JP2003306876A - Substrate for flame-retardant leather-like sheet, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a halogen-free substrate for a flame-retardant leather-like sheet, having excellent flame retardancy and soft feeling. <P>SOLUTION: The substrate for the leather-like sheet is obtained by laminating a layer (A) and a layer (B) regulated so that the ratio [(A)/(B)] of the laminates by weight is (10/90) to (90/10). The layer (A) comprises an entangled nonwoven fabric comprising an ultrafine fiber (a) having ≤0.5 dtex size and obtained from a polymer colored with carbon black, and a macromolecular elastomer. The layer (B) comprises an entangled nonwoven fabric comprising an ultrafine fiber (b) having ≤0.5 dtex size and obtained from a polymer colored with carbon black or not colored, and a macromolecular elastomer. The ultrafine fibers (a) and (b) comprise a copolyester with a copolymerized organophosphorus component, and the macromolecular elastomer contains aluminum hydroxide. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is halogen-free and excellent in flame retardancy, and is suitable for the field of interiors, especially for applications requiring flame retardancy such as vehicle seats, and particularly when used in a dark color. The present invention relates to a flame-retardant leather-like sheet substrate having a soft texture, which is made of ultrafine fibers and a polymer elastic material.

[0002]

2. Description of the Related Art Artificial leather is used for interior, clothing, shoes,
It has been used for various purposes such as bags and gloves, but recently, in the interior field, especially in the field used for upholstery such as seats for railroad cars, seats for cars, seats for aircraft, it is safe and environmentally friendly. From the viewpoint, giving halogen-free flame-retardant performance is an extremely important theme. Furthermore, in order to express a sense of fashion and corporate image,
The variety of colors required for materials is expanding, and there is a demand for artificial leather materials that combine color development and non-staining properties such as fastness.

[0003] Artificial leather is roughly classified into two types, silver-tone and suede-tone, and the base layer as the base has a structure having a polymer elastic body in the entangled space of the ultrafine fiber nonwoven fabric. . As a method for imparting flame retardancy to such an artificial leather base layer, a suede-like artificial leather in which the surface of the base layer is raised and dyed, or a silver surface is provided on the base layer by a dry method or a wet method. A method in which artificial leather with silver is applied by impregnating a flame retardant (hereinafter referred to as a post-processing method), a method in which a sheet based on a woven or knitted fabric having flame retardancy is adhered to the back surface, and flame retardant fine particles are used as fibers. A method of kneading a formed thermoplastic polymer or a polymer elastic body with which a fiber-entangled nonwoven fabric is impregnated is generally performed. Further, in the product obtained by dyeing a leather-like sheet substrate, the amount of the dye used varies depending on the color density, and the darker the color, the larger the amount of the dye used, so that the friction fastness and the light fastness tend to deteriorate. As a means for solving this, a method of kneading carbon black into the fibers or polymer elastic body constituting the artificial leather substrate has been adopted.

First, the prior art for imparting flame retardancy will be specifically described. Among the above methods, in the case of a post-processing method, a method of impregnating a leather-like sheet substrate with a flame retardant-containing liquid and drying is common, but in the case of such a method,
When the fiber is an ultrafine fiber bundle and the flame retardant is fine particles, the flame retardant hardly penetrates into the ultrafine fiber bundle,
Most of the flame retardant is present on the outside of the fiber bundle or the outside surface of the elastic polymer. In this case,
The flame retardant is easily removed, and a durable flame retardant effect cannot be obtained. There is also a method of kneading a flame retardant into a binder resin and impregnating the leather-like sheet substrate with this binder resin liquid in order to prevent the flame retardant from falling off. Does not penetrate, and the flame retardant is covered with resin, so the flame retardancy is greatly reduced, and since the leather-like sheet substrate is also filled with resin, the flexibility of the leather-like sheet substrate is impaired, and There was a defect that a good napped state could not be obtained.

Further, in the case of a method of sticking a flame-retardant sheet to the back surface, a sheet-like material obtained by applying a flame-retardant such as a phosphorus-based compound or a halogen-based compound to a woven or knitted fabric is generally used as artificial leather or synthetic leather. The method of sticking to the backside of the leather is used, but especially in the case of artificial leather based on non-woven fabric, by sticking a flame-retardant sheet based on woven fabric or knitted fabric, the high-class texture and sensitivity unique to non-woven fabric Will be damaged.

In the case of the addition method in which the flame retardant is kneaded into the thermoplastic polymer, the specific method generally used is
In this method, a flame retardant containing a phosphorus-based compound or a halogen-based compound as an active ingredient is kneaded into a molding material such as polyethylene, polypropylene, a polyethylene-polypropylene copolymer, or polystyrene to impart a flame-retardant effect. On the other hand, kneading the flame retardant into a polyamide-based polymer, a polyester-based polymer or the like has a restriction on the setting of the spinning temperature, the selection of the polymer and the flame retardant from the viewpoint of the stability of the flame-retardant and the polymer at the melt spinning temperature. , There was a problem with productivity.

In particular, in the case of the method of kneading the above flame retardant into fibers, the fiber physical properties are extremely deteriorated due to the relationship between the particle size of the flame retardant fine particles and the fiber cross-sectional area, and those which can be used practically are obtained. Absent. Further, even when a flame-retardant organic substance or the like is dispersed without deteriorating the physical properties of the fiber, in the case of the sea-island structured fiber, the flame-retardant organic substance used in the sea component removing step which is usually used in the case of ultrafineness In many cases, the target flame retardancy level could not be achieved due to the substance falling out. Further, a flame retardant containing a halogen-based compound as an active ingredient can give excellent flame retardant performance, but on the other hand, there is a problem that a substance harmful to the human body is generated during combustion. Therefore,
The use of halogen-containing compounds is not preferable for applications such as seats for vehicles.

As a method of solving these problems and imparting flame retardancy to the ultrafine fibers, there is a method of using an organic phosphorus component copolymer resin. As the organic phosphorus component copolymer resin, a copolymer resin to cellulose, polyester, phenol and the like is known. For example, JP-A-51-8239.
No. 2, JP-A-55-7888, JP-B-55-
Known organic phosphorus component copolymerized polyesters such as those described in Japanese Patent No. 41610 can be used. However, these inventions relate to the flame-retardant polyester itself, do not mention the flame-retardant property when imparting an elastic polymer to those obtained by processing them into ultrafine fibers, and further dyeing them. When the carbon black was originally deposited to obtain a dark color, the flame retardancy was obstructed by the carbon black, and the coping method was not mentioned.

Next, a conventional technique for depositing fibers or polymer elastics with carbon black in order to obtain a dark colored product made of artificial leather will be described. In order to obtain a dark color, the method of depositing the ultrafine fibers themselves with carbon black is a commonly used method, but carbon black itself is flammable and burns as the amount added increases to increase the blackness. The property is improved. Therefore, in order to obtain a leather-like sheet substrate having flame retardancy, there is a limit to the amount added,
For example, there is a problem that dyeing products with high blackness cannot be obtained, or even if the amount of dye used is increased, dyeing friction fastness is deteriorated and flame retardancy is reduced. It was

On the other hand, in order to obtain a dark-colored product, a method in which carbon black is kneaded into a polymeric elastic body is generally used. However, since carbon black is easily flammable as described above, it becomes flame-retardant. It is expected that the required amount of added flame retardant will inevitably increase. Further, since a flame retardant such as a phosphorus flame retardant or a metal hydroxide is generally a white powder in many cases, it becomes a factor that hinders the effect of the added carbon black. In this case, in order to obtain a dark-colored product having flame retardancy, the flame retardant added to the elastic polymer, the fiber and / or
Alternatively, it is necessary to adjust the amount of carbon black added to the elastic polymer within a certain suitable range.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a halogen-free, flame-retardant leather-like sheet base material having excellent durability, which is dyed in a deep color. It is to provide a suitable leather-like sheet substrate when used.

