JPS6017872B2 - Method for manufacturing leather-like sheet material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a leather-like sheet material having an appearance and feel similar to natural leather.

Today, many types of artificial leather are emerging as substitutes for natural leather.

Among these artificial leathers, conventionally, the mainstream is artificial leather consisting of three layers: a nonwoven fabric layer containing porous polyurethane elastomer inside, a woven fabric layer containing porous polyurethane elastomer inside, and a porous coating layer. However, this two-layer artificial leather had a hard texture and lacked flexibility, and was far from natural leather. Today, instead of artificial leather having a three-layer structure, it now has a two-layer structure consisting of a base layer made of non-woven fabric with a porous polyurethane elastomer inside and a porous covering layer (so-called silver surface layer) of polyurethane elastomer. This is becoming the mainstream of artificial leather. This two-layered artificial leather is considerably more supple and has a softer feel than the three-layered artificial leather. Furthermore, in this two-layer artificial leather, the fibers constituting the nonwoven fabric of the base layer are
When using ultrafine fibers or porous fibers obtained by forming two or more types of polymers into mixed paper threads or composite threads and extracting and removing at least one component from the resulting fibers, ordinary natural leather or single fibers are used. Compared to the case where single thread fibers are used, artificial leather can be obtained which is more supple and has a softer texture. Today, artificial leather, which has been made more flexible through these improvements, can be used in a variety of products such as shoes, school bags, school bags, and sports equipment by providing finishing layers on the surface of the porous coating layer to meet various requirements. It is said that it can be processed into various products. However, these two-layer artificial leathers still have a stiff feel and poor drapability compared to natural leather, so they are not suitable for clothing or interior decoration. If it were possible to produce artificial leather that is even more resilient than two-layer artificial leather, in other words, it is similar to natural leather and does not have a rubbery feel, it would be possible to use it for clothing and interior goods. Even more demand is expected in the fields of shoes, bags, sporting goods, etc., in which leather was previously used. As a result of repeated research aimed at obtaining artificial leather with For this reason, it was discovered that the appearance and texture of the leather is far from that of natural leather, leading to the present invention.

That is, the present invention consists of a nonwoven fabric formed by entangling ultrafine fibers and a porous polymer mainly composed of polyurethane elastomer, and the porous polymer in parentheses is present inside the nonwoven fabric. An aqueous emulsion liquid (b) of a polymer mainly composed of polyurethane elastomer is applied onto the base layer (A) and dried to form a non-porous packing layer (B).
After forming a non-porous pigment layer (C), a solution (c) of a polymer mainly composed of polyurethane elastomer containing a pigment is applied and dried to form a non-porous pigment layer (C). A solution (d) of a polymer mainly composed of polyurethane elastomer using glycol as at least a part of the soft segment is applied and dried to form a dye-adsorbing non-porous resin layer (D), and then A leather-like sheet material characterized by forming a gloss-adjusting non-porous layer (E) by applying and drying a solution (e) of a polymer mainly composed of polyurethane elastomer containing gloss-adjusting fine particles. This is a manufacturing method.

The leather-like sheet material obtained by the method of the present invention does not have a porous coating layer on the base layer.

In other words, if we use the expression of artificial leather, the leather-like sheet material of the present invention has a single layer structure,
A non-porous surface finishing layer is directly laminated on this single-layered sheet material. The leather-like sheet material of the present invention does not have a rubbery feel because the porous coating layer is omitted, and the appearance, especially the color tone, is extremely similar to natural leather due to the special surface finishing layer provided on the base layer. It has become. Note that the non-porous layer referred to in the present invention does not refer only to a film-like non-porous membrane layer with a uniform thickness, but also a non-porous layer with a non-uniform thickness, and in some cases discontinuous spots. It also includes a non-porous resin layer.
Next, the present invention will be explained in detail.

First, the base layer (A) of the present invention is composed of a nonwoven fabric in which ultrafine fibers are entangled, and a polymer mainly composed of porous polyurethane elastomer present inside the nonwoven fabric.

