JP4021093B2 - Suede-like artificial leather having a pattern and method for producing the same - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a suede-like artificial leather used for clothing, gloves, shoes, bags, etc., having a patterned pattern and an elegant appearance.
[0002]
[Prior art]
Artificial leather with ultra-fine fiber napping has a high-grade appearance similar to natural leather suede and is uniform in quality, lightweight, and easy to care for. It is widely used in fields where natural leather is used such as shoes and bags.
However, the appearance was basically the same color, too uniform, and many monotonous things. In recent years, there has been an increasing demand for a changed appearance, and numerous attempts have been made to obtain artificial leather having a patterned pattern.
For example, after uniformly dyeing, applying a pigment with a gravure roll having a pattern is practiced. Also, pigment printing using a screen is widely performed.
Attempts have also been made to obtain an appearance having a handle pattern composed of a silver surface and a suede portion by grinding and removing a part of the silver surface.
[0003]
[Problems to be solved by the invention]
However, in the method of applying a pigment to the suede surface, a pattern can be obtained, but in the portion where the pigment is applied, the ultrafine fiber napping is collected and fixed by a binder resin for fixing the pigment. The lighting effect and graceful tactile feel are reduced. In addition, in the method of grinding a part of the silver surface, the appearance cannot be said to be suede, and the lighting effect and elegant touch feeling made of ultrafine fiber napping cannot be obtained.
[0004]
The present invention is a suede in which the entire surface is covered with ultrafine fiber napping, has a lighting effect and soft touch that are characteristic of suede, and has an elegant appearance brought out from a pattern with the same color tone or a different color tone. It is to provide artificial leather.
[0005]
[Means for Solving the Problems]
In order to achieve the above-mentioned object, the present inventors have conducted research, and as a result, it is possible to obtain a suede-like artificial leather having a patterned pattern while maintaining the suede appearance without impairing the ultrafine fiber napping. I found out.
That is, the present invention provides a three-dimensional entangled nonwoven fabric composed mainly of ultrafine fibers having a denier of 0.3 denier or less and a substrate surface composed of a polymer elastic body covered with napped fibers composed of the ultrafine fibers. Is a suede-like artificial leather characterized in that it has a pattern formed by two or more colors of the same hue which are not bonded and converged, or having the same hue.
[0006]
More preferably, in the above-described suede-like artificial leather, the napped portion of a part or all of the surface portion and the color density or hue of the base portion are different.
[0007]
The suede-like artificial leather according to the present invention can be obtained by sequentially performing the following steps (1) to (9).
(1) A step of curling staples mainly made of ultrafine fiber generating fibers that generate ultrafine fibers of 0.3 denier or less, and (2) a step of laminating the webs and needle punching into a nonwoven fabric. , (3) a step of pressing a needle punched nonwoven fabric, (4) a step of impregnating a polymer elastic body solution or dispersion and coagulating the polymer elastic body, (5) generating ultrafine fibers from ultrafine fiber generating fibers is, artificial leather based body obtained Ru process, and buffed with sandpaper substrate surface obtained (6), to obtain a surface napped, (7) applying a dye solution to the handle-like, (8) the coating (9) a step of dyeing the entire surface of the substrate using a dye in the dip dyeing method, and in this manufacturing method, steps (4) and (5) are reversed in order, ie, step (5). Do it first, Or a method of performing later step (4). Alternatively, it can also be obtained by sequentially performing the following steps (7) to (9) after the steps (1) to (6).
(7) Dyeing step of applying step (8) dye solution to the handle-like staining the entire substrate surface using a dye method, as engineering to fix the dye was applied (9),
It can also be obtained by sequentially performing the following steps (7) and (8) after the steps (1) to (6) .
(7) The step of applying the dye solution in a pattern on the napped surface and the step of applying the dye on the entire napped surface in two steps,
(8) a step of fixing the applied dye;
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The ultrafine fiber-generating fiber for generating ultrafine fibers (A) having a fineness of 0.3 denier or less used in the present invention is obtained by composite spinning or mixed spinning of two or more thermoplastic polymers having no compatibility. It is done. A typical fiber form is a so-called sea-island type cross-sectional fiber.
As the fiber island component polymer, a polymer that can be melt-spun and sufficiently exhibits fiber physical properties such as strength, a polymer having a higher melt viscosity and higher surface tension than the sea component polymer under the spinning conditions is preferable, such as 6-nylon, copolymers mainly 66- polyamide polymers such as nylon, and this, polyethylene terephthalate, polybutylene terephthalate polyester polymer, and copolymers mainly comprising this preferred Used for.
In addition, the sea component polymer has a lower melt viscosity than the island component polymer, has a different solubility and decomposability from the island component, and has a greater solubility in the solvent or decomposing agent used to dissolve and remove the sea component. A polymer having a low compatibility with the island component is preferable. For example, polyethylene, modified polyethylene, polypropylene, polystyrene, modified polyester and the like are preferably used.
