JPH02242980A - Production of suede-toned sheet excellent in color fastness - Google Patents

Abstract

PURPOSE:To obtain the subject sheet excellent in color fastness and form stability by treating a sheet prepared by dyeing a raised suede-toned sheet comprising polyamide ultrafine fiber and polyurethane polymer with a swelling agent which falls the swelling degree of said polymer within a specified range in terms of area swelling rate. CONSTITUTION:(A) A suede-toned sheet prepared by dyeing a raised suede-toned sheet comprising polyamide ultrafine fiber and/or bundled fiber therefrom and a polyurethane elastomer with a dye selected from bat dyes, sulfurized dyes and sulfurized bat dyes, or (B) such a sheet prepared by dyeing the sheet A with an acid dye and/or metal complex salt dye for the purpose of color matching as a whole, is treated with a liquid inert to the materials making up said sheet (e.g. halogenated ethane) so that the swelling degree of said elastomer fall between 20 and 100% in terms of area swelling degree, thus obtaining the flexible objective suede-toned sheet giving feeling like that of natural leather, excellent in color fastness and good in from stability to laundering and dry cleaning.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a polyamide ultrafine fiber napped suede-like sheet that has excellent color fastness, morphological stability, and good texture.

<Prior art> Conventionally, when dyeing an ultrafine fiber napped suede-like sheet made of a fiber-entangled nonwoven fabric of polyamide ultrafine fibers and/or their derived fibers and a polymer mainly composed of polyurethane,
Many proposals have been made for methods of producing products with high color fastness, and the applicant has already dyed polyamide fiber napped suede-like sheets with sulfur dyes or sulfur vat dyes, and processed them with soaping and brushing to improve color fastness. Japanese Patent Publication No. 61-25834 describes a method for improving the
1-46592, or JP-A-59-537
This is proposed in Publication No. 88. Furthermore, Japanese Patent Publication No. 62731O discloses that dyed products dyed with sulfur dyes or vat dyes are oxidized under specified pH and temperature conditions, and polyamide-based fiber structures are treated with compounds that have the ability to crystallize fiber polymers. JP-A-62-191585 discloses a method of dyeing a polyamide ultrafine fiber sheet with an anionic dye having a molecular weight of 900 or more and then dyeing it with a fiber fixing agent. The dyeing method for the treatment is described in Japanese Patent Publication No. 63-31596, and a fiber sheet made of polyamide fibers and polymeric elastomer is dyed with a metal complex dye, and then treated with tannic acid and tartarite.
Then, treatment with a surfactant was proposed in Japanese Patent Publication No. 63-575.
This is proposed in Publication No. 54.

<Problems to be Solved by the Invention> In the conventional dyed product of a polyamide ultrafine fiber napped suede-like sheet composed of polyamide ultrafine fibers and/or bundled fibers thereof and a polymer mainly composed of polyurethane, the fibers are thin. In addition, in order to increase color development, a large amount of dye must be used to deepen the color.

As a result, a large amount of dye adheres to the dye, resulting in a large decrease in color fastness, especially color fastness to rubbing and washing fastness. Although measures to prevent such a decrease in color fastness have been investigated, a dyed suede-like sheet product with sufficiently improved color fastness has not yet been obtained.

The present invention is a dyed product of a napped suede-like sheet made of ultrafine polyamide fibers, and an object of the present invention is to provide a suede-like sheet that is excellent in color fastness, morphological stability upon washing or dry cleaning, and has a good texture.

Means for Solving the Problems> The present invention provides a fiber-raised suede-like sheet composed of polyamide ultrafine fibers and/or bundled fibers thereof and a polymer mainly composed of polyurethane. A suede-like sheet obtained by dyeing with a dye selected from the group of vat dyes, or a suede-like sheet obtained by further dyeing the dyed suede-like sheet with an acid dye or a metal complex dye, is Swelling degree is 20~20 in terms of area swelling rate.
This is a method for producing a suede-like sheet with excellent color fastness, which is characterized by treating with a swelling agent or a liquid containing the swelling agent and drying.

