JP2002173879A - Method for producing leathery sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a leathery sheet by which the leathery sheet excellent in feeling such as flexibility, a appearance and a solid feeling and further in various kinds of durabilities such as light resistance without having stickiness on the surface can be produced without using organic solvents in relation to an impregnated resin. SOLUTION: This method for producing the leathery sheet is characterized in that a resin composing a water-based resin composition has core-shell structure and is a copolymer of a specific monomer in the method for producing the leathery sheet by supplying the water-based resin composition having crosslinking and curing properties to a fabric and then napping the surface of the fabric or forming a resin layer on the surface of the fabric.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a leather-like sheet having excellent durability, such as flexibility, surface appearance, and fullness, as well as light resistance and water resistance. It relates to a method of manufacturing without.

[0002]

2. Description of the Related Art Conventionally, as a leather-like sheet, a sheet in which a microfiber nap is present on the surface of a base obtained by adding a polymer elastic body to a nonwoven fabric made of a microfiber or a resin layer laminated on the surface of the base It has been known. Urethane-based elastic bodies, acrylic-based elastic bodies, and the like are known as polymer elastic bodies imparted to the nonwoven fabric, and polyurethane-based elastic bodies are preferably used from the viewpoint of the feeling of a leather-like sheet, mechanical properties, and the like. ing. As a general method for producing a leather-like sheet in which a polymer elastic body is provided to a nonwoven fabric made of ultrafine fibers, a nonwoven fabric made of ultrafine fibers or ultrafine fiber-generating fibers is prepared by using an organic solvent such as dimethylformamide as a solvent. A method of impregnating and coagulating a solution of a molecular elastic body or the like is used, but a manufacturing method using an organic solvent is not preferable from the viewpoint of environment, safety, and the like. Various methods have been proposed for producing a leather-like sheet by impregnating an aqueous dispersion of an elastic polymer, instead of using an organic solvent solution of an elastic polymer. However, many of these proposed methods are inventions relating to a leather-like sheet impregnated and coagulated with an aqueous dispersion of a polyurethane-based elastic material, and a leather-like sheet impregnated and coagulated with an aqueous dispersion of an acrylic-based elastic material. No satisfactory seats have yet been proposed.

[0003] Acrylic elastomers are excellent in durability, such as light resistance and hydrolysis resistance, as compared with polyurethane elastomers, and are attractive polymer elastomers. In this respect, it is inferior to a leather-like sheet provided with a polyurethane-based elastic body. Also,
When an aqueous dispersion of an acrylic elastic material is impregnated and coagulated into a nonwoven fabric made of microfibers or microfiber-generating fibers to produce a leather-like sheet with excellent flexibility and fullness, the surface of the leather-like sheet becomes sticky. Have the nature,
If a leather-like sheet is put on top of the manufacturing process, it is difficult to peel it off, and the productivity is extremely poor. In addition, even during use after commercialization, dust and dirt are adsorbed and the touch is unfavorable. It is conceivable to change the composition of the acrylic elastic body in order to reduce the tackiness. However, when the composition is changed, there is a problem that the flexibility of the leather-like sheet is reduced. Further, when the polymer elastic body is exposed on the surface of the leather-like sheet, such as a suede-like leather-like sheet, the color unevenness is noticeable when dyed.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an acrylic elastic material having excellent durability, such as light resistance and hydrolysis resistance, on a fabric or a fabric composed of ultrafine fibers. Impregnated with a dispersion liquid, and since the polymer elastic body liquid does not substantially contain an organic solvent, it is a preferable production method from the viewpoint of environment and safety, and has a softness, a sense of solidity, and a surface that have been difficult in the past. An object of the present invention is to provide a method capable of stably producing a leather-like sheet excellent in texture such as feel, color development and dyeing fastness.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have given an aqueous acrylic resin composition comprising a resin component having a specific core-shell structure and a curing agent to a fabric. It has been found that the above object can be achieved by shaving the surface of the fabric or forming a resin layer on the surface of the fabric.

That is, the present invention relates to a method for producing a leather-like sheet. That is, the present invention provides a leather-like sheet by applying a water-based resin composition (i) having cross-linking curability to a cloth and shaving the surface of the cloth or forming a resin layer on the surface of the cloth. The resin constituting the aqueous resin composition (i) has a core-shell structure, and the shell portion mainly has a functional group reactive with the monofunctional ethylenically unsaturated monomer (ds1). (Ds2), the core portion of which is a monofunctional ethylenically unsaturated monomer (dc1) and a bifunctional or higher polyfunctional ethylenically unsaturated monomer (dc
A method for producing a leather-like sheet, which is the copolymer of 2). Further, the present invention is a leather-like sheet manufactured by the above-described manufacturing method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. Examples of the fabric used in the present invention include a nonwoven fabric, a woven fabric, a knitted fabric, and a combination of two or more of them. Particularly, a nonwoven fabric is preferable because a natural leather-like texture and physical properties can be obtained. The fibers constituting these fabrics may be any of ordinary natural fibers, semi-synthetic fibers, and synthetic fibers, but are preferably ultrafine synthetic fibers or synthetic fibers that can be made ultrafine, and among them, a plurality of polymers. And a multicomponent fiber in which a plurality of polymers have a laminar or sea-island cross section in the fiber cross section. By laminating the laminated portion, by removing the laminated one-component polymer, and in the case of a sea-island-shaped multi-component fiber, the laminated multi-component fiber is By removing them, ultrafine fibers can be obtained. In particular, 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 trichlorne and toluene that are harmful to the human body, as in the conventional method of extracting sea components and producing ultrafine fibers. It is excellent in terms of environment and safety, and even in the case of removing one layered component to remove the sea component of ultrafine or sea-island-like fibers, removal is performed with water or aqueous solution When this is possible, it is not necessary to use an organic solvent in the same manner, and it is excellent in terms of environment and safety.

[0008] Such a multicomponent synthetic fiber comprises a component (ii) containing at least 60% by weight of the polymer (A), a polymer (B) incompatible with the polymer (A), or water or It is preferable to use a polymer having a structure in which the component (iii) containing at least 60% by weight of the polymer (C) removable by an aqueous solution is arranged.

The polymer (A) may be selected from polyester, polyester copolymer, polyester block copolymer, polyamide, polyamide copolymer, polyamide block copolymer, vinyl polymer and the like in consideration of melt viscosity. It can be arbitrarily selected according to the application and required performance.
Hereinafter, this will be described more specifically. As polyester,
Polyalkylene terephthalate such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypentamethylene talephthalate, polyhexamethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polypentamethylene naphthalate,
And polyalkylene naphthalate such as polyhexamethylene naphthalate. Further, a part of the diol component and the dicarboxylic acid component constituting the polyester is replaced with 1,4-cyclohexanedimethanol, cyclohexanediol, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, decahydro- 1,
Alicyclic diols such as 4: 5,8-dimethanonaphthalene-2,3-dimethanol; aromatic diols such as 1,4-bis (β-hydroxyethoxy) benzene, bisphenol A and bisphenol S; -Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3
-Propanediol, neopentyl glycol, 1,5
-Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-
1,8-octanediol, 1,9-nonanediol,
Diol components such as aliphatic diols such as 1,10-decanediol, glycerin, trimethylolpropane,
Tri- or more functional polyol components such as butanetriol, hexanetriol, trimethylolbutane, trimethylolpentane, and pentaerythritol; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid; and 2,6-naphthalenedicarboxylic acid , 1,5
Aromatic dicarboxylic acids such as -naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, isophthalic acid, sodium sulfoisophthalate, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, succinic acid, and glutaric acid And dicarboxylic acid components such as aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, and sebacic acid; and polyesters substituted with a trifunctional or higher functional polycarboxylic acid component such as trimellitic acid. Examples of the polyester block copolymer include a block copolymer of the above polyester with an aliphatic polyester, an aliphatic polyether, an aliphatic polycarbonate, or the like.

As polyamides, nylon 6, nylon 11, nylon 12, nylon 46, nylon 66,
Nylon 96 (nonamethylenediamine and / or 2-methyl-1,8-octanediamine and nylon composed of adipic acid), Nylon 910 (nonamethylenediamine and / or 2-methyl-1,8-octanediamine and sebacic acid Nylon), nylon 91
2 (nylon composed of nonanemethylenediamine and / or 2-methyl-1,8-octanediamine and dodecanedioic acid); and nylon 6/12 which is a copolymer of caprolactam and laurolactam.

Examples of the polyamide block copolymer include a block copolymer in which the above polyamide and an aliphatic polyester, an aliphatic polyether, an aliphatic polycarbonate or the like are linked by an ester group, an amide group or the like.

Examples of the vinyl polymer include polyolefins such as polyethylene and polypropylene; polystyrene polymers such as polystyrene and polystyrene block copolymers; ethylene-vinyl acetate copolymers; and saponified ethylene-vinyl acetate copolymers. And the like.

The content of the polymer (A) in the component (ii) is at least 60% by weight, preferably at least 70% by weight, more preferably at least 80% by weight. 6
If the amount is less than 0% by weight, the fiber properties and the like are inferior, which is not preferable.

As the polymer (B), the same polymer as the polymer (A) can be used, but it is preferably incompatible with the polymer (A). Incompatible polymer (A) /
Examples of the combination of the polymer (B) include polyester / polyamide, polyamide / polyester, polyester block copolymer / polyamide, polyamide / polyester block copolymer, polyester / polyamide block copolymer, polyamide block copolymer / polyester, Polyester / polyolefin, polyolefin /
Polyester, polyamide / polyolefin, polyolefin / polyamide, polyester / polystyrene-based polymer, polystyrene-based polymer / polyester, polyamide / polystyrene-based polymer, polyolefin / polystyrene-based polymer, polystyrene-based polymer / polyolefin, ethylene-vinyl acetate copolymer Coalescence / Polyester, Ethylene-vinyl acetate copolymer / Polyamide, Ethylene-vinyl acetate copolymer / Polystyrene-based polymer, Saponified ethylene-vinyl acetate copolymer / Polyester, Saponified ethylene-vinyl acetate copolymer / Polyamide, Ethylene vinyl acetate Copolymer / polystyrene-based polymer and the like.