Ultrafine Fiber East is a product obtained by mixing two or more polymers that are incompatible and have different solubility into paper threads, and then extracting and removing sea components from the resulting sea-island fibers using a solvent. It is. Polymers used to obtain the sea-island structure fibers include, for example, polyethylene phthalate, 6-nylon, 6,6-nylon, 6,10-nylon, polyethylene, polypropylene, polyacrylonitrile, polyvinyl alcohol, polypynychloride, polystyrene, etc. Examples include paperable polymers. Among these polymers,
Which one is used as the island component polymer and which one is used as the sea component polymer may be determined based on the requirements of the final product. Examples of combinations of island component polymers, sea component polymers, and solvents for extracting and removing the sea component polymers are as follows. Polyethylene terephthalate - nylon - benzyl alcohol or calcium chloride containing methanol 6 - nylon - polyvinyl alcohol - water polyethylene terephthalate - polyethylene tonolene polypropylene - polystyrene tricrene 6 - nylon - polyethylene tricrene The thus obtained sea-island structure fiber , stretching and striping as necessary,
After performing operations such as cutting, it is formed into a web, and then subjected to an entangling process such as needle punching to form a nonwoven fabric.

The sea-island structure fibers used for nonwoven fabrics usually have a weave of about 1.
It ranges from 0 denier to 20 denier, preferably from 1.5 denier to 15 denier. If the weave of the sea-island structure fibers is outside the above range, problems will arise in the process when the fibers are entangled to obtain a nonwoven fabric. In addition, the number of islands in each cross section of the sea-island structure fiber used to produce the nonwoven fabric is preferably 100 or more, and the thickness of the island component is 0.1 denier or less, particularly 0.01 denier or less, 0. It is preferable that it is .0001 denier or more. If the thickness of the islands is larger than 0.1 denier, the suppleness of the resulting leather-like sheet material will be poor, and irregularities on the surface of the base layer will appear on the sheet surface even after the surface finishing layer is applied, resulting in a leather-like sheet material that is similar to natural leather. It becomes difficult to obtain the desired appearance.
Conventionally, Senihigashi, which is made by removing sea components from composite paper yarn fibers in which 10 to 30 island components with a thickness of 0.1 to 0.4 denier are present in one fiber, is used as a base material for artificial leather. It is widely known that it can be done. However, "if such composite paper yarn fibers are used in the artificial leather of the present invention without a porous coating layer, the unevenness of the substrate surface will appear on the surface of the artificial leather after surface finishing due to the large degree of weaving, and the present invention It is difficult to obtain the desired artificial leather.The basis weight of the nonwoven fabric that is the base of the artificial leather of the present invention is 100% by weight after removing the sea component.
~1500 evenings/that range is preferable.

For the nonwoven fabric in which sea-island structure fibers are entangled, a method of temporarily fixing the fibers is adopted as necessary.

By temporarily fixing the fibers, it is possible to prevent inconveniences in the process such as the fibers coming apart during subsequent impregnation with a solution of a polymer mainly composed of polyurethane elastomer. As a specific method for temporarily fixing the fibers, when the sea component of the sea-island structure fiber is a heat-easy twilling polymer, a method of temporarily fixing the fibers by heat treatment can be adopted. Also,
A method of temporarily fixing using a glue such as starch, polypinyl alcohol, or carboxymethyl cellulose can also be adopted. These glues must be removed from the nonwoven fabric after it has been impregnated with a solution of a polyurethane elastomer-based polymer and solidified. It is preferable to use a water-soluble polymer as the adhesive because the adhesive can be removed simply by washing the nonwoven fabric with water, and the temporary fixation can be released. The nonwoven fabric thus obtained is impregnated with a solution of the following polymer mainly consisting of polyurethane elastomer and wet-coagulated.

The polyurethane elastomer used for impregnation is made by using one or more polymer diols of polyester diol, polyether diol, or polyester ether diol as a soft segment, and polymerizing this soft segment with an organic diisocyanate and a compound having two active hydrogen atoms. The polyurethane elastomer is preferably a polyurethane elastomer in which the polymerization percentage (hereinafter referred to as N%) of the nitrogen atoms constituting the isocyanate group of the organic diisocyanate relative to the polyurethane elastomer is 2.5 to 7. be. When a polyurethane elastomer with an N% of 2.5 or more is used, solvent resistance, heat resistance, and heat fixability decrease. Furthermore, if a polyurethane elastomer with an N% of more than 7 is used, the sponge will become hard and its bending resistance will decrease. The solution of a polymer mainly composed of polyurethane elastomer used for impregnation refers to polyurethane elastomer or a small amount of other polymers, such as polyurethane elastomer such as polypylene chloride, polymethyl acrylate, polyvinyl formal, etc. A composition prepared by mixing a polymer that is compatible with the polymer is dissolved in a solvent. The concentration of polymer in solution is 10
~2% blood weight is preferred. The solution may contain colorants such as pigments and dyes, coagulation regulators, various stabilizers, and other fillers. The amount of impregnation of this solution into the nonwoven fabric is 2 per 100 days of nonwoven fabric from which sea components have been removed, calculated as 2% of the polymer in the solution.
A range of 0 to 150 days is preferred.