That is, the sheet-like substrate made of a fiber-entangled nonwoven fabric of ultrafine fibers and/or ultrafine fiber bundles and a polyurethane-based polymer used to produce the polyamide ultrafine fiber napped suede-like sheet of the present invention is: The boramid fibers constituting the fiber-entangled nonwoven fabric are, for example, 6-nylon, 6-row nylon, 610-nylon, 12-nylon, or other fiber-forming spinnable polyamides,
Ultrafine fiber obtained by spinning spinnable polyamide alone and drawing it. Alternatively, the above-mentioned spinnable polyamide and other spinnable polymers may be combined to form an ultra-fine fiber-generating multi-component fiber containing polyamide as an ultra-fine fiber component, and the resulting fiber may be drawn until the final product is produced. In the process, the multicomponent fibers are processed into polyamide ultrafine fiber bundles.

That is, ultrafine fibers or ultrafine fiber-generated multicomponent fibers are made into a fiber web by a normal method, and the fiber web is subjected to an entanglement treatment to form a fiber entangled nonwoven fabric.

Then, the fiber-entangled nonwoven fabric of polyamide ultrafine fibers is made to contain an elastic polymer to form a sheet-like substrate.

On the other hand, in the case of a fiber-entangled nonwoven fabric made of ultrafine fiber-generating multicomponent fibers, after temporarily fixing the fiber entangled nonwoven fabric, the nonwoven fabric fibers are processed to form polyamide ultrafine fiber bundles, and then an elastic polymer is added. A sheet-like substrate is obtained. Alternatively, after incorporating an elastic polymer into a fiber-entangled nonwoven fabric, the nonwoven fabric fibers are treated to form a bundle of polyamide ultrafine fibers into a sheet-like substrate.

The average single fiber fineness of the ultrafine fibers or ultrafine fiber bundles constituting the substrate is 0.3 denier or less, preferably 0.1 to 0.001 denier. In addition, the basis weight of the polyamide ultrafine fiber entangled nonwoven fabric is
The basis weight of the fiber-entangled nonwoven fabric as a final product is 80 to 300.
g/+a'' range.

Next, the polyurethane to be contained in the fiber-entangled nonwoven fabric is a polyester diol having an average molecular weight of 500 to 2500,
At least one polymer diol selected from the group of polyether diols, polyester ether diols, polylactone diols, and polycarbonate diols, and diisocyanates containing aromatic rings, aliphatic diisocyanates having cyclic groups, alicyclic diisocyanates, etc. At least one type of organic diisocyanate selected from the group of and at least one type of compound having two active hydrogen atoms, for example, at least one type selected from the group of diols, diamines, hydroxyamines, etc., are used as chain extenders, and the polymer diol and It is a polyurethane obtained by reacting an organic diisocyanate with a chain extender. A preferable polyurethane has a stress of 0.20 to 1.5 at 100% elongation.
It is a polyurethane in the range of 0 Kg/mm2. If the stress at 100% elongation of the polyurethane is outside the above range, the elastic behavior will increase or the texture will become stiff, making it impossible to obtain a product with a soft, puffy texture like natural leather. Further, a polyurethane composition may be used in which a polymer selected from synthetic rubber, vinyl chloride polymer, silicon atom-containing elastic polymer, etc. is mixed with polyurethane. The weight ratio of polyurethane or polyurethane composition in the sheet-like substrate is 10 to 5.
0% by weight, preferably in the range of 15-40% by weight.

If the amount of the polymer in the sheet-like substrate is outside the above range, it will be undesirable because it will lose its stiffness, it will not be able to provide a feeling of fullness, and its elastic behavior will become large.

A sheet-like substrate made of an ultrafine fiber-entangled nonwoven fabric and a polymer mainly composed of polyurethane has a raised fiber surface mainly composed of ultrafine fibers formed on at least one surface. In other words, after or before adjusting the thickness to a desired thickness, the sheet-like substrate is subjected to a napping treatment using a napping machine, a puffing treatment using sandpaper, etc. on at least one side of the sheet-like substrate to mainly make the fibers stand up. A raised surface is formed to produce a fiber raised suede-like sheet.