The combination of polymer (A) / polymer (B) can be suitably applied to a multicomponent fiber having a cross section shown in FIGS. 1 to 6. In particular, in the case of forming a nonwoven fabric using a card, it is preferable that the splittable fiber is not split in each of the steps of spinning, drawing, crimping, and forming a nonwoven fabric such as a card in order to secure the processability. In the carding process, when the fineness of the fiber to be opened is equal to or less than a specific value, the processability through the card decreases. Therefore, it is preferable that the adhesive force between the component (ii) and the component (iii) constituting the multicomponent fiber is such that the adhesive force is not divided by mechanical stress in each of the steps from spinning to carding. further,
When a polymer (B) incompatible with the polymer (A) is used as the component (iii) of the multicomponent fiber, hot water immersion, chemical treatment, high-pressure liquid For example, a method of peeling the laminated portion of the multi-component fiber by a physical impact or the like is used. Such a preferable polymer (A) having a moderate adhesive strength and excellent fiber properties and the like.
Examples of the combination of / polymer (B) include polyester / polyamide and polyester / polyamide block copolymers. The polyester is preferably a polyester mainly composed of alkylene terephthalate, and is preferably a polyester mainly composed of ethylene terephthalate units. More preferably, there is. The polyester mainly composed of alkylene terephthalate is a polyester containing 60% by weight or more of alkylene terephthalate units, more preferably 70% by weight or more, and most preferably 80% by weight or more. The polyamide is a polyamide satisfying carbon number / amide group> 7, preferably carbon number / amide group> 8, and more preferably carbon number / amide group> 9. More specifically, nylon 11, nylon 12, nylon 610, nylon 61
2, Nylon 910, Nylon 912, Nylon 6/1
2 and so on. As the polyamide block copolymer, a block copolymer in which a polyamide satisfying the above-mentioned carbon number / amide group> 7 and an aliphatic polyester, an aliphatic polyether, an aliphatic polycarbonate, or the like are bonded by an ester group, an amide group, or the like. And the like. More specifically, a block copolymer in which nylon 12 and polytetramethylene glycol are bonded by an ester group can be used.

When a polyamide or a polyamide block copolymer is used as the polymer (B), spinnability, especially continuous spinning operation is improved. , The concentration of the amino group is preferably 30 μeq / g or less. More preferably, it is 25 μeq / g or less. As a method for reducing the terminal group concentration, a known method can be used.

The polymer (C) is a polymer which can be dissolved and removed or decomposed and removed in water or an aqueous solution such as an alkaline aqueous solution or an acidic aqueous solution under conditions such as heating and pressurizing. As such a polymer (C), a polyester copolymer,
Examples thereof include polyvinyl alcohol, a polyvinyl alcohol-based copolymer, and polyethylene oxide.
Preferably, a polyester copolymer, a polyvinyl alcohol-based copolymer, or the like can be given because of excellent spinning stability and the like. As the polyester copolymer,
Examples include polyesters obtained by copolymerizing polyethylene glycol, a compound containing an alkali metal salt of sulfonic acid, and the like. Examples of the polyvinyl alcohol copolymer include α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-
Vinyl ethers such as propyl vinyl ether and n-butyl vinyl ether; ethylene glycol vinyl ether; 1,3-propanediol vinyl ether;
Hydroxy-containing vinyl ethers such as -butanediol vinyl ether, allyl acetate, propyl allyl ether, butyl allyl ether, allyl ethers such as hexyl allyl ether, monomers having an oxyalkylene group, 3-buten-1-ol, 4-pentene
1-ol, 5-hexen-1-ol, 7-octen-1-ol, 9-decen-1-ol, 3-methyl-
Examples thereof include polyvinyl alcohol-based copolymers obtained by copolymerizing monomers derived from hydroxy group-containing α-olefins such as 3-buten-1-ol in polyvinyl alcohol at 0.1 to 20 mol%.

The content of the polymer (B) or the polymer (C) in the component (iii) is preferably 60% by weight or more. It is more preferably at least 70% by weight, and even more preferably at least 80% by weight. If the content is less than 60% by weight, the multicomponent fiber is not preferable because it has poor passability in the nonwoven fabric step, division property after the nonwoven fabric step, dissolution and removal in water and an aqueous solution, and decomposability.

It is desirable that the multicomponent fiber suitably used in the present invention can be dyed with a dye containing no heavy metal or the like, that is, a disperse dye which is preferable from an environmental point of view. Fibers composed of a polymer having a low glass transition temperature are dyed with a disperse dye, but have poor color fastness. In the multicomponent fiber of the present invention, when the glass transition temperature of the polymer (A) or the polymer (B) is about 50 ° C. or less, the glass transition temperature is 50 ° C. or more, preferably 60 ° C. or more, and further, Preferably, a polymer having a temperature of 70 ° C. or higher is added to component (ii) and / or component (iii) in an amount of 3 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 30% by weight, respectively, of component (ii) and component (iii). May be contained in the range of 10 to 30% by weight. Examples of such a polymer include polyamide, polystyrene, and polymethacrylate having a glass transition temperature of 50 ° C. or higher, preferably 60 ° C. or higher, and more preferably 70 ° C. or higher. Preferred are polyethylene terephthalate and polyethylene terephthalate copolymerized with isophthalic acid.

FIGS. 1 to 6 show examples of cross sections of the multicomponent fiber suitably used in the present invention. In the figure, 1 is the component (ii), 2 is the component (i) incompatible with the component (ii).
ii) (main component is polymer (B)) or component (iii) (main component is polymer (C)) that can be decomposed and removed with an aqueous solution. The multi-component fiber of the present invention is preferably a type in which at least one component is divided into two or more components out of two components as shown in FIGS. 1 to 5, but is not particularly limited thereto. From an environmental point of view, using an incompatible polymer (B) that emits less waste, the cross section of the fiber is such that at least one component is divided into multiple layers by the other component as shown in FIGS. The type of arrangement is preferred. FIG.
It is also preferable to use a multicomponent fiber having a sea-island cross section such that the sea component polymer can be removed with water or an aqueous solution. In order to obtain fibers of each cross-sectional shape, a corresponding nozzle hole structure may be used.

Further, the component (iii) is composed of the polymer (B), and the adhesiveness between the component (ii) and the component (iii) is insufficient. Is insufficient, it is preferable to use one having the following specific cross-sectional shape (e.g., corresponding to FIG. 2). The entire outer periphery of the cross section of the multicomponent fiber of the present invention is coated with the component (ii) or the component (iii), and the thickness of the component (iii) coating covering the component (ii) portion, or the component (iii) The thickness of the coating of the component (ii) covering the portion is preferably 0.05 to 2.0 μm, and more preferably 0.1 to 1.5 μm.
When the coating is thinner than 0.05 μm, the coating is rubbed in the steps of carding and needle punching, so that the fiber is liable to be separated and split in the longitudinal direction of the fiber, and the processability tends to be insufficient. When the thickness exceeds 2.0 μm, there is no problem in the carding and needle punching steps, and the processability is good. However, after the nonwoven fabric forming step, it cannot be divided by physical impact such as a high-pressure liquid flow, and the alkali weight is reduced. In such processing, it is necessary to reduce a large amount, which is not preferable. In order to produce a multicomponent fiber in which the entire outer periphery of the cross section of the splittable fiber is coated with the component (ii) or the component (iii), the component (ii) and the component (ii) are used.
i) is made into a molten state, and the melted state is led to a die nozzle hole in a state where they are alternately arranged by a conventional method, and the liquid is discharged from the nozzle hole. That is, the component (ii) and the component (i
ii) are alternately arranged, and before discharging from the pores inside the die, at a portion where one component and the die are in contact with the metal, the end is rounded due to the surface tension of the component, and When the other component flows into the gap, a multicomponent fiber having a coating in which the entire outer periphery of the cross section is covered by the other component can be obtained. The production of multicomponent fibers in which the entire outer periphery of the cross section is coated with the component (ii) or the component (iii) adjusts the balance between the apparent melt viscosities during the spinning of the component (ii) and the component (iii). Similarly, the desired multicomponent fiber can be obtained by spinning.

In the aqueous resin composition (i) having a cross-linking curability used in the present invention, the resin component has a core / shell structure, and the core portion is a monofunctional ethylenically unsaturated monomer (dc).
1) and difunctional or higher functional polyfunctional unsaturated monomers (dc
The shell portion mainly consists of a copolymer of a monofunctional ethylenically unsaturated monomer (ds1) and an ethylenically unsaturated monomer (ds2) having a reactive functional group. When the functional group of the resin shell portion is not self-crosslinkable, the crosslinkable and curable aqueous resin composition (i) contains an aqueous resin dispersion (D) and a functional group reactive with the functional group in the molecule. It is necessary to comprise a water-soluble or water-dispersible curing agent (E) containing at least one hardener.

Examples of the monofunctional ethylenically unsaturated monomer (dc1) constituting the core portion include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate,
(Meth) acrylic acid, glycyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamido, dimethylaminopropyl (meth) acrylamido, diethylaminoethyl (meth) acrylate, 2-hydroxy (meth) acrylate (Meth) acrylic acid derivatives such as ethyl and 2-hydroxypropyl (meth) acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene;
(Meth) acrylamide, diacetone (meth) acrylamide, N- [3- (dimethylamino) propyl]
Acrylamides such as (meth) acrylamide; maleic acid, fumaric acid, itaconic acid and derivatives thereof; heterocyclic vinyl compounds such as vinylpyrrolidone; vinyl compounds such as vinyl chloride, acrylonitrile, vinyl ether, vinyl ketone, vinylamide; ethylene, propylene And the like, and one or more of these can be used. Among them, monofunctional ethylenically unsaturated monomers (dc1) include:
The proportion of the (meth) acrylic acid derivative is preferably at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight.

Examples of the bifunctional or higher functional polyfunctional ethylenically unsaturated monomer (dc2) constituting the core portion include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene 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 (meth) acrylate,
Di (meth) such as dimethylol tricyclodecane di (meth) acrylate and glycerin di (meth) acrylate
Acrylates; trimethylolpropane tri (meth)
Tri (meth) acrylates such as acrylate and pentaerythritol tri (meth) acrylate; tetra (meth) acrylates such as pentaerythritol tetra (meth) acrylate; polyfunctional aromatic vinyl compounds such as divinylbenzene and trivinylbenzene; allyl (Meta)
Two or more different ethylenically unsaturated bond-containing compounds such as acrylate and vinyl (meth) acrylate; a 2: 1 addition reaction product of 2-hydroxy-3-phenoxypropyl acrylate and hexamethylene diisocyanate, pentaerythritol triacrylate and hexamethylene Urethane acrylates having a molecular weight of 1500 or less, such as a 2: 1 addition reaction product of diisocyanate and a 2: 1 addition reaction product of glycerin dimethacrylate and tolylene diisocyanate, may be used alone or in combination of two or more. it can.

The core portion has a two-layer structure of an inner layer and an outer layer,
The inner layer is a monofunctional ethylenically unsaturated monomer (dc1-1)
And a difunctional or higher polyfunctional unsaturated monomer (dc2-
The polymer of 1) has a glass transition temperature of 50 ° C. or higher, and the outer layer is composed of a monofunctional ethylenically unsaturated monomer (dc1-2) and 2
The polymer having a glass transition temperature of 20 ° C. or lower for a polymer of a polyfunctional unsaturated monomer (dc2-2) having a functionality higher than or equal to 20 is required to have a dyeing property and a color fastness with a dye such as a disperse dye of the obtained leather-like sheet. This is preferable in terms of balancing the feeling of the leather-like sheet such as flexibility.