If the amount of impregnation in terms of the polymer is less than 20 ta, there will be a disadvantage that the embossing cannot be fixed, and if the polymer is impregnated for more than 150 ta, the excess polymer solution will form a layer on the surface of the nonwoven fabric. As a result, a porous coating layer may be formed on the surface of the nonwoven fabric, and the nonwoven fabric may become rubbery, thereby defeating the purpose of the present invention. By immersing a nonwoven fabric impregnated with a solution of a polymer mainly composed of polyurethane elastomer into a coagulation bath containing a liquid that has an affinity for the polymer solvent but not for the polymer. ,
A nonwoven fabric having a porous polymer mainly composed of polyurethane elastomer is formed inside.

Furthermore, in order to extract and remove the sea component of the sea-island structure fibers, the sea-island structure fibers are transformed into ultra-fine fibers by soaking the non-woven fabric in an extraction bath or by traversing the non-woven fabric while sprinkling citrus on the surface. The base layer used in the present invention is completed. The surface of the base material is made of a polymer mainly composed of ultrafine fiber bundles and polyurethane elastomer, just like the inside, but when wet coagulated, the surface contains slightly more polymer mainly composed of polyurethane elastomer than the inside. However, in such a case, the surface finish layer is more beautiful and easier to finish than in the case where the ultrafine fibers forming the ultrafine fibers are scattered and fluffy on the surface of the substrate.Leather-like sheet of the present invention The material does not have a thick porous silver surface layer on the surface of the base layer as in conventional artificial leather.When a polymer solution for surface finishing is applied directly to the surface of such a base layer and dried, In the present invention, the unevenness of the substrate surface affects the leather-like sheet material after surface finishing, and cracks and depressions appear in the surface layer, making it impossible to obtain a good appearance.In the present invention, the surface of the substrate layer is mainly made of polyurethane elastomer. A layer for flattening the substrate surface by filling the depressions on the substrate surface with a polymer mainly composed of polyurethane elastomer by coating and drying an aqueous emulsion liquid [liquid (b)] of the polymer. (In the present invention, this non-porous layer is referred to as the (B) layer). Such defects were removed by forming a so-called packing layer.
b) The polyurethane elastomer constituting the liquid may use polyether glycol, polyester glycol, or polyether ester glycol as a soft segment, but in particular polyether glycol may be used as a soft segment. It is preferable to use it as it has a large packing effect. Furthermore, the polyurethane elastomer used for this layer (8) has a tN% of 3
A value in the range of 6 to 6 is preferable in terms of texture and heat fixability. For layer (B), instead of the aqueous emulsion liquid of a polymer mainly composed of polyurethane elastomer [liquid (b)], a solution of a polymer mainly composed of polyurethane elastomer or a solution of other polymers is used. If it is applied and dried, almost no filling effect will be obtained. The filling effect can only be obtained by applying and drying an aqueous emulsion of a polymer mainly composed of polyurethane elastomer. The liquid (b) may contain a small amount of resin other than polyurethane elastomer, such as acrylic resin, polyvinyl chloride, or the like. (b) to obtain a filling effect
The optimum amount of the liquid to be used is in the range of 5 to 60 hours per hour in terms of the solid content of the polyurethane elastomer.

If it is less than 5 days, large cracks and pinholes will remain in the surface layer after packing, which will spoil the appearance.