[0009]
In the present invention, the preferred sea-island volume ratio of the ultra-fine fiber-generating fiber that generates the ultra-fine fiber (A) having a fineness of 0.3 denier or less, that is, the sea-island fiber is in the range of sea: island = 30/70 to 70/30. If the sea component is less than 30%, there are too few components to be dissolved or decomposed and removed with a solvent or a decomposing agent, etc., and sufficient flexibility cannot be expressed. If the sea component exceeds 70%, the island component after dissolution or decomposition is removed. It is inappropriate from the viewpoint of productivity that the absolute amount of the resulting fibers is small and sufficient physical properties as a leather-like sheet cannot be secured, and that many components are dissolved or decomposed and removed.
[0010]
The average fiber denier of the preferred island component after dissolving and removing the sea component in the present invention is 0.3 denier or less, preferably 0.1 denier or less, more preferably 0.05 denier or less. When the fiber denier of the island exceeds 0.3 denier, the flexibility of the substrate is impaired, and the texture becomes stiff. In particular, in the case of 0.1 denier or less, it becomes a suede-like one covered with fine napped fibers having a high-class feeling.
The ultrafine fiber-generating fiber is processed into a staple through processes such as drawing, crimping, heat setting, and cutting by a conventionally known method.
[0011]
For example, an oil agent such as silicon may be applied to the staple of the ultrafine fiber generating fiber. The types of oils include polyorganosiloxane, which has the effect of reducing the friction between fibers, various modified silicon-based oils, and the mineral oil-based oils that have the effect of reducing the friction between metals by combining the fibers. In addition, a known oil agent such as an antistatic agent is blended and applied in consideration of the properties of the fiber. The step of applying may be performed before crimping of each fiber, after crimping, or when both fibers are mixed. Different types of oil agents may be applied to the ultrafine fiber generating fiber. Extra fine fiber-generating fibers are prone to troubles such as wrapping and fiber cracking in the card and needle process, and therefore it is preferable to give oils with a focus on reducing the friction coefficient. Subsequently, the ultrafine fiber generating fiber staple can be obtained by laminating these webs by using a known method to form a random web or a cross-wrap web through a card and a webber.
[0012]
As the felt needle of the needle punch in the present invention, a known one is used, but a 1 barb needle that is less likely to cause fiber breakage is suitably used for sewing in the thickness direction of the web. Moreover, in order to raise the specific gravity of the surface of a nonwoven fabric, the needle | hook of multiple barbs, such as 3 barb, 6 barb, and 9 barb, can be used. These needles may be combined depending on the purpose.
[0013]
The number of punches in the needle punching process varies depending on the shape of the needle used and the thickness of the web, but is set in the range of 200 to 2500 punches / cm ² . Generally, in the needle punch of the ultra fine fiber generating fiber, if the needle punch condition is too strong, the ultra fine fiber generating fiber is cut or broken, the entanglement is not improved, and the needle punch condition is too weak. In some cases, the number of fibers arranged in the thickness direction is insufficient, and the entanglement is not improved, and it is difficult to obtain a high-quality suede surface having a beautiful fluff density.
[0014]
The needle punched nonwoven fabric is then pressed in the thickness direction to smooth the surface and regulate the thickness. A conventionally known method such as a method of passing between a plurality of heating rolls or a method of passing a preheated nonwoven fabric between cooling rolls can be used as a pressing method, and a sea component in an ultrafine fiber generating fiber, that is, a low melt viscosity component such as polyethylene Further smoothing of the nonwoven fabric can be achieved by melting and pressure bonding. In this step, a removable adhesive such as polyvinyl alcohol, starch or resin emulsion may be applied for the purpose of suppressing the change in the form of the step due to tension or pressing.
[0015]
The nonwoven fabric having a smooth surface is then impregnated with a polymer elastic body solution or dispersion and solidified in a sponge form. As the polymer elastic body, a resin conventionally used for producing a leather-like sheet is preferably used. That is, a polyurethane resin, a polyvinyl chloride resin, a polyacrylic acid resin, a polyamino acid resin, a silicon resin, a copolymer thereof, a mixture thereof, and the like are preferable. Of these, a polyurethane resin is preferred because it provides a natural leather-like texture and feel. These resins are impregnated into the nonwoven fabric as an aqueous emulsion or an organic solvent solution, and then solidified in a sponge form by wet coagulation or the like.
[0016]
The fibrous base material impregnated and solidified with the polymer elastic body solution or dispersion liquid is then a non-solvent for the ultrafine fibers and the polymer elastic body, and is a solvent or a decomposing agent for the sea component of the ultrafine fiber-generating fiber. By dissolving or decomposing and removing the sea component, ultrafine fibers of 0.3 denier or less are generated, and an artificial leather base made of ultrafine fibers and a polymer elastic body is obtained.