The glass transition temperature of the polymer comprising the monofunctional ethylenically unsaturated monomer (dc1-1) and the difunctional or higher polyfunctional ethylenically unsaturated monomer (dc2-1) constituting the inner layer of the core portion is as follows. It is preferably at least 60 ° C, more preferably at least 70 ° C. Ethylenically unsaturated monomer (dc1-1) constituting the inner layer of the core portion
Can be selected from the above-mentioned monofunctional ethylenically unsaturated monomers (dc1). Examples of such ethylenically unsaturated monomers (dc1-1) include methyl methacrylate, ethyl methacrylate and the like. (Meth) acrylic acid derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene;
One or more of these can be used. Further, a polyfunctional ethylenically unsaturated monomer (dc2-
1) is not particularly limited as long as it is the above-mentioned polyfunctional ethylenically unsaturated monomer (dc2).

The glass transition temperature of the polymer composed of the monofunctional ethylenically unsaturated monomer (dc1-2) and the bifunctional or higher polyfunctional ethylenically unsaturated monomer (dc2-2) constituting the outer layer of the core portion is as follows. Preferably 0 ° C. or less,
More preferably, it is -20 ° C or lower. As the ethylenically unsaturated monomer (dc1-2) constituting the outer layer of the core portion, the above-mentioned monofunctional ethylenically unsaturated monomer (d1-2)
c1), but such ethylenically unsaturated monomers (dc1-2) include butyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, acrylic (Meth) acrylic acid derivatives such as stearyl acid; vinyl ethers such as methyl vinyl ether; α-olefins such as ethylene and propylene; and one or more of these can be used. The polyfunctional ethylenically unsaturated monomer (dc2-2) includes the above-mentioned polyfunctional ethylenically unsaturated monomer (dc
If it is 2), there is no particular limitation.

The monofunctional ethylenically unsaturated monomers (dc1), (dc1-1), (dc1-
2) and a polyfunctional ethylenically unsaturated monomer (dc2),
The molar ratio of (dc2-1) and (dc2-2) is preferably in the range of monofunctional ethylenically unsaturated monomer / polyfunctional ethylenically unsaturated monomer = 80/20 to 99.9 / 0.1. , More preferably 85/15 to 99.5 /
0.5, more preferably 90/10 to 9
It is in the range of 9.5 / 0.5. If the amount of the polyfunctional ethylenically unsaturated monomer exceeds 20 mol%, the mechanical properties of the obtained leather-like sheet tend to be reduced, or the feel of the surface tends to be rough, which is not preferable.

As the monofunctional ethylenically unsaturated monomer (ds1) constituting the shell portion, the same monomer as the monofunctional ethylenically unsaturated monomer (dc1) constituting the core portion can be used. Constituent monofunctional ethylenically unsaturated monomer (ds1) and ethylenically unsaturated monomer having reactive functional group (ds1)
The glass transition temperature of the copolymer (2) is 50 ° C. or lower, preferably 20 ° C. or lower, more preferably 0 ° C. or lower. When the glass transition temperature exceeds 50 ° C., the texture of the leather-like sheet obtained by applying the aqueous resin composition (i) becomes hard, which is not preferable. Preferred monofunctional ethylenically unsaturated monomers (ds1) include (meth) acrylic acid derivatives such as butyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and stearyl acrylate; methyl vinyl ether Vinyl ethers such as ethylene;
Olefins and the like.
More than one species can be used.

Examples of the ethylenically unsaturated monomer (ds2) having a reactive functional group constituting the shell portion include:
(Meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, 2- (meth) acryloyloxyethyl succinic acid,
Glycidyl (meth) acrylate, vinyl oxazoline,
A carboxyl group such as 4- (1-propenyloxymethyl) -1,3-dioxolan-2-one, diacetone acrylamide, N-methylol (meth) acrylamide, an epoxy group, a cyclocarbonate group, an oxazoline group, a carbonyl group; Examples thereof include an ethylenically unsaturated monomer having a functional group such as an N-methylol group, and methacrylic acid is preferable. When an ethylenically unsaturated monomer having a carboxyl group is used, it is necessary to neutralize at least a part of the carboxyl group.
It is preferable because a leather-like sheet can be stably manufactured. Neutralization of the carboxyl group, after polymerization of the aqueous resin dispersion (D),
Sodium bicarbonate, alkali metal-containing compounds such as sodium carbonate, trimethylamine, triethylamine,
Trialkylamines such as methyldiethylamine, N,
It can be carried out by adding a dialkylalkanolamine such as N-dimethylethanolamine or N, N-diisopropylethanolamine; or an alkyldialkanolamine such as N-methyldiethanolamine.

The molar ratio of the monofunctional ethylenically unsaturated monomer (ds1) constituting the shell portion to the ethylenically unsaturated monomer (ds2) having a reactive functional group is defined as ethylenically unsaturated monomer / reactive functional group. The ethylenically unsaturated monomer having a group is preferably in the range of 50/50 to 99.9 / 0.1, more preferably 70/30 to
99/1, more preferably 80/20 to
It is in the range of 98/2. If the amount of the ethylenically unsaturated monomer having a reactive functional group exceeds 50 mol%, the texture of the obtained leather-like sheet becomes undesirably hard. Also,
When the content of the ethylenically unsaturated monomer having a reactive functional group is less than 0.1%, the surface of the leather-like sheet becomes sticky, which is not preferable. Further, a small amount of a bifunctional or higher polyfunctional ethylenically unsaturated monomer may be used in combination.

The resin component of the aqueous resin dispersion (D) of the present invention is excellent in light resistance. However, in order to further improve the light resistance, the ethylenically unsaturated monomer (A) constituting the resin component of the aqueous resin dispersion (i) is used. dc1), as a part of (ds-1), a hindered amine group having a light stabilizing effect and / or
Alternatively, it is possible to copolymerize an ethylenically unsaturated monomer having an ultraviolet absorbing group. Examples of the ethylenically unsaturated monomer having a hindered amine 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 amine group such as 2,2,6,6-tetramethylpiperidine and 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine; -Hydroxy-5 '
— (Meth) acryloyloxyethylphenyl ”-2H
-Benzotriazole, 2-hydroxy-4- (meth)
Examples thereof include ethylenically unsaturated monomers having a benzotriazole group or a benzophenone group, such as acryloyloxybenzophenone and 2-hydroxy-4- (meth) acryloyloxyethylbenzophenone.

When dyeing the leather-like sheet of the present invention,
From the viewpoint of the environment, it is preferable to dye with a disperse dye which is a dye containing no metal component. )) As a part of the monofunctional ethylenically unsaturated monomers (dc1) and (ds-1) constituting the resin component,
1), dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminoethyl (meth) acrylamido, dimethylaminopropyl (meth) acrylamido, (meth) acrylic acid described above as (ds-1) 3 such as diethylaminoethyl
It is preferable to use a monomer having a secondary amine group.

The core / shell weight ratio is 98/2.
４０40/60, preferably 95/5 to 50/50, more preferably 92/8 to 70/30. When the weight ratio of the shell portion is 2% or less, the obtained leather-like sheet tends to be tacky when it is intended to be flexible, and tends to be hard when the adhesion is reduced, which is not preferred. If the weight ratio of the shell portion exceeds 60% by weight, the texture of the obtained leather-like sheet becomes undesirably hard.

When the core portion has a two-layer structure of an inner layer and an outer layer, it is preferable to consider the ratio of the inner layer of the core portion to the entire core-shell particles. The inner layer of the core portion is preferably 5 to 70% by weight, more preferably 10 to 70% by weight.
-50% by weight, more preferably 15-40% by weight. If the inner layer of the core portion exceeds 70% by weight of the whole particles, the smoothness of the surface of the leather-like sheet is reduced, and the leather-like sheet tends to be harder. If the inner layer of the core portion is less than 5% by weight of the whole particles, it is not preferable because the effect of improving the color developability when the leather-like sheet is dyed with a disperse dye is low.

After synthesizing the aqueous resin dispersion (D), it is preferable to add 1 to 20 parts by weight of a nonionic surfactant to the aqueous resin dispersion (D) based on the resin component of the aqueous resin dispersion. It is more preferable to add 2 to 10 parts by weight.
By adding a nonionic surfactant, a leather-like sheet can be stably manufactured. Specifically, conventionally,
When the aqueous resin dispersion (D) is impregnated into the nonwoven fabric, some of the particles of the aqueous resin dispersion agglomerate, and the surface of the obtained leather-like sheet may have a rough feel. By adding the surfactant, the stability of the aqueous resin dispersion is improved, and the leather-like sheet can be stably manufactured without such a problem.
Examples of the nonionic surfactant include ethylene oxide adducts of higher alcohols, ethylene oxide adducts of alkyl phenols, ethylene oxide adducts of fatty acids, ethylene oxide adducts of alkyl phenols, ethylene oxide adducts of fatty acids, and polyhydric alcohols. Examples thereof include an ethylene oxide adduct of a fatty acid ester, an ethylene oxide adduct of a higher alkylamine, and an ethylene oxide adduct of polypropylene glycol.

The core / shell structure of the resin component of the aqueous resin dispersion (D) used in the present invention is different from the core / shell structure of the particle, and is a seed emulsion which is polymerized first. The emulsion having a core / shell structure can be obtained by variously changing the composition of the polymer and the composition of the polymer to be polymerized later. The particles of the core-shell structure of the present invention, according to a known production method for producing particles of the core-shell structure, including a polymerization reaction operation for forming an inner layer of the core portion, a polymerization reaction for forming a shell layer,
By performing a polymerization reaction operation for forming a predetermined polymer layer in a predetermined order, the polymer layer can be manufactured by sequentially forming a layer from the center to the outside.
For example, in the emulsion polymerization method, by performing polymerization for forming each layer according to a known means, the polymer particles having a core-shell structure of the present invention can be obtained. The temperature of the emulsion polymerization is not necessarily limited, but a general range is from 0 to 100 ° C. Examples of the emulsifier used herein include fatty acid salts such as sodium oleate, sodium laurate, and sodium stearate; sulfates of aliphatic alcohols such as sodium lauryl sulfate; rosinates such as potassium rosinate; dodecylbenzene sulfone Alkylarylsulfonates such as sodium silicate;
Dialkyl sulfosuccinates; alkyl diphenyl ether disulfonates; phosphates, and the like.
These are used in one kind or two or more kinds in combination. As the polymerization initiator used in the emulsion polymerization, a radical polymerization initiator is generally used. As specific examples of the radical polymerization initiator, persulfates such as potassium persulfate and peroxides such as benzoyl peroxide can be used alone. Also, peroxides such as cumene hydroperoxide,
Redox initiators based on a combination of reducing agents such as ferrous salts can also be used.