[0012]

[Means for Solving the Problems] In order to obtain a leather-like sheet substrate that has flame retardancy and is used for dyeing in a particularly dark color, as a result of diligent studies on carbon black used as a raw material and flame retardant, The present invention has been completed by finding out that both objects can be achieved by stacking a layer that attaches importance to black dyeing and a layer that attaches importance to flame retardancy.

That is, the present invention has the following layers (A) and (B) (A) of 0.5 decitex or less, and 1.5 parts by weight or more based on 100 parts by weight of the resin component constituting the ultrafine fibers. Entangled non-woven fabric consisting of ultrafine fibers (a) sown with carbon black and a layer made of a polymer elastic material contained therein, (B) comprising 0.5 decitex or less and comprising ultrafine fibers 1.5 parts by weight per 100 parts by weight of the resin component
A layer composed of an entangled nonwoven fabric composed of ultrafine fibers (b), which is or is not originally dyed with less than 1 part by weight of carbon black, and a polymer elastic body contained therein;
However, the stacking weight ratio (A) / (B) = 10/90 to 90 /
In a leather-like sheet substrate laminated in the range of 10, the ultrafine fibers (a) and (b) respectively constituting the (A) layer and the (B) layer are composed of an organic phosphorus component copolymerized polyester A flame-retardant leather-like sheet substrate, characterized in that the elastic body contains aluminum hydroxide.

Further, the ratio of the weight part (Ca) of the carbon black on which the ultrafine fiber (a) is deposited and the weight part (Cb) of the carbon black on which the ultrafine fiber (b) is deposited is Cb / Ca.
≦ 0.5, further, the phosphorus atom concentration in the organic phosphorus component copolymerized polyester constituting the ultrafine fibers (a) and (b) is 4000 ppm or more, and the polymeric elastomer contains aluminum hydroxide. Polymer elastic body (C) 10
It relates to a flame-retardant leather-like sheet substrate which is 10 to 200 parts by weight relative to 0 parts by weight. The present invention relates to a suede-like artificial leather using these bases or a silver-like artificial leather, and relates to a vehicle seat in which such artificial leather is used as an upholstery material.

Further, in the present invention, when the flame-retardant leather-like sheet substrate is produced, the polyester containing an organic phosphorus component in the steps of the following steps is used as an ultrafine fiber component,
The carbon black content of the ultrafine fibers is the ultrafine fiber component 1
1.5 parts by weight or more of ultrafine fiber-generating fiber (a ') per 100 parts by weight, and ultrafine fiber generating fiber having a carbon black content of less than 1.5 parts by weight relative to 100 parts by weight of the resin component. The step of producing (b '), the ultrafine fiber generating fiber (a') is added to the web (W
a ′) and the ultrafine fiber-generating fiber (b ′) as the web (W
b '), and then laminating (Wa') and (Wb ') and entangled and integrated to produce a non-woven fabric, a process of applying a polymeric elastic body containing aluminum hydroxide to the non-woven fabric, 0.5 for the fiber-forming fibers (a ') and (b')
The method for producing a flame-retardant leather-like sheet substrate is characterized in that the step of converting into ultrafine fibers (a) and (b) having less than decitex is performed in the order of or.

In the present invention, when the flame-retardant leather-like sheet substrate is manufactured, the polyester containing an organic phosphorus component described in the following steps is used as an ultrafine fiber component,
The carbon black content of the ultrafine fibers is the ultrafine fiber component 1
A nonwoven fabric is produced by using 1.5 parts by weight or more of ultrafine fiber-generating fibers (a ') per 100 parts by weight, and the carbon black content of the ultrafine fibers is 1. Ultrafine fiber generation type fiber (b ') of less than 5 parts by weight
A step of producing a non-woven fabric using the above, a step of applying a polymeric elastic body containing aluminum hydroxide to each non-woven fabric, and 0.5% of the ultrafine fiber-generating fibers (a ′) and (b ′).
Converting the ultrafine fibers (a) and (b) below decitex to produce respective base layers, and laminating the base layer comprising the ultrafine fibers (a) and the base layer comprising the ultrafine fibers (b). A method for producing a flame-retardant leather-like sheet substrate, which is characterized in that the steps are performed in the order or.

The present invention will be described in detail below. The ultrafine fibers of 0.5 decitex or less used in the present invention are produced by a conventionally known method. For example, at least one component is composed of at least two types of polymers having low compatibility, at least one type of polymer is an island component in the cross section, and at least one type of polymer other than that is a sea component (Usually, sea component polymer) is obtained by dissolving or decomposing and removing it, or a laminated type ultrafine fiber generating fiber having a cross-sectional shape in which two or more incompatible polymers are joined is mechanically or chemically There is a method of obtaining by peeling at the interface of two components by treatment. Furthermore, there is a method of directly producing ultrafine fibers such as melt blown. In order to adjust the single fiber fineness of the resulting ultrafine fibers and / or the ultrafine fibers constituting the ultrafine fiber bundle to 0.5 decitex or less, particularly 0.2 decitex or less, it is preferable to use a laminated type ultrafine fiber generating fiber. It is advantageous in terms of process to use ultrafine fiber-generating fibers having a sea-island structure in fiber section.

It is essential for the fibers constituting the present invention that the average single fiber fineness is 0.5 dtex or less in order to obtain a soft texture and a natural leather-like fullness. That is, when it exceeds 0.5 decitex, the texture and fullness of the obtained leather-like sheet substrate tends to be poor,
Particularly when the suede-like artificial leather is used, the feeling of fuzz and the lighting effect tend to be poor.

Polyester is preferably used as the island component resin constituting the ultrafine fiber-generating fiber, and polyester resin obtained by copolymerizing an organic phosphorus component is used. Here, the method for producing the organophosphorus component copolymerized polyester is not particularly limited, but for example, a method of adding an organophosphorus compound in the transesterification reaction by a transesterification method of a dicarboxylic acid diester and a diol, a polycondensation reaction before or a reaction There is a method of adding an organic phosphorus compound in the initial stage of. Further, also in the case of the esterification method of a dicarboxylic acid and a diol, a method of adding an organic phosphorus compound in any esterification reaction stage can be adopted. As the organic phosphorus compound used in the reaction, known phosphorus atom-containing compounds such as oxaphospholane, phosphinic acid derivatives, and phosphaphenanthrene derivatives as mentioned in the above publications can be used. As the base polyester, known polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and modified polymers thereof, mixed polymers, copolymers and the like can be used.

When the organic phosphorus component copolymerized polyester is used, since the phosphorus component is copolymerized, that is, bonded to the polymer by a covalent bond, the flame retardant is removed during spinning and in the subsequent steps of manufacturing the leather-like sheet substrate. The trouble such as does not occur. In addition, it is possible to avoid the use of halogen-containing compounds, which have been avoided due to recent environmental circumstances. At this time, the organophosphorus component copolyester is preferably a resin that exhibits sufficient fiber physical properties such as strength and has a larger melt viscosity than the sea component polymer under spinning conditions and a large surface tension. It is preferably a spinnable resin. For example, orifice diameter: 2 mmφ, load: 325
melt flow rate at spinning temperature measured in g of 5
A resin having a fiber strength of 1.0 to 5.0 g / decitex at -50 g / 10 minutes is preferable.