Moreover, if it is more than 60 minutes, the texture becomes hard and a comb feeling appears. More preferably, the solid content of the polyurethane elastomer is 30% and the following is used in the smallest possible amount (
B) to form a layer, for which (b)
Prior to applying the liquid, it is preferable to calender the base layer to smooth the surface. An example of this calendering device is the device described in Japanese Utility Model Publication No. 48-14671, that is, a calendering device having a smooth metal belt in which the crimping part is heated but the peeling part is cooled. Pressing and peeling the substrate onto the metal belt using a device and calendering the substrate facilitates the subsequent formation of a surface finishing layer, and also (
B) This is a preferable additional step for obtaining a leather-like sheet material with a good hand, since the amount of resin used in the layer can be reduced. (B) Used to form a layer (b)
Preferably, the liquid has a polymer concentration of 20-6% by weight. If it is less than 20%, it will easily penetrate into the inside of the substrate and the packing effect will be low.

Moreover, when it is 60% or more, a continuous film is likely to be formed and the physical properties are deteriorated. (b) Methods for applying the liquid include the gravure method, the spraying method, and the like, and among them, the gravure method is the most preferred since it can reliably perform plugging. (b) By drying the substrate coated with the liquid, a non-porous packing layer (B) is completed. Next, on the surface of the leather-like sheet material on which the packing layer (B) is laminated, a solution of a polymer mainly composed of polyurethane elastomer containing a pigment [(c)
A non-porous layer (C) formed from a liquid] is laminated.

This is to hide color spots caused by variations in the composition ratio of fibers and porous polyurethane in the base layer and variations in the thickness of the packing layer (B). This layer (C) is essential for the leather-like sheet material of the present invention, which does not have a layer. The layer (C) is formed at a rate of 0.5 to 50 m/m with solid content;
The layer C) contains 3 to 35 parts by weight, preferably 20 to 30 parts by weight, of pigment per 100 parts by weight of the polymer mainly composed of polyurethane elastomer.

If the solid content of the layer (C) is less than 0.5 mm, there will be a disadvantage that color spots will appear, and if it is more than 50 mm/〆, there will be a disadvantage that the texture will be hard. Furthermore, when the pigment content of the layer (C) is less than 3 parts by weight, it is difficult to hide the color spots with a solid content of 50 parts by weight or less, and when it exceeds 30 parts by weight, ( The adhesive strength between layer C) and packing layer (B) may become weak, resulting in peeling. (C)
The polymer used in the layer is polyurethane elastomer alone or a mixture of this and other polymers.

The polyurethane elastomer used in this layer may be polyether-based, polyester-based, or polyether-ester-based. Further, the N% of this polyurethane elastomer is preferably in the range of 3 to 6 from the viewpoint of hand feel and heat fixability. Examples of polymers that can be used in combination with the polyurethane elastomer include acrylic resins and vinyl chloride resins. The layer (C) is formed by applying and drying a solution of a polymer mainly composed of polyurethane elastomer containing a pigment [liquid (c)]. The concentration of is 3
A range of 20% by weight is preferable from the viewpoint of coating operation. (C)
Examples of methods for applying liquid (c) onto layer (B) to form a layer include the gravure method and the spraying method, but the gravure method is particularly effective because it can easily form a layer of uniform thickness. preferable. In addition to the pigment, this layer (C) may also contain dyes, softeners, various stabilizers, antistatic agents, and the like. On the surface of the sheet material on which the layer (C) is laminated, a non-porous transparent layer (D ) are stacked. Layer (D) is for giving a deep and elegant color to the leather-like sheet material of the present invention, and since the polyurethane elastomer used contains polyethylene glycol as a soft segment component, post-dying was carried out. In some cases, the dye is well adsorbed, and even when a solution in which dye is dissolved is used as the solution [(d) solution] for forming the (D) layer, the migration of dye molecules to other layers (
migration).

The layer (D) is formed from a resin having a solid content of 0.2 to 20 m/m. When the solid content is less than 0.2%, it is difficult to obtain a deep color. Also, if there are more than 20 evenings/prefecture,
The texture of the leather-like sheet material tends to deteriorate. This (D
) Methods of adding dye to the layer include dyeing it later;
There are two methods: (d) the dye is dissolved in the liquid. The dyes used for dyeing the layer (D) include acid dyes, disperse dyes, metal-containing dyes, etc., and among them, alloy dyes are preferred in terms of light resistance, washing resistance, etc. (
D) The polymer used in the layer is a polyurethane elastomer alone using polyethylene glycol as at least a part of the soft segment, or a combination of this polyurethane elastomer and another polymer, such as polypropylene glycol or polycaprolactone glycol. It is a mixture of a small amount of the used polymer such as polyurethane.