[0017]
The thickness of the artificial leather substrate can be arbitrarily selected according to the application and is not particularly limited, but is preferably 0.3 mm to 3 mm. The weight ratio between the fibrous material mainly composed of ultrafine fibers and the polymer elastic body is preferably 35/65 to 65/35 by weight. If it is out of this range, the balance between the fiber and the elastic polymer is deteriorated, and a sense of fulfillment and flexibility as a product cannot be obtained.
[0018]
Next, at least one surface of the artificial leather base composed of the ultrafine fiber entangled nonwoven fabric and the polymer elastic body is raised to form a fiber raised surface mainly composed of ultrafine fibers. As a method for forming the fiber raised surface, a buffing method using a sand paper or the like is representative after the substrate is adjusted to a desired thickness or before the thickness is adjusted. If the thickness is not adjusted, the thickness is adjusted to a desired thickness to obtain a napped fibrous substrate.
[0019]
In order to develop a pattern without impairing the napping of the obtained napped fibrous substrate, any of the following methods is used.
First, a dye solution is applied to a fibrous substrate in a pattern using a screen or the like, and the applied dye is fixed in hot water or the like, and a pattern is first dyed. Subsequently, the entire surface of the substrate is dyed using a dye by a dip dyeing method. In this way, the pattern dyed first remains, and the whole can be dyed in a predetermined color with the dye dyed later.
In this method, the pattern part dyed first will be dyed twice, resulting in a subtle shade with soft warmness that is blurred by the dye that arrived first and the dye after the dye, and dyed first. The nap of the handle portion is strongly dyed with a dye dyed later, and the color density or color tone of the base layer dyed earlier is different, and a subtle change is obtained.
[0020]
The following method may be used.
First, the napped fibrous substrate is dyed as a whole by the dip dyeing method, and then the dye solution is applied in a pattern with a screen or the like, the applied dye is fixed, and the pattern is first dyed. In this method, the pattern to be dyed later has a clearer boundary and color difference than the previous method, and a clear pattern can be obtained.
[0021]
Furthermore, the following method is also possible more simply.
That is, the entire napped fiber substrate is coated with the dye at once with a print roll or a screen or the like other than the pattern portion, and then the dye coated in hot water is fixed. However, in the case of this method, since it is difficult to obtain a deep color tone in the obtained pattern, it is inferior in terms of a high-quality color tone as compared with the above-described method.
[0022]
For the method of applying the dye to the napped fiber substrate, a print roll engraved with a pattern or a screen having slits in the pattern is preferably used. For dyeing by the dip dyeing method, conventionally known dyeing machines such as wins, dash lines, and circulars are used. The dye used for the pattern and the dye used for dyeing the entire pattern may be the same color or different colors. When the same color dyes are used, a pattern with color shading is obtained, and when different color dyes are used, a pattern with different color effects is obtained.
In the present invention, the pattern may be a multicolor pattern using a plurality of screens.
[0023]
The dye to be used is preferably a dye for dyeing polyamide ultrafine fibers and polyurethane, such as an acid dye or a metal complex dye, and a 2: 1 type metal complex dye is particularly preferable. Prior to dyeing with a 2: 1 type metal complex dye, it is preferable to preliminarily dye with a dye that does not reduce the fastness to washing such as a sulfur dye or a vat dye. In dyeing, the higher the dye concentration in the dyeing solution, the deeper the color is obtained. However, since the fastness to washing tends to be low, it is preferable that the dye concentration is 3% or less. It is also preferable to brush the dyed sheet in a wet state in order to improve fastness.
[0024]
The dye solution to be applied is preferably one in which the above dye is dissolved in water for handling, but a solution in an organic solvent can also be used. When an aqueous solution is used, a surfactant or a solvent such as isopropyl alcohol or dimethylacetamide may be added in order to facilitate application and penetration into the fiber napped substrate. The pattern to be applied may be any of a geometric pattern, a logo mark, a character pattern, a camouflage pattern, and the like.
[0025]
The dyed napped fibrous base material is subjected to finishing treatment such as light resistance treatment, stagnation, softening treatment, and brushing as necessary to obtain a fiber napped sheet product.
Since the suede-like artificial leather of the present invention is not colored with a pigment unlike the conventional patterned suede-like artificial leather, it is not necessary to use a binder resin for adhering the pigment to the napped surface. In the suede-like artificial leather, the napped fibers are not substantially bonded to each other, and therefore, a very important lighting effect is not impaired in the suede-like artificial leather.
The suede-like artificial leather of the present invention has the entire surface covered with ultrafine fiber napping, has a lighting effect and soft touch that are the characteristics of suede, and has an elegant appearance brought about by a pattern feeling with the same color tone or different color tone. It is suitable for interiors, shoes, bags, various gloves, etc. as well as for clothing.
