JPH03113082A - Dyeing method for polyamide fiber raised suede - Google Patents

Abstract

PURPOSE:To obtain a densely colored raised suede-toned dyed product rich in soft touch with puffy feel by imparting the raised surface of a suede-toned sheet made up of raised hair consisting of ultrafine polyamide fiber with a swelling agent contg. composition solution followed by heat treatment and then dyeing. CONSTITUTION:A suede-toned sheet made up of raised hair consisting of ultrafine polyamide fiber and/or bundled fiber thereof <=0.1 denier in fineness produced by treating a fibrous structure made up of multi-component fiber capable of developing ultrafine polyamide fiber is put to immersion treatment in a solution containing a swelling agent such as benzoic acid. The resulting sheet is heat-treated, washed to eliminate said swelling agent, and then dyed with e.g. an acid dye, thus giving the objective densely colored polyamide fiber raised suede-toned dyed product rich in soft touch with puffy feel and excellent in color fastness.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a method for producing a suede-like sheet which is obtained by dyeing a raised suede-like sheet made of ultrafine polyamide fibers in a deep color and which has a plump, soft texture and feel.

[Conventional technology]

Several proposals have been made to improve the dyeability of napped suede-like sheets made of ultrafine polyamide fibers. For example, Japanese Patent Publication No. 55-506 describes dyeing by applying an easily dyeable polymer to the surface of fiber-napped suede, and dyeing with a dye that becomes water-soluble when reduced in the presence of an alkali, and then oxidizing. It is disclosed in Japanese Patent Publication No. 61-25834 and Japanese Patent Publication No. 61-4 that dyes fiber-raised suede using a dyeing method that fixes the dye.
This method has been proposed in Japanese Patent Laid-Open No. 6592, Japanese Patent Laid-Open No. 59-53788, and the like.

[Problem to be solved by the invention]

Conventional dyeing of polyamide ultrafine fiber napped suede-like sheets was based on a dyeing method that deepened the color and improved color fastness. Therefore, the obtained suede-like sheet product had a deep color and excellent color fastness, but on the other hand, the texture of the suede-like sheet and the texture of the raised fiber surface were rather stiff, bulky and thin. It was something like that. The object of the present invention is to provide a method for producing a suede-like sheet which can be dyed in a deep color and has a soft texture and feel with a bulge-like feel.

[Means to solve the problem]