A polyurethane elastomer using polyethylene glycol as at least a part of the soft segment is a polyurethane elastomer in which 5% or more by weight of the total soft segment is polyethylene glycol, but as the content of polyethylene glycol increases, In the present invention, a polyurethane elastomer with a high proportion of polyethylene glycol is preferred as far as possible, since the affinity between the dye and the polyurethane elastomer is increased. Further, the polyurethane elastomer used for this layer (D) preferably has an N% in the range of 4 to 7 in terms of surface tackiness and friction durability. Layer (D) is formed by applying and drying a solution of a polymer mainly composed of polyurethane elastomer using polyethylene glycol as at least a part of the soft segment (liquid (d)). d) The concentration of polymer in the liquid is 3-2
A range of 0% by weight is preferable from the viewpoint of color development.

Examples of the method for applying the liquid (d) onto the layer (C) include the gravure method and the spraying method, and among them, the gravure method is preferred because it can easily form a layer of uniform thickness. Substantially no pigment should be present in this (D) layer, but various stabilizers may be added within the range that the (D) layer does not become opaque. Finally, on layer (D), a non-porous layer (E) formed from a solution of a polymer mainly composed of polyurethane elastomer containing fine particles for matting [liquid (e)] is provided. By controlling the surface gloss, a leather-like sheet material having a gloss suitable for various purposes can be obtained.

In particular, the sheet material consisting of layers (A), (B), (C), and (D) has a stronger surface gloss than artificial leather with a conventional porous coating layer, and it is necessary to reduce the surface gloss. In the present invention, the problem regarding surface gloss is solved by providing the layer (E). (E) The type of fine particles added to the layer may have a matting effect;
Especially among silica, calcium carbonate, titanium oxide, etc.
A material with good dispersibility in polyurethane elastomer solution, or a hard resin such as polycarbonate,
(E) A resin powder is used which is incompatible with the polymer constituting the layer.

Further, these fine particles preferably have a particle size of 0.01 to 0.1. Furthermore, as for the fine particles used in the (E) layer, when the (E) layer is formed, the (E)
Powders that color the layer white or nearly white are preferred. The amount of fine particles added is preferably in the range of 30 to 6 parts by weight per part by weight of the polymer 10 mainly composed of polyurethane elastomer constituting layer (E). (E) The thickness of the layer cannot be determined unconditionally because the optimum surface gloss varies depending on its purpose, such as clothing, interior decoration, sporting goods, etc., but it is usually 0.5 to 30 mm thick in terms of solid content. It is preferable that the thickness be such that it will become thicker. The polyurethane elastomer used in the layer (E) may be polyether-based, polyester-based, or polyether-ester-based.

The polyurethane elastomer used in layer (E) preferably has an N% of 3 to 7 in terms of texture and heat fixability. The polymer constituting the layer (E) may be the above polyurethane elastomer alone or a mixture with other polymers. Polymers that can be used in combination with the polyurethane elastomer include: Examples include acrylic resin and vinyl chloride resin. The (E) layer is formed by applying and drying a solution of a polymer mainly composed of polyurethane elastomer containing fine particles, and the concentration of the polymer in this polymer solution is 3 to 1. A range of % by weight is preferred.

Although it is essential that the layer (E) contains fine particles for matting, it may also contain dyes, softeners, various stabilizers, antistatic agents, and the like. Examples of methods for applying the (e) liquid onto the (D) layer to form the (E) layer include a gravure method and a spraying method.

A preferred method for forming the layer (E) is to first prepare a solution of a polymer mainly composed of polyurethane fester containing fine particles in an amount such that the solid content is 0.5 to 30 minutes per layer (D). This method involves applying it on top, drying it, and then embossing it. If this method is insufficient for matting, it is preferable to use a method of further laminating the fine particle-containing layer having a thickness of 0.5 to 15 mm on the surface after embossing. (A), (B), (C), (D) and (
E) The artificial leather consisting of layers is dyed, manipulated, calendered, etc. as necessary, and further, if necessary,
By providing a surface finishing layer, it is possible to obtain a leather-like sheet material that has an appearance, especially color and texture, that is very similar to natural leather, and these leather-like sheet materials can be used in shoes and bags where conventional artificial leather was used. Not only for fields such as clothing,
It is also suitable for interior use and sports equipment.