The phosphorus atom concentration in the organic phosphorus component copolymerized polyester is preferably 4000 ppm or more. If it is less than 4000 ppm, it is difficult to obtain satisfactory flame retardancy when using a leather-like sheet substrate. Further, the phosphorus atom concentration is more preferably increased from the viewpoint of flame retardancy as the amount of carbon black used for fiber fiber deposition is increased. For example, the weight of carbon black is 2 with respect to 100 parts by weight of the resin component constituting the ultrafine fibers. 6 for parts by weight
In case of 000ppm or more and 3 parts by weight, 8000pp
It is preferably m or more. Also, the phosphorus atom concentration is
From the viewpoint of productivity, it is preferably 20,000 ppm or less, and when it exceeds 20,000 ppm, the viscosity of the resin tends to decrease, and the stability of the sea-island structure fiber tends to decrease.

The fibers constituting the present invention are ultrafine fibers (a) which are pre-deposited with 1.5 parts by weight or more of carbon black with respect to 100 parts by weight of the organic phosphorus component copolymerized polyester resin component which constitutes the ultrafine fibers. ) And 2 of the ultrafine fibers (b) which have been rawly dyed with less than 1.5 parts by weight of carbon black.
There are types.

When the ultrafine fibers (a) are processed into, for example, suede-like artificial leather, in order to develop a deep color feeling on the surface,
Even when processed into silver-tone artificial leather, if a thin face-forming film is applied to express natural creases, the underlying color is transparent, so a color with a density that matches the face-forming color is required. In order to further approximate the appearance of natural leather, it is necessary to make the cut cross-section part dark. And to satisfy them, the amount of carbon black used is 1.5.
It is essential that the amount is at least parts by weight. From the viewpoint of spinnability, the weight of carbon black added is preferably 8 parts by weight or less. Even if the amount exceeds 8 parts by weight, the flame retardance can be satisfied by increasing the phosphorus atom concentration and also increasing the amount of the flame retardant used in the impregnated polymer elastic body, but the spinnability tends to decrease. is there.

On the other hand, the ultrafine fibers (b) have improved flame retardancy,
Alternatively, from the viewpoint of improving the fastness of the back surface and achieving an appearance in which the surface is a dark color and the back surface is a light color like natural leather, it is essential that the amount is less than 1.5 parts by weight. It is preferable that the ratio of the part by weight of carbon black (Ca) on which (a) is deposited and the part by weight of carbon black (Cb) on which ultrafine fibers (b) are deposited be Cb / Ca ≦ 0.5. If it is less than 1.5 parts by weight, it is sufficient to make the leather-like sheet substrate of the present invention flame-retardant together with the flame-retardant property of the polymer elastic body, but a higher flame-retardant level is achieved. In order to achieve a natural leather-like appearance, in particular, a color gradient as described above, a smaller amount of carbon black is preferable, and 1 part by weight or less is more preferable. The ratio of carbon black added to the ultrafine fibers (a) and (b) is also preferably Cb / Ca ≦ 0.5 and more preferably Cb / Ca ≦ 0.4 for the same reason.

On the other hand, as the sea component polymer, the island component polymer has a different solubility or degradability in a solvent or a decomposing agent (greater solubility or degradability than the island component polymer), and compatibility with the island component polymer. Is a small resin,
For example, at least one polymer selected from polymers such as polyethylene, polystyrene, polyethylene-propylene copolymer, and modified polyester obtained by copolymerizing sodium sulfoisophthalate. For example, polystyrene and polyethylene can be easily extracted with toluene and trichlene, and modified polyester such as sodium sulfoisophthalate copolymerized polyethylene terephthalate can be decomposed and removed with alkali. The sea-island structure fibers can be converted into ultrafine fiber bundles by extracting or decomposing and removing sea components from the sea-island structure fibers. In the present invention, the sea-island structured fiber may have a sea component divided into a plurality of island components in the fiber cross-section, and for example, the sea component and the island component may each be a layer and may be in a laminated state. Any fiber may be used. The island components may be continuously connected in the fiber length direction or may be discontinuous.

Further, the number of islands in the fiber cross section of the sea-island structure fiber is not particularly specified, but it is necessary to set the single fiber fineness to be 0.5 decitex or less after conversion into an ultrafine fiber bundle. Examples of the method for producing the sea-island structured fiber used in the present invention include various melt spinning methods (chip blending method, needle pipe method, laminating method, etc.). When the fiber used in the present invention is a sea-island structure fiber,
The weight ratio of the sea component and the island component constituting the fiber is preferably in the range of 8: 2 to 2: 8. Sea component weight ratio is 8
When it exceeds the above range, the physical properties of the nonwoven fabric tend to be deteriorated due to an increase in the amount of extracted components. In addition, when the weight ratio of sea components is less than 2, the amount of extracted components decreases,
The texture and fullness of the obtained leather-like sheet substrate tends to be deteriorated.

In the present invention, the thickness of the ultrafine fibers constituting the ultrafine fiber bundle formed after removing the sea component polymer from the sea-island structure fiber is 0.5 decitex or less from the viewpoint of appearance and texture. Is essential as described above, and a range of 0.001 to 0.2 decitex is particularly preferable. In addition to the above-mentioned organic phosphorus component copolymer polyester, the island component of the fiber may be added with a coloring agent such as a dye or a pigment and various stabilizers, etc., within a range that does not impair the effects of the present invention. .

In the present invention, it is essential to include a flame retardant in the elastic polymer. Examples of the elastic polymer include at least one type of polymer diol selected from diols having an average molecular weight of 500 to 3000, such as polyester diols, polyether diols, polycarbonate diols, and composite diols such as polyester polyether diols, and 4 Aromatic compounds such as 4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate,
A predetermined mole of at least one kind of diisocyanate selected from alicyclic and aliphatic diisocyanates and at least one kind of low molecular weight compound having two or more active hydrogen atoms such as ethylene glycol and isophoronediamine. Polyurethanes obtained by reacting in a ratio and modified products thereof, polyester elastomers,
Polymer elastic materials such as hydrogenated products of styrene-isoprene block copolymers and acrylic resins are also included. A polymer composition obtained by mixing these may also be used. However, the above-mentioned polyurethane is preferably used because of its flexibility, elastic recovery property, porous polymer elastic body forming property, durability and the like.

As the flame retardant to be dispersed in the polymer elastic material, known flame retardants generally used for resins, such as phosphorus-based or nitrogen-based organic flame retardants, metal hydroxide or red phosphorus, Although a silicon-based inorganic compound or the like is considered, it does not accelerate the deterioration of the polymer elastic body and the ultrafine fibers, and in the manufacturing process of the present invention, it is substantially more than the treatment liquid in the coagulation bath or the ultrafine fiber conversion process. It is required not to dissolve or decompose. In addition to these conditions, a leather-like sheet substrate is prepared by dispersing it in a polymer elastic body and combining it with the ultrafine fibers made of the above-mentioned organic phosphorus component copolyester. As a result, it was found that aluminum hydroxide, which is one kind of metal hydroxide, is the most suitable. Here, the content of aluminum hydroxide is preferably 10 to 200 parts by weight, and more preferably 30 parts by weight, based on 100 parts by weight of the polymer elastic body.
~ 100 parts by weight. It is preferable to increase the amount of aluminum hydroxide used as the amount of carbon black used as the raw material for the fibers constituting the present invention increases, from the viewpoint of further improving flame retardancy.