If the thickness of the sheet has not been adjusted, the back side is processed to the desired thickness and the thickness is adjusted. The fiber-raised suede sheet has a product thickness of 2.0 to 0-
It is a fiber-raised suede-like sheet having a thickness of 25 mm, preferably a thickness of 1.5 to 0.30+ nm.

Next, dyeing of the fiber-raised suede-like sheet is done using vat dyes.
Dyeing with dyes selected from the group of sulfur dyes and sulfur vat dyes. Dyeing methods include applying a dye or a dye composition to the surface of the fibers, then treating the dye-applied sheet in a reducing solution to dye it, or immersion dyeing, in which the sheet is immersed in a dye reducing solution and dyed. Any law is fine. In the former dyeing method, a dye composition containing at least one type of dye selected from the group of vat dyes, sulfur dyes, and sulfur vat dyes, or a penetrating agent added as necessary, is applied to the sheet as a solution or dispersion. , and then apply it to at least the raised fiber surface of the
It is immersed in a reducing agent solution at 50 to 100° C. for about 5 seconds to 60 minutes to perform a reduction dyeing treatment, followed by an oxidation treatment, washing with water, and soaping to obtain a dyed suede-like sheet. In the latter dyeing method, at least one dye selected from the group of vat dyes, sulfur dyes, and sulfur vat dyes is reduced with one type of alkali selected from caustic soda, soda carbonate, etc. After reducing the dye solution in the presence of a dye solution, the fiber-raised suede-like sheet is heated to a temperature of 50 to ioo°C.
, preferably in a dye liquor at 60 to 95°C for about 5 seconds to 60 minutes, and then, after removing the dye liquor, air oxidation or chemical oxidation is performed.

Further, after removing the dye liquor as necessary, the sheet is washed with water or neutralized, and then subjected to air oxidation or chemical oxidation to obtain a dyed suede-like sheet. The reducing agent used here is at least one type of reducing agent selected from, for example, nohydrosulfite, Rongalit C10 Ngarit CL, sodium hydrogen sulfide, and sodium sulfide. , for example, an oxidizing agent selected from potassium dichromate, potassium permanganate, perboric acid, hydrogen peroxide, and the like.

The dyed suede-like sheet may be dyed with an acid dye or a metal complex dye in order to match the overall color or the color between the fiber and the polymer.

The dyed suede-like sheet is then dried and treated in an organic liquid that does not dissolve most of the dye and the sheet materials, such as the fibers and polymers or other materials that make up the suede-like sheet. . Preferably, a swelling agent whose degree of swelling of the polymer is in the range of 20 to 100% in area swelling ratio is used.

Organic liquids with a swelling degree of less than 20% do not provide sufficient dye rearrangement and fixation. On the other hand, organic liquids with a large swelling degree exceeding 100% are undesirable because they cause structural deformation of the polymer and shedding of the dye. Examples of organic liquids for treatment include halogenated ethane or halogenated ethylene in which hydrogen atoms in hydrocarbon compounds are replaced with chlorine atoms or fluorine atoms, petroleum-based liquid hydrocarbons, aromatic hydrocarbons such as xylene, and ketones such as methyl ethyl ketone. kind,
It is a liquid that is inert to the sheet constituent materials such as. However, the degree of swelling may be adjusted by mixing liquids with a high swelling degree with non-swelling or low swelling liquids, such as alcohols, water, petroleum hydrocarbons, etc. Further, the swelling agent may be used by dispersing it in a non-swelling agent such as water or alcohol. Swelling agent treatment conditions are determined by the temperature dependence of the organic liquid used for the polymer.

In other words, organic liquids with a high degree of swelling can be heated at room temperature to 5.
Process at a high temperature of about 0°C, or 50°C or higher if the degree of swelling is small. This treatment mainly allows the dye attached to the polymer to be rearranged within the polymer and stabilized.
Color fastness can be improved. Furthermore, it is possible to alleviate the distortion that occurs during the production of the fiber-raised suede-like sheet, thereby making it possible to stabilize the shape.