The present invention will be specifically explained below using Examples.

Parts and percentages used in the Examples and Comparative Examples are by weight unless otherwise specified. Example 1 A mixed yarn of 6-nylon 10 anchor part and polyethylene 10 base part was drawn, crimped, and cut to create raw cotton in which 6-nylon had an average twill of 0.002 denier and was an island component. did.

A web is made from this raw cotton using a random webber,
An intertwined nonwoven fabric with a size of 75 pieces/end was formed by needle punching. Next, this nonwoven fabric was immersed in an aqueous polyvinyl alcohol solution, dried, and then heat treated at a temperature of 120 to 150 qo to fuse the sea component polyethylene to temporarily fix the sheet. Thereafter, 12% dimethylformamide of a mixture of a polyurethane elastomer with an N% of 4.0% having polyethylene polypropylene adipate as a soft segment and a polyurethane elastomer with an N% of 4.0 having a polyethylene glycol as a soft segment. The solution was impregnated and immersed in a coagulation tank at 30° C. consisting of 7 parts of water and 3 parts of dimethylformamide for overflow coagulation. Subsequently, this sheet material was immersed in toluene to extract the polyethylene as a sea component, thereby obtaining a nonwoven fabric having a porous polyurethane elastomer inside a tangled body of ultrafine 6-nylon fibers. The component ratio of nylon 6 to polyurethane elastomer was 6 to 40.

This sheet with a thickness of 1.5 mm was sliced into two pieces and then buffed to form two base layers (A). Approximately 40% aqueous emulsion liquid of polyether polyurethane (Vondic 1310; Dainippon Ink & Chemicals Co., Ltd.
Co., Ltd.) was coated using a gravure method in a 16-day coat and dried to form a packing layer (B).

This packing layer (B) is a non-porous layer, but it is not a film-like dry film with a uniform thickness, but is a discontinuous layer with large thickness changes due to minute irregularities on the surface of the layer (A). .
200% polyurethane elastomer on its surface
A 14.3% solution (solvent: ethyl cellosolve) of a polyester-based polyurethane elastomer with N% of 4.0 containing a yellowish brown pigment was applied using a gravure method, dried, and solidified for 5 days. A colored layer (C) was formed. Next, on the surface of the sheet material on which the layer (C) was formed, polyethylene glycol was used as a soft segment and N% was 5.
A 7% solution of 0% easily dyeable polyurethane elastomer (solvent: acetone-cyclohexanone-dimethylformamide mixture) was applied and dried, and (D) was laminated on the solid matter for 2 days/time. (D) On top of the layer is a polyurethane elastomer with an average particle diameter of 4 and a siliency of 30% compared to the polyurethane elastomer and N% of 4.0.
．． An 8% solution (solvent: cyclohexanone-tetrahydrofuran mixture) is applied using the grapple method so that two coats are applied per coat, and dried to form the (E) layer, which produces a leather-like sheet material with low gloss. I got it. A pattern similar to natural leather was applied to this using heated empos rolls. In addition, Irugaran Yellow 2RL, Irugaran Brown Momme L,
8 with an aqueous dye solution mixed with Irgalan Olive BGL.
A leather-like sheet material dyed brown was produced by dyeing at 5-9-0 for 1 hour. Since this sheet material for leather was slightly lacking in luster compared to natural leather, it was calendered to give it luster to obtain a leather-like sheet material whose texture and appearance were extremely similar to natural leather. Example 2 In Example 1, Example 1 was added to the same polyurethane elastomer solution used to form layer (0).
5% of the same three dyes used to dye the leather-like sheet in polyurethane elastomer.
This solution was applied on the (C) layer in place of the solution used to form the (D) layer in Example 1, and the "different (D) layers were laminated," Example 1. Staining after staining was omitted.

Other treatments were carried out in the same manner as in Example 1 to obtain a leather-like sheet material. This leather-like sheet material had a texture and appearance similar to those obtained in Example 1, and was extremely similar to natural leather. Example 3 In Example 1, before forming layer (B), a sheet material was crimped onto a smooth metal belt whose temperature was controlled so that the temperature of the crimping part was 120 qo and the temperature of the peeling part was 100°C. A leather-like sheet material was obtained in the same manner as in Example 1, except that the surface of layer (A) was smoothed by peeling it off.