When the amount of aluminum hydroxide is less than 10 parts by weight, it is difficult to obtain sufficient flame retardancy when used as a leather-like sheet substrate, and when it exceeds 200 parts by weight, the polymer elastic body can sufficiently retain aluminum hydroxide. Is difficult to obtain, and the texture of the obtained leather-like sheet substrate tends to be hard, which is not preferable. The particle size of the aluminum hydroxide used is within the common sense and is not particularly limited, but in consideration of dispersion stability in the impregnating liquid and flame retardant effect, the average particle size is 2 μm or less. In particular, aluminum hydroxide fine particles of 1 μm or less are preferable. The aluminum hydroxide particles may be subjected to various treatments for improving performance such as moisture resistance, heat resistance, water resistance, and acid resistance, if necessary.

Further, carbon black may be added to the elastic polymer for the purpose of improving the deep color feeling of the obtained leather-like sheet substrate. In particular, when processing to a high density color such as black, it is preferable to add it. In this case, the addition amount of carbon black to be used is 100
It is 7 parts by weight or less, and preferably 5 parts by weight or less with respect to parts by weight. Thus, when carbon black is added to the polymer elastic body, it is preferable that the amount of aluminum hydroxide used is increased within the range of 10 to 200 parts by weight from the viewpoint of flame retardancy. When 3 parts by weight of black is used, the addition amount of aluminum hydroxide is preferably 25 parts by weight or more, and more preferably 40 parts by weight or more in order to stably obtain the flame retardant effect.

Next, the manufacturing method of the present invention will be described. The present invention can be roughly classified into two methods. <Manufacturing Method 1> Steps of the following steps using an organic phosphorus component-containing polyester as an ultrafine fiber component,
The carbon black content of the ultrafine fibers is the ultrafine fiber component 1
1.5 parts by weight or more of ultrafine fiber-generating fiber (a ') per 100 parts by weight, and ultrafine fiber generating fiber having a carbon black content of less than 1.5 parts by weight relative to 100 parts by weight of the resin component. The step of producing (b '), the ultrafine fiber generating fiber (a') is added to the web (W
a ′) and the ultrafine fiber-generating fiber (b ′) as the web (W
b '), and then laminating (Wa') and (Wb ') and entangled and integrated to produce a non-woven fabric, a process of applying a polymeric elastic body containing aluminum hydroxide to the non-woven fabric, 0.5 for the fiber-forming fibers (a ') and (b')
A method for producing a flame-retardant leather-like sheet substrate, which comprises performing the step of converting ultrafine fibers (a) and (b) having a decitex or less in the order of or.

<Production Method 2> Steps of the Following Steps Using an organic phosphorus component-containing polyester as an ultrafine fiber component,
The carbon black content of the ultrafine fibers is the ultrafine fiber component 1
A nonwoven fabric is produced by using 1.5 parts by weight or more of ultrafine fiber-generating fibers (a ') per 100 parts by weight, and the carbon black content of the ultrafine fibers is 1. Ultrafine fiber generation type fiber (b ') of less than 5 parts by weight
A step of producing a non-woven fabric using the above, a step of applying a polymeric elastic body containing aluminum hydroxide to each non-woven fabric, and 0.5% of the ultrafine fiber-generating fibers (a ′) and (b ′).
A step of converting the ultrafine fibers (a) and (b) having a decitex or less to produce respective base layers, a step of laminating a base layer made of the ultrafine fibers (a) and a base layer made of the ultrafine fibers (b), A method for producing a flame-retardant leather-like sheet substrate, which is carried out in the order of or.

First, the manufacturing method 1 will be described. <Production of Ultrafine Fiber Generating Fiber> First, the ultrafine fiber generating fiber (a ′) and (b ′) using the organic phosphorus component copolymerized polyester as the island component is spun by the known spinning method as described above. In the case of melt spinning, for example, the carbon black used for the primary coating may be dry blended with resin pellets as a spinning raw material, or a master batch based on a raw material resin or another resin in a range not impairing spinnability is prepared. , It may be blended. afterwards,
Staples are manufactured through processes such as stretching, crimping, and cutting. As a fiber staple, the fineness is 1.0 to 10.0
Decitex is preferable in terms of ensuring good card passage, and more preferably 3.0 to 6.0 decitex. Next, the fiber staple is defibrated with a card, a web is formed through a web bar, and the obtained webs are laminated to have a desired weight and thickness. that time,
In the production method 1 of the present invention, a web (W
a ') and (Wb') are prepared, respectively, and these are superposed on each other in a desired weight and thickness. The superposition method is as follows: (Wa ') is used as the upper layer of the leather-like sheet substrate.
b ') is generally laminated in two layers so as to serve as the lower layer of the leather-like sheet substrate. (Wa'), (Wb '),
(Wa ') or (Wb'), (Wa '), (W
b ′) as a three-layer sandwich structure, the laminated webs are entangled, impregnated with a polymeric elastic material, and sliced at any timing after the ultrafine fiber-generating fibers are made into ultrafine fibers. You may take two.

The layering ratio is from the layer (A) consisting of ultrafine fibers (a) containing 1.5 parts by weight or more of carbon black to the ultrafine fibers (b) containing less than 1.5 parts by weight. The weight ratio of the layer (B) is (A) / (B) =
10/90 to 90/10 is essential, and 15
It is more preferably / 85 to 60/40. (A)
When it is less than 10, fibers with different carbon black deposits are likely to appear near the surface when the entangled nonwoven fabric is formed, which leads to a deterioration in appearance particularly when applied to suede-like artificial leather. On the other hand, when (A) exceeds 90, the flame retardance level tends to decrease, which is not preferable.

Then, a woven material is subjected to an entanglement treatment by a known method, for example, a needle punching method or a high-pressure hydroentanglement treatment method or the like, or a knitted or woven fabric on which the staples are superposed is subjected to a water current or the like 3 Dimensionally entangled to form a composite nonwoven fabric. The non-woven fabric is preferably formed into a form suitable for the purpose in consideration of the thickness of the artificial leather, etc., but the basis weight is 200 to 1500 g / m ² , and the thickness is 1 to 1.
The range of 10 mm is preferable from the viewpoint of easy handling during the process. If necessary, a non-woven fabric produced by the above method may be provided with a polyvinyl alcohol-based sizing agent or the surface of the constituent fibers may be melted to bond the constituent fibers of the non-woven fabric to temporarily fix the non-woven fabric. You may go. By performing this treatment, it is possible to prevent the structural destruction of the nonwoven fabric due to tension or the like in the subsequent step of impregnation of the polymer elastic body solution, particularly when the surface of the constituent fibers is melted, The surface smoothness of the obtained leather-like sheet substrate can be improved.

<Applying Polymer Elastic Material> When applying the polymer elastic material to the ultrafine fiber-generating fiber-entangled nonwoven fabric, the nonwoven fabric is immersed in a liquid composition containing the polymer elastic material. After that, the non-woven fabric is immersed in a coagulation bath to solidify the polymer elastic body to form a porous polymer elastic body, or the non-woven fabric is immersed in a polymer elastic body emulsion liquid and the emulsion is heated to gel. The method of making it etc. are used. The above-mentioned flame retardant, that is, aluminum hydroxide, must be dispersed in advance both when using a liquid composition containing a polymer elastic body and when using a polymer elastic body emulsion. In order to improve the dispersion stability of aluminum hydroxide, a liquid substance containing such a polymer elastic body and a flame retardant may be mixed with additives such as a coagulation regulator and a dispersant, if necessary. In addition, a stabilizer such as a deterioration preventing agent for the resin, a coloring agent such as carbon black, a dye, a pigment or the like may be added within a range not impairing the gist of the present invention.