When the reactive functional group of the resin shell component is not self-crosslinkable, the aqueous resin composition (i) contains an aqueous resin dispersion (D) and a functional group reactive with the functional group in the molecule. It is necessary to comprise two or more water-soluble or water-dispersible curing agents (E). Examples of the combination of the functional group in the aqueous resin dispersion (D) and the functional group in the curing agent (E) include a reaction between a carboxyl group and a carbodiimide group [R′-N = C = NR, and a carboxyl group. ;
R'-N = C = NR + R "COOH → R'-
NH—C (OOCR ″) = NR], carboxyl group and oxazoline group —CH ₂ —CH ₂ —NＣＨC (R) —O
[Link to leftmost CH ₂ ; cyclic compound) and carboxyl group; -CH ₂ -CH ₂ -N２−C (R) —O +
R'-COOH → R'-COO-CH2-CH2
—NH—C (R) ＝ O], a combination of a carboxyl group and an epoxy group, a carboxyl group and a cyclocarbonate group, a carboxyl group and an aziridine group, and a carbonyl group and a hydrazide group. Among them, a combination of a resin having a carboxyl group and a curing agent having a carbodiimide group or an oxazoline group is preferable because the leather-like sheet has excellent flexibility and the surface of the leather-like sheet has no tackiness. The combination of a resin having a carboxyl group and a curing agent having a carbodiimide group is more preferable since the compatibility of the flexibility sheet and the low tackiness of the surface of the leather-like sheet is particularly excellent. Such compounds include, for example, Nisshinbo Carbodilite E-
01 and Carbodilite E-02. The amount of the curing agent (E) applied is such that the solid content of the curing agent (E) is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, based on the resin component of the aqueous resin dispersion (D). %,
More preferably, the content is 1.0 to 10% by weight. If the content exceeds 20% by weight, the resulting leather-like sheet is undesirably reduced in flexibility. If the amount is less than 0.1% by weight, the tack of the leather-like sheet is large, and the leather-like sheet cannot be manufactured stably.

The aqueous resin composition (i) used in the present invention may contain other resin components in the aqueous resin composition (i) as long as the properties of the obtained leather-like sheet are not impaired. Examples of such a resin component include polyurethane, polyurethane-acrylic composite resin, polyacrylate, polyacrylic copolymer, acrylonitrile-butadiene copolymer, polybutadiene, polyisoprene, olefin-based copolymer, silicone, and polyvinyl acetate. And an elastic resin component such as ethylene-vinyl acetate copolymer, polyvinyl chloride, polyester elastomer and polyamide elastomer.

Further, a penetrant, a thickener, a bulking agent, a curing accelerator, an antioxidant, an ultraviolet absorber, a fluorescent agent, a fungicide, a polyvinyl alcohol are added to the aqueous resin composition (i) of the present invention. And a water-soluble polymer compound such as carboxymethylcellulose, a dye, a pigment and the like may be appropriately compounded.

As described above, it is essential that the resin constituting the aqueous resin composition (i) used in the present invention has a core-shell structure. When the shell component polymer is separated and present as a mere mixture, or when the core component and the shell component are reversed to form a core-shell structure, the surface of the leather-like sheet is made to have tackiness. In addition, it is difficult to remove the leather-like sheet when it is put on during production, and it is not only extremely poor in productivity, but also when it is used after being commercialized, it absorbs dust and dirt and feels bad, and leather Inferior surface smoothness, the object of the present invention can not be achieved, even when only consisting of the core component,
For the same reason, the object of the present invention cannot be achieved, and when it is composed solely of a shell component, the obtained leather-like sheet has reduced flexibility, resulting in inferior hand and cannot achieve the object of the present invention.

The leather-like sheet of the present invention can be obtained by combining the following steps. That is, it can be obtained by sequentially performing the following steps (a) to (d). (B) a step of preparing a fiber, preferably a step of producing a multicomponent fiber in which at least one component is divided and arranged by the other component in a multicomponent fiber composed of component (ii) and component (iii); (B) a step of producing a fabric, preferably an entangled nonwoven fabric, comprising the fibers; (c) when the fibers are multicomponent fibers, a step of separating and separating the fibers; Dissolving and removing with water, decomposing and removing with an aqueous alkaline solution to generate ultrafine fibers, (2) forming nap of the fiber bundle on at least one surface, or forming a resin layer on at least one surface, and It is necessary to include the following step (e) between the above steps (b) and (c) or between (c) and (2). (E) a step of impregnating and coagulating the aqueous resin dispersion (i) to apply the resin composition to the fabric, and if necessary, prior to impregnating the aqueous resin dispersion (i),
The following steps (f) and (g) may be added, or the following step (h) may be added after the above step (d). (F) a step of shrinking the cloth, (g) a step of temporarily fixing the cloth with a water-soluble glue or the like, and (h) a step of dyeing the obtained sheet.

Next, the above steps will be described in detail focusing on a preferred method. First, fibers used in the present invention, preferably multicomponent fibers, are obtained. The obtained multicomponent fiber is stretched, and if necessary, subjected to processing steps such as crimping, heat setting, and cutting to obtain a fiber having a fineness of 2 to 15 denier.

The multicomponent fiber is used as a fabric. Preferably,
Disintegrate with a card to make a nonwoven fabric. That is, a fiber defibrated with a card is formed through a webber to form a random web or a cross-wrap web. If necessary, other fibers may be mixed. The resulting fibrous web is laminated to the desired weight and thickness. Next, needle punching is performed by a known method to obtain a needle punched nonwoven fabric. The number of punches is usually in the range of 200 to 2500 punches / cm ² .

The multicomponent fibers constituting the fiber entangled nonwoven fabric are
Finer. The cross section of the multicomponent fiber is as shown in FIGS.
At least one component is divided into multiple layers by the other component.
If they are arranged separately, hot water
Or immerse in an alkaline aqueous solution, and if necessary,
(Ii) dissolving, decomposing and removing a part of the component (iii)
Physical impact such as peeling and splitting by high pressure water flow
Applying a method such as peeling and splitting while giving
be able to. The cross section of the multicomponent fiber is sea as shown in Fig. 6.
If it is divided into islands, it constitutes a sea component
Dissolve and remove component (iii), polymer (C), with hot water
Removed or decomposed and removed with an aqueous alkaline solution or acidic aqueous solution
By doing so, extra fine fibers are generated. Similarly, multi-component fibers
The cross section of the fiber has at least one component as shown in Figs.
Is divided into multiple layers by the other component.
If any, either polymer is dissolved and removed with hot water.
Or can be decomposed and removed with an aqueous alkaline or acidic solution
In such cases, ultrafine fibers may be formed using such a method.
No. The thickness of the obtained ultrafine fiber is 0.001 to 2 d.
The range of tex is that the resulting leather-like sheet is flexible,
It is preferable in that the feeling becomes good. In addition,
100-2000g / m for woven fabric ², Preferred
Or 200 to 1500 g / m²Range is mechanical
It is preferable in terms of texture, fullness, flexibility and the like.

Then, the fiber entangled nonwoven fabric is heated to 50 to 150 ° C.
, And more preferably, the fiber-entangled nonwoven fabric is heated in a hot water tank at 50 to 95 ° C to shrink the fiber-entangled nonwoven fabric. By shrinking,
The feeling of fulfillment of the seat is significantly improved. The shrinkage is determined by the types and weight ratios of polyester and polyamide, spinning conditions, stretching conditions, and the like. To improve the sheet's fullness and flexibility, the area shrinkage is in the range of 10 to 60%. It is more preferable that the content be in the range of 20 to 50%.

If necessary, a resin which can be dissolved and removed, for example, a water-soluble sizing agent such as a polyvinyl alcohol resin may be applied to the nonwoven fabric to temporarily fix the nonwoven fabric.

Further, the leather-like sheet of the present invention needs to be provided with the aqueous resin composition (i) in order to supplement the surface appearance, the feeling such as fullness, and the mechanical properties. The aqueous resin composition (i) may be coagulated so as to be uniformly applied to the entire nonwoven fabric, or may be applied to the surface thereof with a gradient in the thickness direction by migration. The coagulation can be performed by a dry coagulation method by heat treatment, or a heat-sensitive coagulation method by heat treatment, hot water treatment or steam treatment. After impregnating, coagulating and drying the aqueous resin composition (i), the polymer and the fiber may be bonded to each other, or a space may be formed between the polymer and the fiber. The amount of the polymer to be applied is 120 parts by weight or less, preferably 100 parts by weight or less, more preferably 80 parts by weight or less, based on 100 parts by weight of the nonwoven fabric. If the amount exceeds 120 parts by weight, the flexibility of the obtained sheet is impaired,
It is not preferable because it becomes a rubber-like sheet.

Next, at least one surface of the sheet comprising the ultrafine fiber entangled nonwoven fabric and the resin is subjected to a brushing treatment to form a fiber fiber raised surface mainly composed of ultrafine fibers, thereby obtaining a suede-like leather-like sheet. A resin layer is laminated on at least one surface to form a leather-like sheet with a silver surface. As a method of forming the fiber raised surface, a method of buffing using a sandpaper or the like is used after the thickness of the fibrous substrate is adjusted to a desired thickness or before the thickness is adjusted. If the thickness has not been adjusted, the thickness is adjusted to a desired thickness. Similarly, in the case of a leather-like sheet on which a resin layer is laminated, the thickness is adjusted.
As the resin layer laminated on the surface, an elastic polymer layer represented by a polyurethane layer is preferably used. In addition, as the resin to be applied to the surface, the above-mentioned aqueous resin composition (i) can be used. An excellent leather-like sheet with a silver surface is obtained. The surface of the nonwoven fabric may be melted by heating the surface and pressing the smooth surface to form a resin layer. Further, the obtained suede-like leather-like sheet or grain surface-like leather-like sheet is dyed as necessary. Dyeing is carried out with a dye mainly comprising a disperse dye or the like by a usual dyeing method. Further, the leather-like sheet can be subjected to a finishing treatment such as embossing treatment, kneading softening treatment, brushing or the like, if necessary, to obtain a final leather-like sheet.

The leather-like sheet obtained in the present invention has excellent dyeing fastness and coloring properties and is excellent in texture, and is available as a suede type or a type with silver. For, shoes, car seats,
It is suitable for bags, bags, various gloves, sporting goods such as gloves and balls, and the like.

[0051]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. The parts and percentages in the examples relate to weight unless otherwise specified.

[Light fastness to light dyeing] After irradiating the leather-like sheet with a fade tester (UV long life fade meter FAL-5H • B • BL, manufactured by Suga Test Instruments Co., Ltd., UV carbon arc lamp, 63 ° C) for 80 hours. The degree of discoloration was determined by gray scale.