When dyeing a suede-like sheet in which at least the surface napped fibers are composed of ultrafine polyamide fibers and/or bundled fibers thereof having a fineness of 0.1 denier or less, the present invention provides a method for dyeing a suede-like sheet in which at least the napped fibers are coated on at least the napped side of the suede-like sheet. This is a method for dyeing raised suede of polyamide fibers, which is characterized by applying a composition containing a swelling agent, heat treating it, and then dyeing it. That is, the dyed suede-like sheet of the present invention is a suede-like sheet in which at least the surface napped fibers are composed of ultrafine polyamide fibers with a fineness of 0.1 denier or less and/or bundled fibers thereof; The structure uses polyamide microfiber-generated multicomponent fibers (hereinafter referred to as multicomponent fibers), and the multicomponent fibers or fibers mainly composed of multicomponent fibers include fiber entangled nonwoven fabrics, fiber napped woven fabrics, fiber napped knitted fabrics, etc. before processing the multicomponent fibers of those fibrous structures to generate ultrafine fibers or bundles of ultrafine fibers, or after generating ultrafine fibers or bundles of ultrafine fibers. A sheet-like base material is formed by containing a polymer that mainly undergoes coalescence. Then, in the sheet-like base material that has not been made into ultrafine fibers, the multicomponent fibers are processed to form polyamide ultrafine fibers or ultrafine fiber bundles. The obtained sheet-like base material made of polyamide ultrafine fibers or ultrafine fiber bundle fibers and a polymer mainly composed of an elastic polymer is subjected to a napping treatment and/or a napping treatment on at least one side using a napping machine.
Alternatively, a suede-like sheet made of raised polyamide ultrafine fibers on at least one side is obtained by raising the sheet with sandpaper. The multicomponent fiber of the present invention includes polyamides such as 6-nylon, 6-row nylon, 610-nylon, 11-nylon, 12-nylon, 26-nylon, 210-knife 7.410-nylon, 7-row nylon, In addition, at least one type of polyamide selected from spinnable polyamides having an aromatic ring. On the other hand, other polymers constituting the multicomponent fibers have different solubility in solvents than polyamide, have a low affinity, and have a melt viscosity lower than that of polyamide under spinning conditions, or Polymers with low surface tension, such as polyethylene, polypropylene, ethylene propylene copolymer, ethylene octene copolymer, ethylene vinyl acetate copolymer, polystyrene, styrene acrylonitrile copolymer, styrene ethylene copolymer, polyester, etc. At least one type of polymer selected from the following. Fibers made of polyamide and other polymers can be mixed at a predetermined mixing ratio and dissolved in the same melting system to form a mixed system and then spun. A method in which joining and splitting is repeated multiple times at the head to form a mixed system for spinning, and a method in which the polyamides occupying the fiber are melted in separate melting systems and spun with the fiber shape defined in the spinneret. Ingredients are 40-80% by weight
and the polyamide ultrafine fiber component in the multicomponent fiber is 5
A multicomponent fiber having a number of fibers or more, preferably in the range of 50 to 800 fibers is obtained. The multicomponent fiber undergoes normal fiber processing processes such as drawing and heat setting to have a fineness of 2 to 15 deniers, and the average fineness (calculated value) of the polyamide ultrafine fiber component in the multicomponent fiber is 0.1.
Fibers with a denier or less. Next, the method for obtaining polyamide ultrafine fibers from multicomponent fibers is to form a fiber structure such as a fiber entangled nonwoven fabric, a raised woven fabric, or a raised knitted fabric using the multicomponent fibers, and then use a polyamide non-solvent or non-solvent. It is a decomposition agent and is removed by treatment with a solvent for other components or a decomposition agent, or in the case of a bonded multicomponent fiber of polyamide and other polymers, it is divided into ultrafine fibers of each component. By this process, a fiber structure in the form of polyamide ultrafine fibers or ultrafine fiber bundles can be obtained. Further, the elastic polymer to be contained in the fiber structure is, for example,
polyester diol with an average molecular weight of 600 to 3000,
At least one polymer diol selected from polyether diol, polyester ether diol, polylactone diol, polycarbonate diol, etc., and tolylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 4.4'-diphenylmethane diisocyanate, 4.4' - at least one type of organic diisocyanate selected from aromatic, alicyclic, and aliphatic organic diisocyanates such as dicyclohexylmethane diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate;