<Ultra-fine fiber formation> The ultra-fine fiber-generating fiber is a non-solvent for the island component polymer or only one component constituting the fiber, and is high when high polymer elasticity is contained. It is also a non-solvent for molecular elastic bodies, and it is converted to ultrafine fiber bundles or ultrafine fibers by treating the sea component polymer or other components constituting the fiber with a solvent or degrading agent. . In this step, even when the elastic polymer is contained in advance, the solvent or the decomposing agent is a non-solvent or a non-decomposing agent for the elastic polymer, so that most of the aluminum hydroxide particles are It remains in the elastic body so that it does not easily fall off.

The ratio of the elastic polymer to the leather-like sheet substrate after the sea component is removed is 10% or more, preferably 30 to 50% by weight as a solid content. If the elastic body ratio is less than 10%, it is difficult to form a dense porous polymer elastic body, and the aluminum hydroxide particles tend to fall off after the generation of ultrafine fibers, and the mechanical strength of the obtained leather-like sheet substrate is Tends to decline.

In the flame-retardant leather-like sheet substrate of the present invention obtained as described above, the step of impregnating the polymer elastic body and the step of forming ultrafine fibers may be performed in this order or vice versa. It doesn't matter.

Next, the manufacturing method 2 will be described. <Manufacture of Ultrafine Fiber Generating Fiber> Also in the manufacturing method 2, the same method as the manufacturing method 1 is used for the spinning method of the ultrafine fiber generating fiber. In the production method 2, only a web (Wb) made of only the web (Wa) made of the ultrafine fiber-generating fiber (a ′) and a web (Wb) made of the ultrafine fiber-generating fiber (b ′) having different carbon black deposits are used. Is used alone in the next step. Then, the webs composed of the web (Wa) and the web (Wb) alone and having a desired weight and thickness are three-dimensionally entangled in the same manner as in the production method 1 to form nonwoven fabrics. Note that the process performed as necessary can be performed in the same manner as in the production method 1.

<Impregnation of High Polymer Elastic Body> The high molecular elastic body is impregnated by the same method as the production method 1.

<Ultra-fine fiber formation> The ultra-fine fiber formation is also carried out by the same method as the production method 1. Also, the order of the step of impregnating the polymer elastic body and the step of forming the ultrafine fibers may be the same as in the manufacturing method 1, or may be the reverse order.

<Lamination> In the production method 2 of the present invention, it is obtained by changing the amount of carbon black deposited by the same steps of production of ultrafine fiber generating fiber, impregnation of polymer elasticity, and ultrafine fiber formation. It is characterized in that two kinds of layers, that is, a layer made of the ultrafine fibers (a) and a layer made of the ultrafine fibers (b) are adhered by using an adhesive resin to be laminated.

The adhesive resin is not particularly limited,
Polymers of the same kind as the polymer constituting the polymeric elastic body are preferably used. For example, when polyurethane is used as the polymeric elastic body contained in the nonwoven fabric, polyurethane resin is also preferably used as the adhesive resin. The method of applying the resin used for adhesion is not particularly limited, but a method of applying the adhesive resin by dissolving it in a solvent,
There is a hot melt method and the like. Regarding the application form of the adhesive resin, it can be present continuously or discontinuously, but the adhesive resin is present discontinuously from the viewpoint of the feel and flexibility of the obtained leather-like sheet substrate. The method using a gravure roll is more preferably used. In this case, it is preferably carried out with 50 to 200 mesh, and the coating amount of the adhesive resin is preferably about 1 to 30 g / m ² in terms of solid content. However, even when it is continuously applied to the entire surface of the adhesive, the texture and flexibility can be improved by a method such as thinning the thickness of the porous or non-porous film to be bonded.

Thus, in the case of adhering two types of layers (A) and (B) consisting of ultrafine fibers and a polymeric elastic material, the weight ratio of each is (A) / (B) = 10 / 90- 90 /
It is essential to design so as to be 10, and more preferably 15/85 to 60/4 for the reasons described above.
The range is 0. The method of adhering two types of layers (A) and (B) consisting of ultrafine fibers and a polymer elastic body, although the number of adhering steps is increased in terms of steps, leads to complication of steps and increase in cost, but the layers Not only changing the amount of carbon black deposited on the fibers constituting (A) and layer (B), but also changing the fineness of the ultrafine fibers and the amount of aluminum hydroxide contained in the polymeric elastomer contained in each layer. It is particularly preferably used because it can have the following structures.

For example, in order to further improve the appearance, the fineness of the ultrafine fibers of the surface layer (A) is made smaller, and the ultrafine fibers of the back surface layer (B) is made thicker to secure the physical properties. For example, in order to obtain a darker color, the amount of aluminum hydroxide added to the polymeric elastic body constituting the surface layer (A) is decreased, and conversely, the amount added to the back surface layer (B) is increased to give leather. It is possible to ensure flame retardancy as a sheet base.

The flame-retardant leather-like sheet substrate thus produced is a combination of ultrafine fibers of an organic phosphorus component copolymerized polyester and a polymer elastic body holding aluminum hydroxide particles. Although it is difficult to theoretically prove that this combination is optimal, a combination of a polyester polymer containing no flame-retardant component and a porous polymer elastic body holding aluminum hydroxide particles, or
In the combination of the ultrafine fibers of the organic phosphorus component copolyester and the porous polymer elastic body not containing aluminum hydroxide, the leather-like sheet substrate obtained even if the concentration of one flame retardant component is as high as possible, It is difficult to achieve a sufficient flame retardancy level. In a composite material such as a genuine leather-like sheet substrate, it is effective to have a flame-retardant component in each constituent element, and details cannot be confirmed. However, a combustion suppressing mechanism by formation of a carbonized film of an organophosphorus compound and aluminum hydroxide. It is presumed that the combustion suppression mechanism by the endothermic effect exerts a synergistic effect by suppressing combustion at multiple points in the combustion process.

The flame-retardant leather-like sheet substrate of the present invention can be made into a suede-like artificial leather by fluffing its surface using a known method. For the purpose of the present invention, it is the main idea to fluff the surface of the layer composed of ultrafine fibers having a higher amount of carbon black deposited, but if necessary, the opposite surface may be fluffed for use. Absent. In addition, by performing the process of melting the surface of the leather-like sheet substrate with a solvent or heat and the process of fluffing in this order or the reverse order, a nubuck-like appearance with short fluff, or an intermediate appearance between suede and silver It is also possible to obtain an artificial leather having The obtained suede-like artificial leather is usually used after being dyed with a dye or the like, but since superfine fibers having different carbon black deposits are used in the surface layer and the back layer, a natural leather-like natural color is obtained. A concentration gradient of is obtained. Furthermore, in general, when obtaining a suede-like artificial leather having a dark surface, the dye used must be excessively added, and the entire layer is excessively dyed singly. However, excessively dyeing lowers the fastness to rubbing on the back surface, and, of course, excessive addition of a flammable dye tends to reduce the flame retardant effect. However, the suede-like artificial leather of the present invention may have the constituent fibers sown, so that the dye for dyeing the fibers is reduced, and it becomes possible to efficiently make only the surface portion a dark color, and the friction fastness is improved. It is possible to prevent deterioration of flame retardancy and flame retardancy.