[Tensile strength of leather-like sheet] Width 2.5 cm
Of the test piece was gripped by a chuck at an interval of 10 cm, stretched at a pulling speed of 10 cm / min using a tensile tester, and the breaking strength was measured. 2.5 cm).

[Measurement of thickness of multi-component fiber coating]
With both ends of the stretched raw cotton fiber fixed and tensed,
After placing in a hot water bath at 100 ° C. for 10 minutes to cause a crack in the joint surface due to a difference in shrinkage between the component (ii) and the component (iii), the cross section is cut and the component (ii) is observed by a scanning electron microscope. The thickness of the coating on the part or component (iii) was measured.

The resins used in the following Examples and Comparative Examples are shown in the following table.

[0056]

[Table 1]

Reference Example 1 532 g of ultrapure water and 0.27 g of sodium di-2-ethylhexyl sulfosuccinate were charged into a 2.0-liter polymerization vessel equipped with a reflux condenser, and stirred under a nitrogen stream. The temperature was raised to 80 ° C., and then kept for 30 minutes. After adding 0.40 g of potassium persulfate as an initiator and stirring for 5 minutes, 97.76 g of methyl methacrylate (hereinafter abbreviated as MMA),
1.00 g of 6-hexanediol acrylate (hereinafter abbreviated as HDDA) and allyl methacrylate (hereinafter ALMA)
A mixture of a monomer and an emulsifier consisting of 1.00 g and 0.40 g of sodium di-2-ethylhexyl sulfosuccinate was gradually added over 90 minutes.
The reaction was driven for 0 minutes to form an inner layer portion of the core portion.
Thereafter, 0.10 g of potassium persulfate was added as an initiator, and after stirring for 5 minutes, butyl acrylate (hereinafter BA) was added.
97.76 g, HDDA 1.00 g, ALMA
A mixture of a monomer and an emulsifier consisting of 1.00 g and di-2-ethylhexyl sodium sulfosuccinate 0.40 g was gradually added over 90 minutes, and after the addition was completed, the reaction was driven for 60 minutes to form an outer layer portion of the core portion. did. Thereafter, 0.07 g of potassium persulfate was added as an initiator and 5
After stirring for 60 minutes, a mixture of a monomer and an emulsifier consisting of 61.18 g of BA, 5.32 g of methacrylic acid (hereinafter abbreviated as MAA) and 0.27 g of sodium di-2-ethylhexyl sulfosuccinate was gradually added over 60 minutes. After the addition, the reaction was driven for 60 minutes to form a shell portion. Next, the mixture was cooled to room temperature, an aqueous solution in which 2.08 g of sodium hydrogen carbonate was dissolved in 39.5 g of water was added to the polymerization system over 1 minute, and then the mixture was stirred for 10 minutes. And a nonionic surfactant (Emulgen 120 manufactured by Kao)
A dispersion in which 8.0 g was dispersed in 32 g of water was added to the polymerization system over 1 minute, and the mixture was stirred for 10 minutes. Further, 4.0 g of Polyflow KL260 manufactured by Kyoeisha Chemical Co., Ltd. was used as a penetrant.
Was added to the polymerization system over 1 minute, and the mixture was stirred for 10 minutes, and then the aperture was 150 (μm).
To obtain an aqueous dispersion having particles having a core-shell structure. Further, Nisshinbo Carbodilite E-01 was added to the resin component of the aqueous resin dispersion (D) such that the solid content of Carbodilite E-01 was 3 parts by weight, and the aqueous resin composition (i) was added. Obtained. The glass transition temperatures of the inner layer, the outer layer, and the shell of the core of the core-shell structure particles constituting the aqueous resin composition were 102 ° C., −48 ° C., and −39 ° C., respectively.

REFERENCE EXAMPLE 2 532 g of ultrapure water and 0.27 g of sodium di-2-ethylhexyl sulfosuccinate were charged into a 2.0-liter polymerization vessel equipped with a reflux condenser, and stirred under a nitrogen stream. The temperature was raised to 80 ° C., and then kept for 30 minutes. After adding 0.26 g of potassium persulfate as an initiator and stirring for 5 minutes, MMA 6
5.17 g, HDDA 0.67 g, ALMA 0.67
g and a mixture of a monomer comprising 0.27 g of di-2-ethylhexyl sodium sulfosuccinate and an emulsifier,
After the addition, the reaction was driven for 60 minutes to complete the inner layer of the core. Thereafter, 0.13 g of potassium persulfate was added as an initiator and stirred for 5 minutes, and then 130.34 g of BA, 1.33 g of HDDA and AL
A mixture of a monomer and an emulsifier consisting of 1.33 g of MA and 0.53 g of di-2-ethylhexyl sodium sulfosuccinate was gradually added over 120 minutes.
The reaction was driven for 0 minutes to form an outer layer portion of the core portion. Then, after adding potassium persulfate 0.07g as an initiator and stirring for 5 minutes, 61.18g of BA, MAA
A mixture of a monomer and an emulsifier consisting of 5.32 and 0.27 g of di-2-ethylhexyl sodium sulfosuccinate was gradually added over 60 minutes, and after the addition was completed, the reaction was driven for 60 minutes to form a shell portion. Next, the mixture was cooled to room temperature, an aqueous solution in which 2.08 g of sodium hydrogen carbonate was dissolved in 39.5 g of water was added to the polymerization system over 1 minute, and then the mixture was stirred for 10 minutes. Then, a dispersion obtained by dispersing 8.0 g of a nonionic surfactant (Emulgen 120 manufactured by Kao) in 32 g of water was added to the polymerization system over 1 minute, and the mixture was stirred for 10 minutes. Further, a dispersion obtained by dispersing 4.0 g of Polyflow KL260 manufactured by Kyoeisha Chemical Co., Ltd. in 36 g of water as a penetrant was added to the polymerization system over 1 minute, and then stirred for 10 minutes. The mixture was filtered through a net to obtain an aqueous dispersion having particles having a core-shell structure. Furthermore, Nisshinbo's Carbodilite E-01 was added to the resin component of the aqueous resin dispersion (D) with respect to Carbodilite E-0.
1 was added so that the solid content was 3 parts by weight, to obtain an aqueous resin composition (i). The glass transition temperatures of the inner layer portion, the outer layer portion and the shell portion of the core portion of the core-shell structure particles constituting the aqueous resin composition are 100 ° C. and −48 ° C., respectively.
-38 ° C.

REFERENCE EXAMPLE 3 532 g of ultrapure water and 0.27 g of sodium di-2-ethylhexyl sulfosuccinate were charged into a 2.0-liter polymerization vessel equipped with a reflux condenser, and stirred under a nitrogen stream. The temperature was raised to 80 ° C., and then kept for 30 minutes. After adding 0.80 g of potassium persulfate as an initiator and stirring for 5 minutes, BA 19
5.51 g, HDDA 2.00 g, ALMA 2.00
g and a mixture of a monomer consisting of 0.80 g of di-2-ethylhexyl sodium sulfosuccinate and an emulsifier.
The solution was gradually added over 0 minutes, and the reaction was driven for 60 minutes after the completion of the addition to form a core portion. Thereafter, 0.07 g of potassium persulfate was added as an initiator and stirred for 5 minutes.
A mixture of a monomer and an emulsifier consisting of 61.18 g of AA, 5.32 of MAA and 0.27 g of sodium di-2-ethylhexyl sulfosuccinate was gradually added over 60 minutes, and after the addition was completed, the reaction was driven for 60 minutes to form a shell portion. did. Next, the mixture was cooled to room temperature, an aqueous solution in which 2.08 g of sodium hydrogen carbonate was dissolved in 39.5 g of water was added to the polymerization system over 1 minute, and then the mixture was stirred for 10 minutes. And a nonionic surfactant (Emulgen 120 manufactured by Kao)
A dispersion in which 8.0 g was dispersed in 32 g of water was added to the polymerization system over 1 minute, and the mixture was stirred for 10 minutes. Further, 4.0 g of Polyflow KL260 manufactured by Kyoeisha Chemical Co., Ltd. was used as a penetrant.
Was added to the polymerization system over 1 minute, and the mixture was stirred for 10 minutes, and then the aperture was 150 (μm).
To obtain an aqueous dispersion having particles having a core-shell structure. Further, Nisshinbo Carbodilite E-01 was added to the resin component of the aqueous resin dispersion (D) such that the solid content of Carbodilite E-01 was 3 parts by weight, and the aqueous resin composition (i) was added. Obtained. Glass transition temperatures of the core part and the shell part of the core-shell structure particles constituting the aqueous resin composition are −48 ° C. and −39, respectively.
° C.

REFERENCE EXAMPLE 4 532 g of ultrapure water and 0.27 g of sodium di-2-ethylhexyl sulfosuccinate were charged into a 2.0-liter polymerization vessel equipped with a reflux condenser, and stirred under a nitrogen stream. The temperature was raised to 80 ° C., and then kept for 30 minutes. After adding 0.40 g of potassium persulfate as an initiator and stirring for 5 minutes, MMA 7
8.20 g, styrene (hereinafter abbreviated as St) 19.55
g, HDDA 1.00 g, ALMA 1.00 g, and di-2-ethylhexyl sodium sulfosuccinate 0.4
A mixture of 0 g of the monomer and the emulsifier was gradually added over 90 minutes, and after completion of the addition, the reaction was driven for 60 minutes to form an inner layer portion of the core portion. Then, after adding 0.10 g of potassium persulfate as an initiator and stirring for 5 minutes, BA
97.76 g, HDDA 1.00 g, ALMA 1.00
g and a mixture of a monomer comprising 0.40 g of di-2-ethylhexyl sodium sulfosuccinate and an emulsifier,
After the addition, the reaction was driven for 60 minutes after completion of the addition to form an outer layer portion of the core portion. Thereafter, 0.07 g of potassium persulfate was added as an initiator, and the mixture was stirred for 5 minutes. After the addition, the reaction was driven for 60 minutes after the addition to form a shell portion. Next, the mixture was cooled to room temperature, an aqueous solution in which 2.08 g of sodium hydrogen carbonate was dissolved in 39.5 g of water was added to the polymerization system over 1 minute, and then the mixture was stirred for 10 minutes. Then, a dispersion obtained by dispersing 8.0 g of a nonionic surfactant (Emulgen 120 manufactured by Kao) in 32 g of water was added to the polymerization system over 1 minute, and the mixture was stirred for 10 minutes. Further, as a penetrant, Polyflow KL260 manufactured by Kyoeisha Chemical Co., Ltd.
Was added to the polymerization system over 1 minute, and then stirred for 10 minutes.
The mixture was filtered through a 0 (μm) plastic net to obtain an aqueous dispersion having particles having a core-shell structure. Further, Nisshinbo Carbodilite E-01 was added to the resin component of the aqueous resin dispersion (D) such that the solid content of Carbodilite E-01 was 3 parts by weight, and the aqueous resin composition (i) was added. Obtained. The glass transition temperatures of the inner layer portion, outer layer portion, and shell portion of the core portion of the core-shell structure particles constituting the aqueous resin composition were 100 ° C., −48 ° C., and −38 ° C., respectively.