diol, diamine, hydroxyamine, hydrazine,
Polyurethane, polyacrylic acid ester, acrylonitrile-butadiene (
At least one type of elastic polymer selected from styrene copolymers, other synthetic rubbers, etc., preferably polyurethane. Polyurethane is used as a polymer composition obtained by adding polymers such as synthetic rubber, polyester elastomer, and polyvinyl chloride as needed. Next, the production of sheet-like substrates involves dissolving a polymer, mainly an elastic polymer, in a solvent or dispersing it in a dispersant. The polymer liquid obtained by mixing the polymer liquid with additives selected from colorants, coagulation regulators, mold release agents, plasticizers, stabilizers, antioxidants, light stabilizers, etc. A wet coagulation method involves impregnating the fiber structure as a combined composition liquid and coagulating it by treating it with a polymer non-solvent, a dry coagulation method in which the solvent or dispersant is removed by heating and coagulation, or a combination of these methods. , wash as necessary, and dry to form a sheet-like base material. Then, at least one side of the sheet-like base material is subjected to a raising treatment using a raising machine and/or a raising treatment using a sandpaper, so that at least one side thereof is made into a suede-like sheet made of napped polyamide ultrafine fibers. The finishing method of the suede-like sheet of the present invention includes adding a swelling agent for polyamide fibers, such as benzoic acid, salicylic acid, lactic acid, phenol, to at least the fiber-raised surface of the suede-like sheet.
At least one selected from benzyl alcohol, calcium chloride, zinc chloride, lithium chloride, lithium bromide, etc.
It is a composition liquid prepared by dissolving or dispersing the type in water, alcohol, or a water-alcohol mixture, and this composition liquid must not dissolve or significantly deteriorate the constituent materials of the suede-like sheet. If the constituent materials are dissolved or significantly deteriorated, reduce the amount of the swelling agent or change the solvent composition. For example, use higher alcohols or It is also good to use a solvent composition containing a solvent such as ethylene glycol. The concentration and adhesion rate of the swelling agent vary depending on the type of polyamide, the thickness of the microfiber, the strength of the swelling agent's action, the heat treatment conditions, etc., so the optimum conditions are determined through testing before treatment. Concentrations range from 1 to 10% by weight. Next, the method of applying the swelling agent solution or dispersion to the suede-like sheet is as follows.
When applying the swelling agent mainly to the surface, methods such as applying the swelling agent liquid with a roll with a smooth surface or a cracked surface, applying it by spraying, or increasing the viscosity of the liquid and applying it using a knife coat can be applied. In addition, when applying it in a pattern, it is preferable to use a method of applying with an engraved roll. When the entire sheet is treated, the suede-like sheet is immersed in a swelling agent solution. The suede-like sheet to which a swelling agent has been applied is heat-treated in a wet heat state, a dry heat state, or in a swelling agent solution. The heat treatment conditions vary depending on the properties of the swelling agent solvent or dispersant, but generally the heat treatment is performed at a temperature of 50 to 120° C. and for a time of 3 to 20 minutes. When the temperature exceeds this range, it is not preferable because it causes welding of ultrafine fiber bundles due to partial dissolution of the fibers, deterioration of the polymer, etc. After the heat treatment, the suede-like sheet is washed to remove the swelling agent. Then, dye the suede-like sheet. Dyeing is done using dyes that are mainly acid dyes, metal complex dyes, etc., and by dyeing using normal dyeing methods, a suede-like sheet with a deep color and good color fastness can be obtained. The dyed suede-like sheet is subjected to finishing treatments such as softening treatment and brushing to obtain a suede-like sheet product. The suede-like sheet obtained by the present invention is dyed in a dark color,
It also has a soft texture and feel with a sense of swelling, gives gloss to the surface fibers, and provides a product with excellent color fastness. This suede-like sheet product is suitable not only for clothing, but also for accessories, interior decoration, shoes, bags, and various types of gloves.