The flame-retardant leather-like sheet substrate of the present invention forms a resin film on the surface of the substrate (hereinafter referred to as a surface-forming surface).
As a result, a silver-tone artificial leather can be obtained. As the surface-forming method, in addition to the known wet method and dry method, there is also a method of dissolving the leather-like sheet substrate surface with a solvent or the like and then smoothing the surface with embossing or the like, or imparting an uneven pattern to the surface,
It is not particularly limited. The resin used for the surface making is preferably the same type of resin as the polymer elastic body resin that constitutes the leather-like sheet substrate. For example, when a polyurethane resin is used for the polymer elastic body, the polyurethane resin is Used. For the thickness of the resin layer to be surfaced,
Although not particularly limited, it is often designed to be about 10 to 300 microns. Particularly when the surface-forming resin layer is thick, for example, exceeding 50 microns, it is preferable to add a known flame retardant, and to add one or more flame retardants selected from phosphorus-based, metal hydroxide-based, etc. Is more preferable. The addition amount in this case is not particularly limited, but from the viewpoint of the process stability of the surface-forming and the strength of the surface-forming film, the flame retardant 0 to 10 relative to 100 parts by weight of the surface-forming resin.
It is often used in the range of 0 parts by weight.

The suede-like or silver-finished artificial leather thus obtained is required to have flame retardancy in vehicle seats, particularly automobile seats, railway car seats, airplane seats, marine seats, etc. It is suitable for use as an upholstery material for seats. The seat upholstery material may be used by adhering a reinforcing material such as a woven or knitted fabric to the back surface, but the artificial leather obtained from the flame-retardant leather-like sheet base material of the present invention is also laminated with the reinforcing material in the same manner. You can In this case, it is needless to say that the reinforcing material is also preferably flame-retarded, and from the point of the present invention, a reinforcing material that is flame-retarded by a non-halogen flame-retardant method is preferable, but it is reinforced. The presence or absence of flame retardancy of the material itself and the flame retardant technique are not particularly limited. The application is not limited to the above-mentioned applications, and other uses include general interior items such as sofa upholstery, sundries such as clothing, shoes, bags, and accessory cases, as well as a wide range of applications. it can.

[0052]

EXAMPLES The present invention will now be specifically described with reference to Examples.
The present invention is not limited to these examples. Parts and% in the examples relate to weight unless otherwise specified. The thickness of the fiber and the average particle diameter of aluminum hydroxide referred to in the present invention were determined by the following methods. The flame retardancy evaluation in the examples was measured according to the following method.

[Thickness of fiber]: 500 to under electron microscope
Converted from measured fiber diameter observed at a magnification of about 2000 times [Average particle size of metal hydroxide]: Measured by electron microscope observation [Flame retardancy test method]: JIS D1201 Flammability test method for organic materials for automobile interior According to the combustion test, flammability: Burning rate exceeds 100 mm / min Slow flammability: Burning rate is 100 mm / min or less Self-extinguishing: Classified as extinguished within 50 mm and 60 seconds from the marked line . Further, the phosphorus atom concentration in the sheets in the examples is determined by ICP emission spectrometer IRI manufactured by Jarrell Ash Co.
It was measured by SAP.

[Color Density]: A suede-like artificial leather in which the surface of a leather-like sheet substrate was buffed and fluffed was dyed under the following conditions, and the appearance was selected from 10 people involved in the manufacture of artificial leather. The deep color feeling and the color depth were comparatively evaluated. ◯: Excellent dark color and depth, Δ: Lack of dark color, ×: Dark color and insufficient depth Dyeing conditions Dyeing: Jet dyeing machine, 120 ° C. × 40 minutes, Dye: Miketon Polyester Blu
e FBL 3% owf [Hand feeling]: Using the sample evaluated for color density, 10 persons involved in the production of artificial leather were selected and evaluated as the highest in the following evaluations. ○: good, ×: bad

Spinning Examples 1 to 6 Using a known polyester polymerization method, a phosphorus-based flame retardant M-
Ester (manufactured by Sanko Co., Ltd., molecular weight 434, phosphorus content 7w
t%) during the polymerization to add phosphorus atom concentration of 7,000 pp
m and 12000 ppm of two phosphorus-based flame retardant copolyesters were obtained. As a control, an unmodified polyester polymerized without adding a phosphorus-based flame retardant was also obtained. Phosphorus flame-retardant copolyester with phosphorus atom concentration of 7000 ppm 1
0 parts by weight of carbon black powder to 100 parts by weight, 100 parts by weight of phosphorus-based flame-retardant copolyester having a phosphorus atom concentration of 12000 ppm, 2,3.5 parts by weight of carbon black powder, phosphorus The unmodified polyester polymerized without adding the flame retardant was dry blended in an amount of 1 and 3.5 parts by weight, respectively, and then a uniaxial kneader was used to obtain pellets of carbon adhering polyester.

Sea-island type composite fibers (sea component / island component = 35/65, number of islands 16) using the polyester as an island component and high-fluidity low-density polyethylene as a sea component were obtained by melt spinning. It was stretched 2.5 times in warm water at 70 ° C., a fiber oil was applied thereto, mechanically crimped and dried, and then cut into 51 mm to obtain 5.0 decitex staple.

[0057]

[Table 1]

[0058] laminated after forming the web of Example 1 spun Example 4, respectively and the resulting staple spinning Example 2 in cross wrapping method basis weight ^{195g / m 2, 455g / m} 2, then in accordance with the alternately from both sides About 2,500 P / cm ² needle punching, further heating, and pressing with a calendar roll produced an entangled nonwoven fabric with a smooth surface. The unit weight of this entangled nonwoven fabric is 1200 g / m ² , and the apparent density is 0.48 g / cm 2.
It was ³ . A 100% dimethylformamide (hereinafter abbreviated as DMF) solution of polyurethane having a solid content of 14% mainly composed of polycarbonate polyurethane is added to the entangled nonwoven fabric.
Impregnation with an impregnating solution (polyurethane / aluminum hydroxide = 100: 50) prepared by adding 17.5 parts by weight of a solution in which 40% of aluminum hydroxide having an average particle diameter of 1 μm is dispersed in DMF with respect to parts by weight. Then, the impregnated non-woven fabric is dipped in a DMF / water mixed solution and wet-coagulated, and then the sea component in the sea-island type composite fiber is eluted and removed in hot toluene to express ultrafine fibers, and flame retardant. Thickness with performance 1.
A 3 mm leather-like sheet substrate was obtained. The average fineness of the ultrafine fibers was 0.2 decitex. The weight ratio of fiber to polyurethane in the leather-like sheet substrate was about 79:21. Further, when the fiber cross section of the obtained leather-like sheet substrate was observed with a microscope, it was confirmed that many aluminum hydroxide particles were present inside the porous polymer elastic body. Table 2 shows the flame retardancy of the obtained leather-like sheet substrate, and the buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardancy, color density, and texture of the dyed product were evaluated. .