REFERENCE EXAMPLE 5 532 g of ultrapure water and 0.27 g of sodium di-2-ethylhexyl sulfosuccinate were charged into a 2.0-liter polymerization vessel equipped with a reflux condenser, and stirred under a nitrogen stream. The temperature was raised to 80 ° C., and then kept for 30 minutes. After adding 0.40 g of potassium persulfate as an initiator and stirring for 5 minutes, MMA 9
7.76 g, HDDA 1.00 g, ALMA 1.00
g and a mixture of a monomer consisting of 0.40 g of di-2-ethylhexyl sodium sulfosuccinate and an emulsifier are mixed with 90
After the addition, the reaction was driven for 60 minutes to complete the inner layer of the core. Then, after adding 0.10 g of potassium persulfate as an initiator and stirring for 5 minutes, 97.76 g of BA, 1.00 g of HDDA, and ALM
A mixture of a monomer and an emulsifier consisting of 1.00 g of A and 0.40 g of di-2-ethylhexyl sodium sulfosuccinate was gradually added over 90 minutes, and after the addition was completed, the reaction was driven for 60 minutes to form an outer layer portion of the core portion. did. Thereafter, after adding 0.07 g of potassium persulfate as an initiator and stirring for 5 minutes, 26.60 g of MMA, 39.90 g of ethyl acrylate (hereinafter abbreviated as EA) and 0.27 g of di-2-ethylhexyl sodium sulfosuccinate were added.
g of a mixture of a monomer and an emulsifier was gradually added over 60 minutes, and after the addition was completed, the reaction was driven for 60 minutes to form a shell portion. Then, the mixture was cooled to room temperature, and 8.0 g of a nonionic surfactant (Emulgen 120 manufactured by Kao) was added to 32 g of water.
Was added to the polymerization system over 1 minute and stirred for 10 minutes. Further, a dispersion obtained by dispersing 4.0 g of Polyflow KL260 manufactured by Kyoeisha Chemical Co., Ltd. in 36 g of water as a penetrant was added to the polymerization system over 1 minute, and then stirred for 10 minutes. The mixture was filtered through a net to obtain an aqueous dispersion having particles having a core-shell structure. Further, Nisshinbo Carbodilite E-01 was added to the resin component of the aqueous resin dispersion (D) such that the solid content of Carbodilite E-01 was 3 parts by weight, and the aqueous resin composition (i) was added. Obtained. The glass transition temperatures of the inner layer portion, outer layer portion and shell portion of the core portion of the core-shell structure particles constituting the aqueous resin composition are 101 ° C. and −4, respectively.
8 ° C and 26 ° C.

REFERENCE EXAMPLE 6 532 g of ultrapure water and 0.27 g of di-2-ethylhexyl sodium sulfosuccinate were charged into a 2.0-liter polymerization vessel equipped with a reflux condenser, and stirred under a nitrogen stream. The temperature was raised to 80 ° C., and then kept for 30 minutes. After adding 1.06 g of potassium persulfate as an initiator and stirring for 5 minutes, BA26 was added.
0.68 g, HDDA 2.66 g, ALMA 2.66
g, and a mixture of a monomer consisting of 1.06 g of di-2-ethylhexyl sodium sulfosuccinate and an emulsifier,
The mixture was gradually added over 0 minutes, and the reaction was driven for 60 minutes after completion of the addition to form an emulsion of particles having a single-layer structure. Next, the mixture was cooled to room temperature, and a dispersion in which 8.0 g of a nonionic surfactant (Emulgen 120 manufactured by Kao) was dispersed in 32 g of water was added to the polymerization system over 1 minute, followed by stirring for 10 minutes. Further, a dispersion obtained by dispersing 4.0 g of Polyflow KL260 manufactured by Kyoeisha Chemical Co., Ltd. in 36 g of water as a penetrating agent was added to the polymerization system over 1 minute, and then stirred for 10 minutes. The mixture was filtered through a net to obtain an aqueous dispersion having particles having a single-layer structure. The glass transition temperature of the polymer constituting the particles was -48 ° C.

Example 1 As a polymer (A), P
ET was used and this was used as component (ii). Nylon 6 was used as the polymer (B), and this was used as the component (iii).
And PET and nylon 6 are melt-extruded with separate extruders, and the weight ratio of PET / nylon 6 is 70/30.
After being metered by a gear pump so as to be supplied into the spinning pack, the mixture is discharged at a die temperature of 290 ° C.
It was wound at 0 m / min. After spinning, it is stretched and has a single yarn fineness of 3.
A splittable fiber of 0 dtex was obtained. The cut surface at five places where the obtained split fiber was cut at intervals of 5 m had a PET coating thickness of 0.4 μm wrapping the outer peripheral surface of the fiber, and PET (6 layer portions) and nylon 6 (5 layer portion) were 11 parts. The layers were alternately arranged. After stretching, mechanical crimping is applied and then 51 m
m to obtain staple fibers. The obtained staple fiber was made into a web through a card and a cross wrapper. There is no process trouble in web production,
Good passability was shown. When the inside of this web was observed with a scanning electron microscope, no split fibers were found. Next, needle punching of 1600 punches / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was immersed 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 16% in the vertical direction and 17% in the horizontal direction.

After drying the contracted nonwoven fabric (hereinafter referred to as nonwoven fabric (A)), 25 parts of the solid content of the aqueous resin composition (i) produced in Reference Example 1 is added to 100 parts of the nonwoven fabric (A). As described above, the nonwoven fabric is impregnated with the aqueous resin composition (i), dried with hot air of 130 ° C., and then pressed with a roller heated to 120 ° C. to smooth the surface and to have a thickness of about 1 mm.
Was obtained. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, one surface of the fibrous substrate was buffed with sandpaper to adjust the thickness to 0.80 mm, and then the other surface was treated with an emery buffing machine to form an extremely fine nap surface, and further a circular jet dyeing machine. Using 10
g / liter aqueous sodium hydroxide solution
By treating at 60 ° C. for 60 minutes, the splittable fibers constituting the fibrous substrate were split (average fineness of ultrafine fibers: 0.1.
32 decitex). Then, it was washed with a circular jet dyeing machine to remove sodium hydroxide. Subsequently, using a circular jet dyeing machine, the product was dyed brown using a disperse dye and then finished to obtain a suede-like leather-like sheet having a specific gravity of 0.47. This product was excellent in fullness and flexibility, and showed a good feeling. The leather-like sheet had good dyeing properties and could be dyed in a deep color with a disperse dye. The light fastness was No. 4-5, and the tensile strength was 23 kg / 2.5 cm, which was an excellent value.

[Example 2] The solid content of the aqueous resin composition (i) produced in Reference Example (2) was added to 100 parts of the nonwoven fabric (A) obtained in Example 1 so that 25 parts thereof were added. The nonwoven fabric was impregnated with the aqueous resin composition (i), dried with hot air at 130 ° C., and then pressed with a roller heated to 120 ° C. to smooth the surface to obtain a fibrous substrate having a thickness of about 1 mm. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, one surface of the fibrous substrate was buffed with sandpaper to adjust the thickness to 0.80 mm, and then the other surface was treated with an emery buffing machine to form an extremely fine nap surface, and further a circular jet dyeing machine. Was treated with an aqueous solution of sodium hydroxide having a concentration of 10 g / liter at 80 ° C. for 60 minutes, thereby dividing the fibrous base constituting the fibrous substrate (average fineness of microfiber: 0.32). Decitex). Then, it was washed with a circular jet dyeing machine to remove sodium hydroxide. Subsequently, the product was dyed brown using a disperse dye with a circular jet dyeing machine and then finished to obtain a suede-like leather-like sheet having a specific gravity of 0.47. Example 1
As in the case of Example 1, it was excellent in fullness and flexibility, and the surface smoothness was more excellent than that of Example 1, showing a good feeling. The dyeability was good, but the color after dyeing was slightly lighter than that of Example 1. The leather-like sheet exhibited excellent light fastness of No. 4 and excellent tensile strength of 24 kg / 2.5 cm.

Example 3 To 100 parts of the nonwoven fabric (A) obtained in Example 1, 25 parts of the solid content of the aqueous resin composition (i) produced in Reference Example (3) was added. The nonwoven fabric was impregnated with the aqueous resin composition (i), dried with hot air at 130 ° C., and then pressed with a roller heated to 120 ° C. to smooth the surface to obtain a fibrous substrate having a thickness of about 1 mm. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, one surface of the fibrous base material was buffed with sandpaper to adjust the thickness to 0.80 mm, and then, using a circular jet dyeing machine, an aqueous solution of sodium hydroxide having a concentration of 10 g / liter at 80 ° C. By treating under the conditions of 60 minutes, the splittable fibers constituting the fibrous substrate were split (average fineness of the ultrafine fibers: 0.32 dtex). Wash with water,
After removing the sodium hydroxide, the fibrous substrate is dried,
The aqueous resin composition (i) obtained in Reference Example (3) was coated and dried to form a resin layer having a thickness of 30 μm on the surface, and a leather-like sheet with silver having a specific gravity of 0.49 was obtained. Was. It was excellent in fullness, flexibility and surface appearance, and showed a good feeling. In addition, the leather-like sheet was extremely excellent in light yellowing resistance as No. 5 without yellowing at all. Tensile strength is 25
kg / 2.5 cm, which was an excellent value.

[Example 4] The non-woven fabric (A) obtained in Example 1 was added to the non-woven fabric (A) by 100 parts by weight.
The nonwoven fabric is impregnated with the aqueous resin composition (i) so as to give 25 parts of the solid content of the aqueous resin composition (i) produced in the above, dried with hot air at 130 ° C, and then heated to 120 ° C. The surface is smoothed by pressing with a thickness of about 1 mm
Was obtained. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, one surface of the fibrous substrate was buffed with sandpaper to adjust the thickness to 0.80 mm, and then the other surface was treated with an emery buffing machine to form an extremely fine nap surface, and further a circular jet dyeing machine. Using 10
g / liter aqueous sodium hydroxide solution
By treating at 60 ° C. for 60 minutes, the splittable fibers constituting the fibrous substrate were split (average fineness of ultrafine fibers: 0.1.
32 decitex). Then, it was washed with a circular jet dyeing machine. After dyeing brown using a disperse dye with a circular jet dyeing machine, finish the specific gravity 0.4
Thus, a leather-like sheet No. 7 was obtained. As in Example 1, a sense of fulfillment,
It was excellent in flexibility and surface appearance, and showed good feeling.
The dyeability was excellent as in Example 1. This leather-like sheet has a light fastness of No. 4-5 and a tensile strength of 25 kg / 2.5.
cm and an excellent value.