【Example】

Next, embodiments of the present invention will be explained 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. Example 1 Average basis weight 730 g made using a multicomponent fiber with a fineness of 4 denier consisting of 65 parts of 6-nylon/35 parts of polyethylene [average number of nylon ultrafine fiber components: 460 pieces, fineness (calculated value) of 0.0057 denier] /m" fiber entangled nonwoven fabric, 13 parts of a polyurethane composition consisting of 90 parts of polyester polyurethane, 10 parts of polyoxyethylene polyurethane, 0.5 part of nonionic activator, 1 part of carbon black, N, N'- Dimethylformamide (hereinafter referred to as DMF)
) 85.5 parts of the composition solution and D! JF40%
The fibers were coagulated in an aqueous solution, washed with water, and then the polyethylene in the multicomponent fibers was dissolved and removed to obtain a sheet-like base material consisting of an entangled nonwoven fabric of 6-nylon ultrafine fiber bundles and polyurethane. This sheet-like base material is divided into two parts in the middle of the thickness,
The surface during coagulation is treated with an emery puff machine to form a raised surface of nylon ultrafine fibers, and the dividing surface is further ground to create an average thickness of 0.
．． A 7 mm suede-like sheet CI) was obtained. Next, a 3% benzoic acid aqueous solution was heated to 90°C, the suede-like sheet [I] was immersed in it and treated for 10 minutes, and then washed in hot water at 90°C to remove the benzoic acid. After that, the sheet was squeezed to remove water and was dyed using a Wins dyeing machine under the following conditions. Black acid dye 7% OVF bath ratio
1: lOO temperature x time 95°C x 60m1n. After dyeing, soaping and drying, a softening treatment and a hair conditioning treatment on the raised surface were performed to obtain a suede-like sheet product I. Comparative Example 1 A suede-like sheet product (■) was obtained by subjecting the suede-like sheet [■] of Example 1 to the dyeing and finishing treatments of Example 1 without performing benzoic acid treatment. The conditions of the obtained suede-like sheet products are compared in Table 1. Table 1 1) Color difference ΔE value measured using color measuring system Z-Σ80 (manufactured by Nippon Denshoku) 2) Evaluation results of a sensory test by 20 arbitrarily selected panelists. ◎: Excellent, O: Good, △: Slightly inferior, ×: Bad. In other words, the difference in color difference between the suede-like sheet products of Example 1 and Comparative Example 1 is 9.2, and the product of Example 1 is darker. It is dyed in different colors, has excellent color fastness, and has a soft texture with a puffy feel. On the other hand, the product of Comparative Example 1 had poor color development and a rough texture. Example 2 1 part of benzyl alcohol, 5 parts of ethylene glycol, and 9 parts of water were added to the fiber raised surface of the suede-like sheet [I] of Example 1.
A swelling agent solution consisting of 4 parts was applied in an amount of about 45 g/m'' with a roll having 50 meshes, and the temperature was about 110°C.
After heat treatment for one part in a steam atmosphere at 90°C
The sheet was washed in hot water (C) to remove the swelling agent and squeezed to remove water, and then dyed using a Wins dyeing machine under the following conditions. Brown metal complex dye 2% owf Brown acid dye 0.7% owf bath ratio
1:100 temperature x time
95°Qx5Qmin. After dyeing, soaping and drying, a softening treatment and a hair conditioning treatment on the raised surface were performed to obtain a suede-like sheet product (■). The obtained suede-like sheet product ■ has a difference in the dyeing state on the front and back sides, the color difference ΔE value on the surface of the fiber nap is 81.5, the color difference ΔE value on the back side is 79, and the difference is 2.5. was dyed dark brown, shiny and soft to the touch, while the back side was a little lighter in color and had a slightly rough texture. However, the sheet as a whole was a suede-like sheet product with a good texture, dominated by the bulge-like flexibility on the surface side. Comparative Example 2 A swelling agent solution consisting of 15 parts of benzyl alcohol and 85 parts of water was applied to the fiber raised surface of the suede-like sheet [■] of Example 1 in an amount of about 45 g/m'' with a roll having 50 meshes. was applied and heat-treated for 10 minutes in a steam atmosphere at a temperature of about 110°C as in Example 2. After the treatment, many of the ultrafine fibers were welded to the fiber-napped surface, making it unsuitable for a suede-like surface. Example 3 An entangled nonwoven fabric of ultrafine fiber bundles [average fineness (calculated value) of ultrafine fibers: 0.035 denier] in which an average of 90 ultrafine nylon fibers containing 5% carbon black were converged. Suede-like sheet Cn) with a thickness of 0.75 m + i, using a sheet-like base material containing polyurethane containing polyoxyethylene chains, and finishing the negative side with a fiber-raised suede-like finish.
was treated in a 7% aqueous calcium chloride solution at a temperature of 80° C. for 10 minutes, resulting in an excellent product. Calcium chloride was removed by washing in hot water at 90°C.
The sheet from which the water had been squeezed was dyed using a dash line dyeing machine under the following conditions. Red metal complex dye 5% owf Yellow metal complex dye 0.3% owl lupine acid dye
2.3%owf Blue acid dye 0.1%ow
f bath ratio 1:10
0 temperature x time 95°OX6
0 min. After dyeing, soaping and drying, a softening treatment and a hair-dressing treatment on the raised surface were performed to obtain a wine-colored suede-like sheet product (■). The color difference ΔE value of the obtained suede-like sheet product ■ is 82.
3, the product was dyed a beautiful wine color, had a glossy feel, was soft to the touch, and had a puffy texture, and was suitable as a material for outer clothing.

【Effect of the invention】

Claims (1)

[Claims] (1) When dyeing a suede-like sheet in which at least the surface napped fibers are composed of ultrafine polyamide fibers and/or bundled fibers thereof with a fineness of 0.1 denier or less, swelling of the polyamide fibers occurs on at least the napped surface of the suede-like sheet. 1. A method for dyeing napped suede of polyamide fibers, which comprises applying a composition solution containing an agent, heat-treating the product, and then dyeing it.