Comparative Example 1 Using only the staples obtained in Spinning Example 4, areal weight 6
A leather-like sheet substrate having a thickness of 1.3 mm was obtained in the same manner as in Example 1 except that a web of 50 g / m ² was formed.
The average fineness of the ultrafine fibers was 0.2 decitex. The weight ratio of fiber to polyurethane in the leather-like sheet substrate was about 79:21. Further, when the fiber cross section of the obtained leather-like sheet substrate was observed with a microscope, it was confirmed that many aluminum hydroxide particles were present inside the porous polymer elastic body. Table 2 shows the flame retardancy of the obtained leather-like sheet substrate, and the buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardancy, color density, and texture of the dyed product were evaluated. .

[0060] Using the staple obtained in Example 2 spun Example 3 and spun Example 1, except that laminated after forming the web of ^{390g / m 2, 260g / m} 2 basis weight, respectively, as in Example 1 To obtain an entangled nonwoven fabric. To this entangled non-woven fabric, 7 parts by weight of 40% by weight of aluminum hydroxide having an average particle size of 1 μm dispersed in DMF with respect to 100 parts by weight of a DMF solution of polyurethane having a solid content of 14% mainly composed of polycarbonate-based polyurethane Part is added to prepare an impregnating solution (polyurethane / aluminum hydroxide = 100: 20), and the impregnated non-woven fabric is dipped in a DMF / water mixed solution for wet coagulation and then in hot toluene. The sea component in the sea-island type composite fiber was eluted and removed to express an ultrafine fiber bundle, and a 1.3 mm thick leather-like sheet substrate having flame retardant performance was obtained. The average fineness of the ultrafine fibers was 0.2 decitex. The weight ratio of fiber to polyurethane in the leather-like sheet substrate was about 82:18. Further, when the fiber cross section of the obtained leather-like sheet substrate was observed with a microscope, it was confirmed that many aluminum hydroxide particles were present inside the porous polymer elastic body. Flame retardancy of the obtained leather-like sheet substrate, and buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardance of the dyed product.
Table 2 shows the results of evaluation of color density and texture.

[0061] Using the staple obtained in Comparative Example 2 spun Example 2 and spun Example 1, except that laminated after forming the web of ^{390g / m 2, 260g / m} 2 basis weight, respectively, similarly to Example 2 Thus, a leather-like sheet substrate having a thickness of 1.3 mm was obtained. The average fineness of the ultrafine fibers was 0.2 decitex. The weight ratio of fiber to polyurethane in the leather-like sheet substrate was about 82:18. Further, when the fiber cross section of the obtained leather-like sheet substrate was observed with a microscope, it was confirmed that many aluminum hydroxide particles were present inside the porous polymer elastic body. Table 2 shows the flame retardancy of the obtained leather-like sheet substrate, and the buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardancy, color density, and texture of the dyed product were evaluated. .

[0062] Using the staple obtained in Example 3 spinning Example 4 and spun Example 2, except that laminated after forming the web of ^{195g / m 2, 455g / m} 2 basis weight, respectively, as in Example 1 To obtain an entangled nonwoven fabric. A solution prepared by dispersing 40% of aluminum hydroxide having an average particle size of 1 μm in DMF in 100 parts by weight of a DMF solution of polyurethane having a solid content of 14% and mainly composed of polycarbonate polyurethane in the entangled nonwoven fabric. After impregnating an impregnating solution (polyurethane / aluminum hydroxide = 100: 50) prepared by adding 5 parts by weight, the impregnated non-woven fabric is immersed in a DMF / water mixed solution and wet-coagulated, and then heat-treated. Elute and remove the sea component in the sea-island composite fiber in toluene to express ultrafine fibers,
A 1.3 mm thick leather-like sheet substrate having flame retardant performance was obtained. The average fineness of the ultrafine fibers was 0.2 decitex. The weight ratio of fiber to polyurethane in the leather-like sheet substrate was about 79:21. Further, when the fiber cross section of the obtained leather-like sheet substrate was observed with a microscope, it was confirmed that many aluminum hydroxide particles were present inside the porous polymer elastic body. Flame retardancy of the obtained leather-like sheet substrate, and buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardance of the dyed product.
Table 2 shows the results of evaluation of color density and texture.

Comparative Example 3 Using the unmodified polyester staples obtained in Spinning Example 6 and Spinning Example 5, 195 g / m ² and 455 g, respectively.
A leather-like sheet substrate having a thickness of 1.3 mm was obtained in the same manner as in Example 4 except that the web having a basis weight of / m ² was formed and then laminated. The average fineness of the ultrafine fibers was 0.2 decitex. The weight ratio of fiber to polyurethane in the leather-like sheet substrate was about 79:21. Further, when the fiber cross section of the obtained leather-like sheet substrate was observed with a microscope, it was confirmed that many aluminum hydroxide particles were present inside the porous polymer elastic body. Table 2 shows the flame retardancy of the obtained leather-like sheet substrate, and the buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardancy, color density, and texture of the dyed product were evaluated. .

Example 4 The entangled nonwoven fabric obtained in the same manner as in Example 3 had an average particle size of 1 μm with respect to 100 parts by weight of a DMF solution of a polyurethane mainly composed of polycarbonate polyurethane and having a solid content of 14%. An impregnation solution (polyurethane / aluminum hydroxide = 100: 150) prepared by adding 52.5 parts by weight of a 40% dispersion of aluminum hydroxide in DMF was impregnated, and the impregnated non-woven fabric was mixed with DMF / 1.3mm thick leather with flame retardant performance by immersing and coagulating in a water mixture and wet-coagulating it to elute and remove sea components in sea-island composite fiber to develop ultrafine fibers Such a sheet substrate was obtained. The average fineness of the ultrafine fibers was 0.2 decitex. The weight ratio of fiber to polyurethane in the leather-like sheet substrate was about 75:25. Further, when the fiber cross section of the obtained leather-like sheet substrate was observed with a microscope, it was confirmed that many aluminum hydroxide particles were present inside the porous polymer elastic body. Table 2 shows the flame retardancy of the obtained leather-like sheet substrate, and the buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardancy, color density, and texture of the dyed product were evaluated. .

Example 5 The staple obtained in Spinning Example 4 was subjected to a cross lap method to form a web having a basis weight of 390 g / m ² and then needle-punched from both sides alternately at about 2500 P / cm ² and further heated, By pressing with a calendar roll, an entangled nonwoven fabric with a smooth surface was prepared. The unit weight of this entangled nonwoven fabric is 720 g / m ² , and the apparent density is 0.48 g / m ² .
It was cm ³ . An average particle size of 1 μm was added to 100 parts by weight of a DMF solution of polyurethane having a solid content of 14% mainly composed of polycarbonate polyurethane.
7% by weight of a solution in which 40% of aluminum hydroxide of 40% is dispersed in DMF is impregnated with an impregnating solution (polyurethane / aluminum hydroxide = 100: 20), which is then impregnated with DMF / water. After being immersed in a mixed solution and wet-solidified, the sea component in the sea-island type composite fiber is eluted and removed in hot toluene to express ultrafine fibers, and the thickness is 0.8 m.
m layers were obtained. Then, the slice was divided into two in the thickness direction to obtain a layer (A) having a thickness of 0.4 mm.

