Examples 1-8,
It is clear that the leather-like sheet impregnated with the resin satisfying the constitutional requirements of the present invention is excellent in texture such as color development, flexibility, surface appearance, and fullness, and durability such as dyeing fastness and light resistance. Is. Also, the resin has a glass transition temperature of 20.
In Comparative Example 1 which does not have a continuous phase of ℃ or less, the flexibility is remarkably low and the texture is poor. On the other hand, Comparative Examples 3, 6 and 6 in which the resin does not have a phase having a glass transition temperature of 60 ° C. or higher.
In No. 8, since the resin is not colored, the color unevenness on the surface is conspicuous and the light resistance is poor. Further, even if the resin has a phase having a glass transition temperature of 60 ° C. or higher, the diameter is 1
In the cases of Comparative Examples 2 and 4 having a thickness of less than 50 nm, the color developability of the resin is still insufficient. Further, in Comparative Examples 5 and 7 in which the disperse dye was not subjected to reduction washing in order to secure the color developability, the color developability was improved but the sublimation fastness was remarkably inferior.

[0078]

Industrial Applicability The present invention is characterized by color development, flexibility, surface appearance,
Provided is a leather-like sheet which is excellent in texture such as fullness and is also excellent in durability such as dyeing fastness and light resistance.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F055 AA02 BA11 DA07 DA13 EA04                       EA05 EA13 EA14 EA24 FA10                       FA15                 4H057 AA01 BA08 DA01 DA17                 4L033 AA07 AA08 AB07 AC11 AC15                       CA18 CA50

Claims (14)

[Claims] 1. A leather-like sheet in which a resin is applied inside a fibrous base material and which is dyed with a disperse dye, wherein the following conditions (I) and (II) and (I) resin are:
A continuous phase and a dispersed phase, the continuous phase is composed of components having a glass transition temperature of 20 ° C. or lower, and the dispersed phase is a single layer structure composed of components having a glass transition temperature of 60 ° C. or higher, or A multi-layer structure having at least one layer having a glass transition temperature of 60 ° C. or higher, (I
I) A leather-like sheet characterized by satisfying that the diameter of the outermost layer in the dispersed phase is 150 nm or more among the layers composed of the components having a glass transition temperature of 60 ° C. or higher. 2. The continuous phase comprises a component having a glass transition temperature of 0 ° C. or lower, and the dispersed phase has a glass transition temperature of 70 to 120.
A single layer structure composed of components having a glass transition temperature of 70 to 120 ° C., or a multilayer structure having at least one layer composed of components having a glass transition temperature of 70 to 120 ° C.
The leather-like sheet according to claim 1, wherein the diameter of the outermost layer in the dispersed phase is 180 to 500 nm among the layers composed of components at 120 ° C. 3. The proportion of the continuous phase in the resin is 20-9.
The leather-like sheet according to claim 1 or 2, which is 5% by weight. 4. The leather-like sheet according to claim 1, wherein the resin mainly comprises a polymer of an ethylenically unsaturated monomer and optionally a polyurethane resin. 5. The ethylenically unsaturated monomer is (meth)
The leather-like sheet according to claim 4, which is mainly composed of an acrylic acid derivative. 6. The leather-like sheet according to claim 1, wherein at least a part of the fibers constituting the fibrous base material is polyester having an alkylene terephthalate unit as a main component. 7. A suede-like leather-like sheet obtained by raising at least one side surface of the leather-like sheet according to claim 1. 8. A fibrous base material in terms of active ingredient (A)
It has a single layer structure having a glass transition temperature of 60 ° C. or more and a diameter of 150 nm or more, or has a glass transition temperature of 60 ° C. or more and a diameter of 150 n.
Resin aqueous dispersion (a) consisting of particles having a multilayer structure having at least one layer of m or more layers (a) 10 to 100 parts by weight, (B) Other resin aqueous dispersion or aqueous solution (b)
0 to 90 parts by weight, (C) a hardening agent (c) 0 to 20 parts by weight and mainly constituting the resin aqueous dispersion (a), or the other resin aqueous dispersion or aqueous solution (b) A resin having a glass transition temperature of 20 ° C. or less is added to one or both of the resins constituting the composition to give a component having a glass transition temperature of 20 ° C. or less and a component having a glass transition temperature of 60 ° C. or more. At least a part of the components having a glass transition temperature of 20 ° C. or less forms a continuous phase, and a layer having a glass transition temperature of 60 ° C. or more and a diameter of 150 nm or more in the dispersed phase A method for producing a leather-like sheet, which comprises: 9. The method for producing a leather-like sheet according to claim 8, wherein the aqueous resin dispersion (a) is an aqueous resin dispersion obtained by emulsion polymerization of an ethylenically unsaturated monomer. 10. Another resin aqueous dispersion or aqueous solution (b) is (i) an aqueous dispersion of a polymer obtained by emulsion polymerization of an ethylenically unsaturated monomer, (ii) an aqueous dispersion of a polyurethane resin. A liquid or an aqueous solution, and (iii) at least one selected from an aqueous dispersion of a composite resin obtained by emulsion polymerization of an ethylenically unsaturated monomer in the presence of an aqueous dispersion or an aqueous solution of a polyurethane resin. 8
Or the method for producing a leather-like sheet according to item 9. 11. The ratio of the continuous phase in the resin is 20 to 20.
It is 95 weight%, The manufacturing method of the leather-like sheet in any one of Claims 8-10. 12. The continuous phase comprises a component having a glass transition temperature of 0 ° C. or lower, and the dispersed phase has a glass transition temperature of 70 to 12.
Single layer structure consisting of 0 ° C components or glass transition temperature 7
It has a multilayer structure having at least one layer having a component of 0 to 120 ° C. and has a diameter of the outermost layer in the dispersed phase of 18 layers having a glass transition temperature of 70 to 120 ° C.
It is 0-500 nm, The manufacturing method of the leather-like sheet in any one of Claims 8-11. 13. The method for producing a leather-like sheet according to claim 8, wherein at least a part of the fibers constituting the fibrous base material is polyester having an alkylene terephthalate unit as a main component. 14. The ethylenically unsaturated monomer is mainly composed of a (meth) acrylic acid derivative.
The method for producing a leather-like sheet according to any one of claims.