Example 5 The polymer (A) was P
ET was used and this was used as component (ii). Polyester (1) was used as polymer (B), and this was used as component (iii). PET is used as an island component, polyester (1) is used as a sea component, and PET and polyester (1) are melt-extruded by separate extruders, respectively. After weighing, the mixture is fed into a spin pack, the fiber shape is defined at the spinneret, and the fiber is discharged at a spinneret temperature of 290 ° C.
Winding was performed at 00 m / min. After spinning, drawing was performed to obtain sea-island fibers having a single yarn fineness of 3.0 dtex. The cut surface obtained by cutting the obtained sea-island fiber was a sea-island shape having 25 islands. After stretching, mechanical crimping was applied and then 51 mm
To obtain staple fibers. The obtained staple fiber was made into a web through a card and a cross wrapper. No process trouble occurred in the web preparation, and good passability was exhibited. Next, 1200 punches / c
and the fiber-entangled non-woven fabric performs a needle punch of m ^2. Subsequently, the fiber-entangled nonwoven fabric was immersed 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 20% in the vertical direction and 21% in the horizontal direction.

After drying the contracted non-woven fabric (hereinafter referred to as non-woven fabric (B)), 20 parts of the aqueous resin composition (i) produced in Reference Example 2 was added to 100 parts of the non-woven fabric (B). As described above, the nonwoven fabric is impregnated with the aqueous resin composition (i), dried with hot air at 130 ° C., and then pressed with a roller heated to 120 ° C. to smooth the surface, and to have a thickness of about 1 mm.
Was obtained. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, the fibrous substrate was immersed in a 40 g / l aqueous solution of sodium hydroxide adjusted to a temperature of 95 ° C., and squeezed with a roller repeatedly to decompose and remove polyester (1), which is a sea component of sea-island fibers. The fibers were ultrafine. The fineness of the ultrafine fibers was 0.089 dtex on average. The ultrafine fibrous base material is washed with water, dried, buffed with sandpaper and adjusted to a thickness of 0.80 mm, and then the other surface is treated with an emery buffing machine to form an ultrafine nap surface. Further, the product was dyed brown using a disperse dye with a circular jet dyeing machine, and finished to obtain a suede-like leather-like sheet having a specific gravity of 0.48. This product was excellent in fullness and flexibility, and showed a good feeling. The leather-like sheet had good dyeability, and could be dyed in a deep color with a disperse dye. Further, the leather-like sheet has a light fastness of No. 4-5 and a tensile strength of 25 kg / 2.
It showed an excellent value of 5 cm.

Example 6 As a high molecular weight polymer (A),
PA-modified PET was used and this was used as component (ii). Using ethylene copolymerized PVA as the polymer (B),
This was designated as component (iii). An IPA-modified PET is used as an island component, and an ethylene copolymerized PVA is used as a sea component.
And ethylene copolymerized PVA were melt-extruded by separate extruders, and the weight ratio of PET / ethylene copolymerized PVA was 60
After being measured by a gear pump so as to be / 40, the mixture was fed into a spinning pack, the fiber shape was defined at a spinneret, discharged at a spinneret temperature of 260 ° C, and wound at a speed of 500 m / min. After spinning, drawing was performed to obtain sea-island fibers having a single yarn fineness of 3.0 dtex. The cut surface obtained by cutting the obtained sea-island fiber was a sea-island shape having 25 islands. After the stretching, a mechanical crimp was applied, and then cut into 51 mm to obtain staple fibers. The obtained staple fiber was made into a web through a card and a cross wrapper. No process trouble occurred in the web preparation, and good passability was exhibited. Next, needle punching of 1200 punches / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was immersed 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.

After drying the contracted nonwoven fabric (hereinafter referred to as nonwoven fabric (C)), 20 parts of the solid content of the aqueous resin composition (i) produced in Reference Example 2 was added to 100 parts of the nonwoven fabric (C). As described above, the nonwoven fabric is impregnated with the aqueous resin composition (i), dried with hot air at 130 ° C., and then pressed with a roller heated to 120 ° C. to smooth the surface, and to have a thickness of about 1 mm.
Was obtained. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, the fibrous base material was immersed in hot water at 95 ° C. and pressed with a roller repeatedly to dissolve and remove the ethylene copolymerized polyvinyl alcohol (1), which is the sea component of the sea-island cross-section multicomponent fiber, to make the fiber extremely fine. . The fineness of the ultrafine fibers was 0.087 dtex on average. After drying the ultrafine fibrous substrate, buffing it with sandpaper and adjusting the thickness to 0.80 mm, the other surface is treated with an emery buffing machine to form an extremely fine raised surface, and furthermore, a circular surface. After dyeing brown with a disperse dye using a jet dyeing machine, the leather-like sheet having a specific gravity of 0.46 was obtained by finishing. It was excellent in fullness and flexibility, and showed a good feeling. The leather-like sheet had good dyeability and could be dyed in a deep color with a disperse dye. The light fastness was No. 4-5, and the tensile strength was 23 kg / 2.5 cm, which was an excellent value.

Example 7 Nylon 6 was used as the polymer (A), and this was used as the component (ii). Polyester (1) was used as polymer (B), and this was used as component (iii). Nylon 6 is used as an island component, polyester (1) is used as a sea component, and nylon 6 and polyester (1) are melt-extruded by separate extruders, respectively, so that the weight ratio of nylon 6 / polyester (1) becomes 60/40. After being measured by a gear pump, it is supplied into the spinning pack,
The shape of the fiber was defined at the spinneret, and the fiber was discharged at a spinneret temperature of 270 ° C. and wound at a speed of 500 m / min. After spinning, it was drawn to obtain a multicomponent fiber having a sea-island cross-sectional structure with a single yarn fineness of 3.0 dtex. The cut surface obtained by cutting the obtained fiber was a sea-island shape having 25 islands. After stretching,
Mechanical crimping was applied and then cut to 51 mm to obtain staple fibers. The obtained staple fiber is a card,
A web was produced via a cross wrapper. No process trouble occurred in the web preparation, and good passability was exhibited. Next, needle punching of 1200 punches / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was immersed 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 10% in the vertical direction and 11% in the horizontal direction.

After drying the contracted nonwoven fabric (hereinafter referred to as nonwoven fabric (D)), 20 parts of the aqueous resin composition (i) produced in Reference Example 2 was added to 100 parts of the nonwoven fabric (D). As described above, the aqueous resin composition (i) is made of a nonwoven fabric (D).
After drying with hot air at 130 ° C., the surface was smoothed by pressing with a roller heated to 120 ° C. to obtain a fibrous substrate having a thickness of about 1 mm. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, the fibrous substrate was immersed in a 40 g / l aqueous solution of sodium hydroxide adjusted to a temperature of 95 ° C., and squeezed with a roller repeatedly to decompose and remove polyester (1), which is a sea component of sea-island fibers. The fibers were ultrafine. The fineness of the ultrafine fibers was 0.082 dtex on average. After the ultrafine fibrous base was washed with water and dried, one surface of the fibrous base was buffed with sandpaper to adjust the thickness to 0.80 mm. Subsequently, the aqueous resin composition (i) obtained in Reference Example (3) was coated and dried to form a 30-micron-thick resin layer on the surface, and the specific gravity was 0.38. I got a sheet. This product was excellent in a feeling of fulfillment, flexibility and surface appearance, and showed a good feeling. In addition, the leather-like sheet was extremely excellent in light yellowing resistance as No. 5 without yellowing at all. The tensile strength showed an excellent value of 27 kg / 2.5 cm.

Example 8 As a high molecular weight polymer (A),
PA-modified PET was used and this was used as component (ii). Nylon 12 was used as the polymer (B), and this was used as the component (iii). IPA modified PET and nylon 12
Are melt-extruded in separate extruders, and IPA-modified PE
After each was measured by a gear pump so that the weight ratio of T / nylon 12 became 70/30, it was supplied into a spinning pack, discharged at a die temperature of 260 ° C, and wound up at a speed of 500 m / min. After spinning, drawing was performed to obtain a laminated splittable fiber having a single yarn fineness of 3.0 dtex. Five cut surfaces obtained by cutting the obtained split fiber at intervals of 5 m were obtained by IPA copolymer P
ET (5 layers) and nylon 12 (6 layers) are 11
The layers were alternately arranged. After stretching, mechanical crimping is applied,
Then, it was cut to 51 mm to obtain staple fibers. The obtained staple fiber was made into a web through a card and a cross wrapper. No process trouble occurred in the web preparation, and good passability was exhibited. Next, punch number 16
A needle punch of 00 punch / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was immersed in a bath containing hot water at 90 ° C. to shrink the nonwoven fabric. Shrinkage ratio [(length of nonwoven fabric after shrinkage / length of nonwoven fabric before shrinkage) x
100] was 20% in the vertical direction and 19% in the horizontal direction.

After drying the contracted nonwoven fabric (hereinafter referred to as nonwoven fabric (E)), 25 parts of the solid content of the aqueous resin composition (i) produced in Reference Example 2 was added to 100 parts of the nonwoven fabric (E). As described above, the aqueous resin composition (i) is
After drying with hot air at 130 ° C., the surface was smoothed by pressing with a roller heated to 120 ° C. to obtain a fibrous substrate having a thickness of about 1 mm. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, the fibrous substrate was immersed in an aqueous solution of sodium hydroxide having a concentration of 40 g / l adjusted to a temperature of 95 ° C., and 3 to 6 wt% of the IPA-modified PET was reduced to thereby split and ultrafine the fibers. The fineness of the ultrafine fibers was 0.35 dtex on average. After the ultrafine fibrous base was washed with water and dried, one surface of the fibrous base was buffed with sandpaper to adjust the thickness to 0.80 mm. Next, the other surface was treated with an emery buffing machine to form an extremely fine nap surface, and further dyed brown using a disperse dye with a circular jet dyeing machine, and then finished to give a suede-like material having a specific gravity of 0.45. A leather-like sheet was obtained. This product was excellent in fullness and flexibility, and showed a good feeling. In addition, the dyeability of this leather-like sheet was good and it was dyed dark. The light fastness is No. 4-5, and the tensile strength is 25 kg / 2.
It showed an excellent value of 5 cm.