On the other hand, the staple obtained in Spinning Example 2 was formed into a web of 455 g / m ² by the cross lap method, and then alternately lapped from both sides to about 2500 P / cm ² needle punching and further heated, and then calendered. A entangled nonwoven fabric with a smooth surface was made by pressing at.
The unit weight of this entangled nonwoven fabric was 840 g / m ² , and the apparent density was 0.48 g / cm ³ . In this entangled nonwoven fabric,
Solid component mainly composed of polycarbonate polyurethane 1
An impregnation solution (polyurethane / hydroxylation solution) prepared by adding 17.5 parts by weight of a 40% dispersion of aluminum hydroxide having an average particle size of 1 μm in DMF to 100 parts by weight of a 4% polyurethane DMF solution. Aluminum = 100:
50) and then the non-woven fabric impregnated with DMF
After being immersed in a water / water mixture and wet-coagulated, the sea component in the sea-island type composite fiber is eluted and removed in hot toluene to express ultrafine fibers, and a 0.9 mm-thick layer with flame retardant performance is obtained. A layer (B) was obtained.

On the sliced surface of the layer (A) thus obtained, DM (Dimichi Seika's product, Heimlen NPU-5: polyether type polyurethane) DM
Immediately after dot-wise coating (coating amount: solid content 3 g / m 2) with a gravure roll 140 mesh using the one dissolved in F, the layers (B) were overlapped and bonded. In the obtained flame-retardant leather-like sheet substrate, the weight ratio of the layer (A) and the layer (B) was 40/45 as calculated from the basis weight. Table 2 shows the flame retardancy of the obtained leather-like sheet substrate, and the buffing of the surface of the leather-like sheet substrate into a suede-like artificial leather, and the flame retardancy, color density, and texture of the dyed product were evaluated.

[0068]

[Table 2]

Application Example 1 (Application to Artificial Leather with Silver) Polycarbonate diol, polytetramethylene glycol, polyethylene glycol, polyurethane mainly composed of polyurethane obtained by polymerization from 4,4'-dicyclohexylmethane diisocyanate, A polyurethane composition solution in which carbon black was added to adjust the color to black was applied on release paper and dried to obtain a film having a thickness of 15 μm. Then, a mixture of two-component polyurethane, a polyisocyanate curing agent, an amine catalyst, and a solvent was applied as an adhesive layer thereon in a solid content of 20 g / m ² and dried to obtain a tacky state immediately after drying. The product was superposed on the surface of the dyed product of the suede-like artificial leather obtained in Example 1 and pressed together. Then, after leaving it at 60 ° C. for 48 hours, the release paper was peeled off to obtain a silver-tone artificial leather. The obtained artificial leather with silver has a smooth and high-grade appearance and a soft texture, and was judged to be flame-retardant by the FMVSS-302 test.

Application Example 2 (Application to Seat Upholstery for Vehicles) Using the dyed suede-like artificial leather obtained in Example 1 and the silver-tone artificial leather obtained in Application Example 1, respectively. When a seat for car seats was manufactured, no problems in processing due to strength etc. occurred, and it became a seat that has a feel and appearance similar to when using natural leather and the flame retardancy required for car seats.

[0071]

Industrial Applicability The leather-like sheet substrate of the present invention is halogen-free and has excellent flame retardancy and also has extremely excellent flame retardancy durability. The leather-like sheet substrate of the present invention has a leather-like soft texture and is extremely excellent as a leather-like sheet substrate of suede-like and silver-tone artificial leather, and is suitable for automobile seats, railroad vehicle seats, aircraft seats. Suitable for applications requiring flame retardant performance, such as sofa upholstery. Then, it is particularly suitable as a material for obtaining a dark-colored product, and brings about a widening of a dyeable color range. Furthermore, the leather-like sheet substrate of the present invention has general applications other than artificial leather,
For example, it can be used as wallpaper, carpet, etc.

Continued front page    F term (reference) 4F055 AA02 AA21 BA12 CA11 EA04                       EA12 EA24 EA34 FA20 FA40                       GA02 HA04 HA22

Claims (8)

[Claims] 1. A carbon black having the following layers (A) and (B) (A) of 0.5 decitex or less, and 1.5 parts by weight or more with respect to 100 parts by weight of a resin component constituting an ultrafine fiber. Entangled nonwoven fabric made of ultrafine fibers (a) and a layer made of a polymer elastic material contained therein, (B) a resin component 100 having 0.5 decitex or less and constituting ultrafine fibers 1.5 parts by weight
A layer composed of an entangled nonwoven fabric composed of ultrafine fibers (b), which is or is not originally dyed with less than 1 part by weight of carbon black, and a polymer elastic body contained therein;
However, the stacking weight ratio (A) / (B) = 10/90 to 90 /
In a leather-like sheet substrate laminated in the range of 10, the ultrafine fibers (a) and (b) respectively constituting the (A) layer and the (B) layer are composed of an organic phosphorus component copolymerized polyester A flame-retardant leather-like sheet substrate, characterized in that the elastic body contains aluminum hydroxide. 2. The ratio of the weight part (Ca) of the carbon black on which the ultrafine fibers (a) are deposited and the weight part (Cb) of the carbon black on which the ultrafine fibers (b) are deposited is Cb / Ca ≦.
The flame-retardant leather-like sheet substrate according to claim 1, which is 0.5. 3. The phosphorus atom concentration in the organic phosphorus component copolymerized polyester constituting the ultrafine fibers (a) and (b) is 400.
The flame-retardant leather according to claim 1 or 2, wherein the content of aluminum hydroxide in the polymer elastic body is 0 ppm or more and 10 to 200 parts by weight based on 100 parts by weight of the polymer elastic body (C). Like sheet substrate. 4. A suede-like artificial leather using the substrate according to claim 1. 5. A silver-tone artificial leather using the substrate according to any one of claims 1 to 3. 6. A vehicle seat in which the artificial leather according to claim 4 or 5 is used as an upholstery material. 7. A method for producing a flame-retardant leather-like sheet substrate, wherein the following steps of polyester containing an organic phosphorus component is used as an ultrafine fiber component,
The carbon black content of the ultrafine fibers is the ultrafine fiber component 1
1.5 parts by weight or more of ultrafine fiber-generating fiber (a ') per 100 parts by weight, and ultrafine fiber generating fiber having a carbon black content of less than 1.5 parts by weight relative to 100 parts by weight of the resin component. Step of producing (b '), the ultrafine fiber generating fiber (a') is used as a web (Wa '), the ultrafine fiber generating fiber (b') is used as a web (Wb '), and then (Wa') A step of laminating (Wb ′) and entanglement-integrating to produce a nonwoven fabric, a step of applying a polymeric elastic body containing aluminum hydroxide to the nonwoven fabric, ultrafine fiber-generating fibers (a ′) and (b ′) ) To 0.5
A method for producing a flame-retardant leather-like sheet substrate, characterized in that the step of converting into ultrafine fibers (a) and (b) having less than decitex is performed in the order of or. 8. A method for producing a flame-retardant leather-like sheet substrate, the steps of the following steps using an organic phosphorus component-containing polyester as an ultrafine fiber component,
The carbon black content of the ultrafine fibers is the ultrafine fiber component 1
A nonwoven fabric is produced by using 1.5 parts by weight or more of ultrafine fiber-generating fibers (a ') per 100 parts by weight, and the carbon black content of the ultrafine fibers is 1. Ultrafine fiber generation type fiber (b ') of less than 5 parts by weight
A step of producing a non-woven fabric using the above, a step of applying a polymeric elastic body containing aluminum hydroxide to each non-woven fabric, and 0.5% of the ultrafine fiber-generating fibers (a ′) and (b ′).
Converting the ultrafine fibers (a) and (b) below decitex to produce respective base layers, and laminating the base layer comprising the ultrafine fibers (a) and the base layer comprising the ultrafine fibers (b). A method for producing a flame-retardant leather-like sheet substrate, which is carried out in the order of or.