In addition, when treating a suede-like sheet with an organic liquid, it is preferable to use a composition liquid in which a softener, a fatliquoring agent, a surfactant, an antistatic agent, etc. are added to the organic liquid. In addition, for organic liquid processing, processing equipment having a rubbing mechanism, such as a wince dyeing machine, a jet dyeing machine, a circular dyeing machine,
It is preferable to use such as in order to impart flexibility.

After treatment, the liquid is removed from the fiber-raised suede-like sheet and it is dried. In the drying method, it is preferable to use a dryer having a rubbing action. Then, the treated suede-like sheet is processed, as necessary, by mechanical rubbing and hair-dressing by brushing the raised fiber surface, to form a product.

The resulting suede-like sheet has the flexibility and plump texture of natural leather, and has excellent napping properties, color fastness,
A napped suede-like sheet made of ultrafine polyamide fibers with excellent color fastness to abrasion. This suede-like sheet is suitable for uses such as clothing, gloves, accessories, interior decoration, shoes, footwear, bags, bags, and upholstery.

<Function> According to the present invention, the distortion that occurs when producing a fiber-raised suede-like sheet can be sufficiently alleviated by treatment with a polymer swelling agent, and furthermore, the dye can be rearranged. . As a result, it is possible to give the product softness with a feeling of swelling, and color fastness is also improved.

<Examples> Next, embodiments of the present invention will be described using specific examples, but the present invention is not limited to these examples. Note that parts and percentages in the examples are by weight unless otherwise specified.

Examples 1 to 3 (Production method of substrate) A drawn multicomponent fiber with a fineness of 6 denier consisting of 55 parts of 6-nylon (dispersion component) and 45 parts of polyethylene (dispersion medium component) was crimped to a fiber length of 51 mm. This fiber entanglement was cut into staple fibers, passed through carding and random univer to create a cross-wrap web with an average basis weight of 530 g/m'', and needle punched to obtain a fiber entangled nonwoven fabric with an average basis weight of 538 g/m2. Polyether polyurethane (stress at 100% elongation: 0, 69 Kg/
13% of the polyurethane composition mainly composed of
The fibers are impregnated with a dimethylformamide solution, coagulated in a non-solvent coagulating solution containing dimethylformamide, washed with water, and the polyethylene in the fibers is extracted with a solvent treatment to form 6-nylon ultrafine fiber bundles (single fiber average fineness 0. Fabric weight 455 made of fiber entangled nonwoven fabric (008 denier) and polyurethane
A sheet-like substrate with a thickness of 1.201!lII+ and a thickness of 1.201!g/m was obtained. This sheet-like substrate was divided into two parts at the middle of the thickness, and the divided surfaces were puffed with sandpaper to give an average basis weight of 220.
After adjusting the thickness to 0.57 mm, the surface during coagulation is treated with emery puffing to form a fiber-raised suede-like surface, resulting in a fiber-raised suede-like sheet base material. (1) was obtained.

(Finishing method) The fiber-raised suede-like sheet [■] was dyed using a dye coating method. That is, Dye composition-1: Vat dye 100g/Q Mikethrene Brilliant Violet 3B (manufactured by Mitsui Toatsu Chemical Co., Ltd.) Penetrant 2g/ff Perex OTP (manufactured by Kao Atlas Co., Ltd.) Dye composition-2: Vat dye 100g/Q Mikethrene Green 4G Penetrant Perex OTP 2g/Q Dye Composition -3 = Sulfur Dye 100g/Q Penetrant
Using a roll engraved with 140 mesh squares, 2g/Q of an aqueous solution of each dye composition was applied to the fiber raised surface of each suede-like sheet to be dyed using a roll method, resulting in a liquid volume of approximately 65g/m''. After coating (approximately 3% dye adhesion rate on the suede-like sheet), reducing agent treatment was performed under the following conditions. Namely, reducing agent composition: Sodium hydrosulfite 30 g/Q Caustic soda 30 g/Q Sodium chloride
60g/Q reducing agent solution temperature
Reduction dyeing treatment was carried out at 85°C for 1 minute, washed with water, then oxidized in a hydrogen peroxide-acetic acid solution, washed with water, soaped, and then brushed with a nylon brush while still wet. , dehydrated.