Example 9 As a high molecular weight polymer (A),
PA-modified PET was used and this was used as component (ii). A nylon 12-based elastomer was used as the polymer (B), and this was used as the component (iii). IPA modified PE
T and nylon 12-based elastomer are melt-extruded by separate extruders, respectively, weighed by a gear pump such that the weight ratio of IPA-modified PET / nylon 12-based elastomer is 70/30, and then supplied into a spinning pack. It was discharged at a temperature of 260 ° C. and wound up at a speed of 500 m / min. After spinning, drawing was performed to obtain a laminated splittable fiber having a single yarn fineness of 3.0 dtex. Five cut surfaces obtained by cutting the obtained split fibers at intervals of 5 m were IPA-modified PET (5
Layers) and nylon 12-based elastomer (six layers) were alternately arranged in 11 layers. After the stretching, a mechanical crimp was applied, and then cut into 51 mm to obtain staple fibers. The obtained staple fiber was made into a web through a card and a cross wrapper. No process trouble occurred in the web preparation, and good passability was exhibited. Next, needle punching of 1600 punches / cm ² was performed to obtain a fiber-entangled nonwoven fabric. Subsequently, the fiber-entangled nonwoven fabric was immersed 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) is 24% in the vertical direction and 23% in the horizontal direction.
Met.

After drying the contracted nonwoven fabric (hereinafter referred to as nonwoven fabric (F)), 25 parts of the solid content of the aqueous resin composition (i) produced in Reference Example 2 was added to 100 parts of the nonwoven fabric (F). As described above, the nonwoven fabric is impregnated with the aqueous resin composition (i), dried with hot air at 130 ° C., and then pressed with a roller heated to 120 ° C. to smooth the surface, and to have a thickness of about 1 mm.
Was obtained. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Subsequently, the fibrous substrate was immersed in an aqueous solution of sodium hydroxide having a concentration of 40 g / l adjusted to a temperature of 95 ° C., and 3 to 6 wt% of the IPA-modified PET was reduced to thereby split and ultrafine the fibers. The fineness of the ultrafine fibers was 0.37 dtex on average. After the ultrafine fibrous base was washed with water and dried, one surface of the fibrous base was buffed with sandpaper to adjust the thickness to 0.80 mm. Next, the other surface was treated with an emery buffing machine to form an extremely fine nap surface, and further dyed brown using a disperse dye with a circular jet dyeing machine, and finished to a specific gravity of 0.4.
Thus, a suede-like leather-like sheet No. 5 was obtained. This product was excellent in fullness and flexibility, and showed a good feeling. In addition, the dyeability of this leather-like sheet was good and it was dyed dark. The light fastness was No. 4-5, and the tensile strength was 23 kg / 2.5 cm, which was an excellent value.

[Comparative Example 1] A solid content of a polyurethane emulsion (Bondick 1310 manufactured by Dainippon Ink and Chemicals, Inc.) was added to 100 parts of the nonwoven fabric (B) obtained in Example 5 so that 25 parts of the solid was added. The polyurethane emulsion was impregnated into a nonwoven fabric, dried with hot air at 130 ° C., and then pressed with a roller heated to 120 ° C. to smooth the surface to obtain a fibrous substrate having a thickness of about 1 mm. The surface of the fibrous substrate was not tacky at all, and the fibrous substrates did not stick to each other even when the fibrous substrates were stacked. Then, 9
The fibrous substrate is immersed in a 40 g / l aqueous solution of sodium hydroxide adjusted to a temperature of 5 ° C., and is repeatedly pressed with a roller to decompose and remove polyester (1) which is a sea component of the sea-island cross-section multicomponent fiber. The fibers were ultrafine. The fineness of the ultrafine fibers was 0.090 dtex on average. After the ultrafine fibrous base material was washed with water and dried, it was buffed with sandpaper and adjusted to a thickness of 0.80 mm.
The other side is treated with an emery buffing machine to form a very fine nap, and after being dyed brown using a disperse dye with a circular jet dyeing machine, it is finished to a suede-like leather with a specific gravity of 0.45. I got a sheet. The sense of fulfillment was excellent, but the flexibility was significantly lacking. The light fastness of this leather-like sheet was No. 3, and the tensile strength was 17 kg / 2.5 cm, which was considerably inferior to the leather-like sheet of the example.

Comparative Example 2 An aqueous dispersion was prepared by adding 100 parts of the nonwoven fabric (B) obtained in Example 5 with 25 parts of the solid content of the aqueous dispersion obtained in Reference Example 5. After drying with hot air of 130 ° C, the surface was smoothed by pressing with a roller heated to 120 ° C, and the thickness was about 1
mm of fibrous substrate was obtained. Although the surface of the fibrous substrate was slightly tacky, when the fibrous substrates were stacked, the fibrous substrates adhered to each other but could be removed. Subsequently, the fibrous substrate was immersed in an aqueous solution of sodium hydroxide having a concentration of 40 g / l adjusted to a temperature of 95 ° C., and pressing with a roller was repeated.
The polyester (1), which is the sea component of the sea-island cross-section multicomponent fiber, was decomposed and removed to make the fiber extremely fine. The fineness of the ultrafine fibers was 0.090 dtex on average. After the ultrafine fibrous base material was washed with water and dried, it was buffed with sandpaper and adjusted to a thickness of 0.80 mm.
The other side is treated with an emery buffing machine to form a very fine nap, and after being dyed brown using a disperse dye with a circular jet dyeing machine, finished to a suede-like leather with a specific gravity of 0.47. I got a sheet. Although the sense of fulfillment was excellent, it lacked flexibility. The light fastness of this leather-like sheet is 4-5.
The tensile strength was 12 kg / 2.5 cm, which was considerably inferior to the leather-like sheet of Example 5.

Comparative Example 3 The acrylic emulsion was mixed with 100 parts of the nonwoven fabric (B) obtained in Example 5 so that the solid content of the aqueous resin dispersion obtained in Reference Example 6 was 25 parts. And dried with hot air at 130 ° C.
The surface was smoothed by pressing with a roller heated to 20 ° C. to obtain a fibrous substrate having a thickness of about 1 mm. The surface of the fibrous substrate is strongly tacked, and when the fibrous substrates are stacked, the fibrous substrates adhere to each other, and the subsequent process passability is extremely poor.
Production stopped.

[0081]

Industrial Applicability The present invention impregnates a leather-like sheet which does not have flexibility, surface appearance, fullness, etc., has no tackiness, and has various durability such as light resistance. The present invention provides a method for producing a leather-like sheet which can be produced without using an organic solvent for a resin.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a cross section of a multicomponent fiber of the present invention, in the case of a multilayer laminated fiber.

FIG. 2 is a schematic view showing another example of the cross section of the multicomponent fiber of the present invention, which is a multilayer laminated type having a coating layer on the outside.

FIG. 3 is a schematic view showing another example of the cross section of the multicomponent fiber of the present invention, which is a multilayer laminated type having a radial cross section.

FIG. 4 is a schematic view showing another example of the cross section of the multicomponent fiber of the present invention, in which a multilayer laminated type has a radial cross section, and one component forms a core in the center. is there.

FIG. 5 is a schematic diagram showing another example of the cross section of the multicomponent fiber of the present invention, which is a multilayer laminated type having a radial cross section and having a hollow central portion.

FIG. 6 is a schematic view showing another example of the cross section of the multicomponent fiber of the present invention, in which the fiber cross section has a sea-island shape.

[Explanation of symbols]

 (1): Component (ii) (2): Component (iii)

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F055 AA02 BA12 DA07 EA04 EA05 EA13 EA24 EA30 EA34 FA10 GA22 HA04 HA22 4J026 AA12 AA13 AA17 AA18 AA25 AA31 AA33 AA45 AA46 AA47 AA49 AA34 BA17 AC12 BB07 DA04 DA07 DB04 DB08 FA07 GA01

Claims (10)

[Claims] An aqueous resin composition having cross-linking curability (i) is applied to a fabric, and the surface of the fabric is fluffed.
Alternatively, in the method for producing a leather-like sheet by forming a resin layer on the surface of the cloth, the resin constituting the aqueous resin composition (i) has a core-shell structure, and the shell portion is mainly a monofunctional ethylenically unsaturated monomer. A copolymer of an ethylenically unsaturated monomer (ds2) having a functional group reactive with (ds1), the core of which is a monofunctional ethylenically unsaturated monomer (dc1) and a bifunctional or higher polyfunctional ethylenically unsaturated monomer A method for producing a leather-like sheet, which is a copolymer of a monomer (dc2). 2. The fabric to which the aqueous resin composition (i) is applied,
A component (ii) composed of the polymer (A) and a polymer (B) incompatible with the polymer (A) or a component (i) composed of a polymer (C) that can be dissolved or decomposed and removed in water or an aqueous solution.
ii) is a nonwoven fabric composed of multicomponent fibers arranged in a laminate or in a sea-island shape having (C) as a sea component in a fiber cross section, wherein a resin layer is formed on the fabric surface prior to fluffing or on the fabric surface. Prior to formation, the multicomponent fiber is peeled off at the interface between (A) and (B), or (C)
The production method according to claim 1, wherein the fibers are made ultrafine by removing water or an aqueous solution. 3. The aqueous resin composition (i) mainly comprises an aqueous resin dispersion (D) and a curing agent (E), and the curing agent (E) is a resin shell portion of the aqueous resin dispersion (D). The production method according to claim 1, which is a water-soluble or water-dispersible curing agent containing two or more functional groups capable of reacting with the reactive functional group in the molecule. 4. A curing agent (E) wherein the reactive functional group in the resin shell portion of the aqueous resin dispersion (D) is a carboxyl group.
The method according to claim 3, wherein the reactive functional group in the group is a carbodiimide group or an oxazoline group. 5. The aqueous resin dispersion (i), wherein the core portion of the resin component has a two-layer structure of an inner layer and an outer layer, wherein the inner layer is a resin having a glass transition temperature of 50 ° C. or higher, and the outer layer is a resin having a glass transition temperature of 20 ° C. The production method according to any one of claims 1 to 4, wherein the resin is a resin having a temperature of not more than ℃. 6. The fiber constituting the fabric is a laminated multi-component fiber in which the component (ii) and the component (iii) are alternately arranged in a cross section of the fiber. The entire periphery of the surface is coated with the component (ii) or the component (iii), and the thickness of the coating of the component (iii) covering the component (ii) or the component (ii) covering the component (iii) The thickness of the film is 0.05-2.0 μm
3. The method according to claim 2, wherein 7. The fiber constituting the fabric is a laminated multicomponent fiber in which component (ii) and component (iii) are alternately arranged, and the polymer (A) is mainly composed of an alkylene terephthalate unit. 7. The method according to claim 2, wherein the polymer (B) is a polyamide satisfying carbon number / amide group number> 7. 8. The fiber constituting the fabric is a laminated multicomponent fiber in which the component (ii) and the component (iii) are alternately arranged, and the polymer (A) is mainly composed of an alkylene terephthalate unit. The method according to claim 2, wherein the production method is a polyester, and the polymer (B) is a polyamide block copolymer. 9. A leather-like sheet produced by the method according to claim 1. 10. A leather-like sheet in which a resin layer comprising the aqueous resin composition (i) according to any one of claims 1, 3, 4 and 5 is formed on a fibrous base material.