This leather-like sheet material was smoother than the leather-like sheet material of Example 1, and its folds and wrinkles were more similar to those of natural leather. Example 4 In the operation of Example 1, in order to form layer (B), polyester polyurethane (Vondic 16
No. 70: A leather-like sheet material was obtained by the same treatment as in Example 1 except that a 40% aqueous emulsion liquid (manufactured by Dainippon Ink & Chemicals Co., Ltd.) was used.

This leather-like sheet material was extremely similar to natural leather in terms of texture and appearance, but compared to the leather-like sheet material obtained in Example 1, the surface of the substrate (A) was slightly uneven. It was reflected on the surface. Example 5 The fibers of the base material of Example 1 were made into a 0.0.
A leather-like sheet material was obtained in the same manner as in Example 1, except that polyethylene terephthalate having a thickness of 0.025 denier was used as a mixed paper thread fiber of 4 denier as the island component.

This leather-like sheet material had a slightly harder feel than the leather-like sheet material of Example 1, but was extremely similar in appearance and performance to natural leather. Comparative Example 1 In the operation of Example 1, (B) layer was not formed and (A
A leather-like sheet material was prepared in the same manner as in Example 1, except that the layer (C) was applied directly on the layer (C).

This leather-like sheet material had poor flatness and embossing properties, lacked the luxurious feel of natural leather, and at first glance could be seen to be an imitation of artificial leather. Comparative Example 2 In the operation of Example 1, (C) layer was not formed and (B
A leather-like sheet material was prepared in the same manner as in Example 1, except that the layer (D) was formed directly on the surface of the sheet material on which the layer (D) had been formed.

In this leather-like sheet material, the spots on the base material appeared as dyed spots, and did not have the appearance of natural leather. Comparative Example 3 A leather-like sheet material was obtained in the same manner as in Example 1, except that layer (0) was not laminated and layer (E) was directly layered on layer (C).

However, this leather-like sheet material could not obtain a good color by dyeing, and had poor color development. Comparative example
4 In the operation of Example 1, instead of using an aqueous emulsion liquid for layer (B), a dimethylformamide solution of polyether-based polyurethane was used, so that the amount of polymer applied was the same as that of layer (B) of Example 1. It was applied in an appropriate amount.

In this case, the solution penetrated into the interior of the substrate (A), the texture became hard, and there was no so-called filling effect that reduces and smoothes the surface irregularities of the substrate. Furthermore, even if the same layers (C), (D), and (E) as in Example 1 were laminated, the surface smoothness was poor, the texture was hard, and the sheet material was far from natural leather. Met. Comparative Example 5 In the operation of Example 1, instead of mixed spun fibers, 6-
Multi-core sheath fibers of nylon and polyethylene (number of cores: 9), the weave of the 6-nylon island component is 0.3 denier, and the weight ratio of sea and island is 1:1. A leather-like sheet material was produced in the same manner as in Example 1 except for the following.

Claims (1)

[Scope of Claims] 1. A nonwoven fabric formed by entangling ultrafine fiber bundles and a porous polymer mainly composed of polyurethane elastomer, and the porous polymer is present inside the nonwoven fabric. After coating and drying a water-based emulsion liquid (b) of a polymer mainly composed of polyurethane elastomer on the base layer (A) to form a non-porous packing layer (B),
A solution (c) of a polymer mainly composed of a polyurethane elastomer containing a pigment is applied and dried to form a non-porous pigment layer (C), and polyethylene glycol is applied thereon as at least a part of the soft segment. Polymer solution (d) mainly composed of the used polyurethane elastomer
is coated and dried to form a dye-adsorbing non-porous resin layer (D), and then a solution of a polymer mainly composed of polyurethane elastomer containing fine particles for gloss adjustment (e
) and drying to form a gloss-adjusting non-porous layer (E). 2. The manufacturing method according to claim 1, wherein the surface of the base layer is calendered prior to applying the liquid (b). 3. The manufacturing method according to claim 1 or 2, wherein the leather-like sheet material is dyed after the liquid (e) is applied and dried. 4. The manufacturing method according to claim 1 or 2, wherein the liquid (d) contains a dye.