Each dyed suede-like sheet is separated by color and placed in a rotating drum processing machine, and 300Q of tetrachlorethylene (swelling degree of about 49% relative to polyurethane) is added as a swelling agent to 30 kg of dyed fabric, and the fabric is placed in the drum at room temperature. The mixture was treated while rotating for about 3 minutes, and after the treatment, tetrachlorethylene was recovered, followed by centrifugal deliquification and drying. The color fastness of the obtained suede-like sheet is shown in Table 1.

Further, for comparison, dyed suede-like sheets without swelling agent treatment are shown as comparative examples.

Table 1 However, the test method was as follows.

Color fastness is JIS L-0844A-1 method (grade) Dry cleaning fastness is JIS L-0860 method (grade)
Class) Color fastness to rubbing is JIS L-0849 method (class)
Although each dyed product exhibited clear and uniform color development, the product of the present invention was superior in dry cleaning fastness and dyeing abrasion fastness.

Example 4 A mixed polyurethane of 20 parts of polyether polyurethane and 80 parts of polyester polyurethane was applied to a fiber-entangled nonwoven fabric made of 6-nylon microfiber bundle fibers with an average fineness of 0.041 denier (stress at 100% elongation of mixed polyurethane). A sheet-like base material with a thickness of 0 to 85 mm containing a porous material of 0.57 Kg/mm'') was used, and one side of the base material was puffed with sandpaper to obtain a fiber-raised suede-like sheet CI).

This fiber-raised suede-like sheet was dyed under the following conditions.
child .

Dyeing conditions: Dye Asadiosol Blue 5-BC 3% owf (manufactured by Asahi Chemical Co., Ltd.) Hydrosil Green 3B 3.5% owf (manufactured by ICI Corporation) Reducing agent Soda hydrogen sulfide 6% Treatment conditions
Dyeing solution temperature: 80°C Immersion time
30 seconds squeezing rate 100% A fiber-raised suede-like sheet was treated in a dye solution, squeezed, air oxidized, washed with water, and further chemically oxidized under the following conditions.

Oxidizing agent Asahi Oxy 150 0.5% (manufactured by Asahi Chemical Co., Ltd.) Acetic acid 1% Treated with the above oxidizing solution at room temperature for 30 minutes, washed with water, and removed the dye adhering to the surface by brushing. Using the same rotating drum processing machine as in Example 1, the fabric was treated at 40°C for about 20 minutes while rotating using a petroleum hydrocarbon as a swelling agent, and the liquid was collected and then centrifuged to remove the liquid and dried. Table 2 shows the color fastness of the dyed suede-like sheets obtained.

For comparison, the color fastness of the dyed suede-like sheet without swelling agent treatment is also shown.

Table 2 The dyed products of the present invention were clearly and uniformly dyed and had excellent fastness.

<Effects of the Invention> The polyamide ultrafine fiber napped suede-like sheet of the present invention has a soft, plump texture similar to natural leather, excellent napped properties, color fastness, and color fastness to abrasion, and is resistant to washing and dry cleaning. However, it is a product with good morphological stability.

Patent applicant RiRashi Co., Ltd. Representative Patent Attorney Ken Honda However, the test method is the same as in Table 1.

Claims (1)

[Claims] (1) A fiber-raised suede-like sheet composed of ultrafine polyamide fibers and/or bundled fibers thereof and a polymer mainly composed of polyurethane is dyed with a dye selected from the group of vat dyes, sulfur dyes, and sulfur vat dyes. A suede-like sheet obtained by dyeing the dyed suede-like sheet, or a suede-like sheet obtained by further dyeing the dyed suede-like sheet with an acid dye or a metal complex dye, has a polymer swelling degree of 20 to 10 in area swelling ratio.
1. A method for producing a suede-like sheet with excellent color fastness, which comprises treating the sheet with a swelling agent of 0% or a liquid containing the swelling agent, and drying the sheet.