[0026]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the examples, “part” and “%” relate to weight unless otherwise specified.
[0027]
Example 1
Island components using a multicomponent fiber manufacturing device that melts and spins a polymer stream melted in two extruder melt systems at the spinning head to form a mixed stream by repeating split and integration. Was made of 50 islands, and the sea component was made of high-fluidity low-density polyethylene (sea component / island component ratio = 40/60). The obtained yarn was drawn, crimped and cut to obtain staple fibers having a 3.5 denier and a cut length of 51 mm.
The staple fiber was passed through a card, made into a web by a cross wrapper method, and laminated. Next, a non-woven fabric having a weight per unit area of 450 g / m ² was obtained by needle punching with a needle penetration density of 980 P / cm ² using a felt needle with one barb on the needle. The nonwoven fabric was impregnated with a 10% PVA solution, squeezed, dried by heating, pressed to smooth the surface, impregnated with a 13% polyurethane dimethylformamide (abbreviated as DMF) solution, solidified with an aqueous DMF solution, and washed with hot water. Then, PVA was removed, and polyethylene as a sea component in the fiber was extracted and removed with hot toluene to obtain a base for artificial leather made of 6-nylon ultrafine fiber having a thickness of 0.045 denier and polyurethane. This artificial leather base is divided into two in the middle of the thickness, the divided surface is buffed with sandpaper to a thickness of 0.5 mm, and then the surface during solidification is treated with an emery buffing machine to form a raised surface, It was dyed into a lattice pattern under the following conditions.
<Dye solution>
Dye: Ilgaran Red 2GL 3%
Solvent: water / isopropyl alcohol = 70/30
The fiber raised sheet printed with a dye was treated in the following hot water and dyed.
<Dyeing>
Hot water temperature: 90 ° C
Immersion time: 10 minutes [0028]
After the fiber napping sheet was washed with water, it was further subjected to dip dyeing with a Wins type dyeing machine using the following 2: 1 type metal complex dye.
Dye: Ranil Blue BW (Sumitomo Chemical) 1.2%
Leveling agent: 1%
After dyeing, it was soaped, washed with water, dried and trimmed to obtain a suede-like artificial leather having a pattern with a thickness of 0.5 mm and a basis weight of 210 g / m ² . This suede-like artificial leather has the entire surface covered with ultra-fine fiber napping, and the napped fibers are not glued and fixed together with a binder, and it has the lighting effect and soft touch that are the characteristics of suede. It had an elegant appearance brought on by a certain pattern.
[0029]
Example 2
A sea-island mixed spun fiber, in which the island component is 6-nylon and the sea component is high fluidity low density polyethylene (sea component / island component ratio = 50/50), was melt-spun. The obtained fiber was drawn, crimped, and cut to obtain staple fiber having a 3.5 denier and a cut length of 51 mm.
The above staples were passed through a card, made into a web by a cross wrapper method, and laminated. Next, using a needle with one barb on the needle, needle punching was performed at a needle penetration density of 980 P / cm ² to obtain a nonwoven fabric having a basis weight of 450 g / m ² . This nonwoven fabric is heated, dried and pressed to smooth the surface, impregnated with 13% ether polyurethane DMF solution, coagulated with DMF aqueous solution, washed with hot water, and extracted and removed with hot toluene, 6-nylon An artificial leather base made of ultrafine fibers and polyurethane was obtained. This artificial leather base is divided into two in the middle of the thickness, the divided surface is buffed with sandpaper to make the thickness 0.5 mm, and then the solidified surface is treated with an emery buffing machine to form a raised surface, Under the following conditions, a print roll was used and dyed into a polka dot pattern.
<Dye solution>
Dye: Irgaran Yellow GRN 2%
Solvent: water / isopropyl alcohol = 70/30
The fiber raised sheet printed with the dye pattern was treated in the following hot water and dyed.
<Dyeing>
Hot water temperature: 90 ° C
Immersion time: 10 minutes [0030]
After the fiber napping sheet was washed with water, it was further subjected to dip dyeing with a Wins type dyeing machine using the following 2: 1 type metal complex dye.
Dye: Ranil Blue BW (Sumitomo Chemical) 1.2%
Leveling agent: 1%
After dyeing, soaping, washing with water, drying and hair shaping were performed to obtain a suede-like artificial leather having a pattern with a thickness of 0.5 mm and a basis weight of 210 g / m ² . This suede-like artificial leather has the entire surface covered with ultra-fine fiber napping, and the napped fibers are not glued and fixed together with a binder, and it has the lighting effect and soft touch that are the characteristics of suede. It had an elegant appearance brought on by a certain pattern.
[0031]
Example 3
First, the sheet obtained by napping with a buffing machine in Example 1 was subjected to dip dyeing under the following conditions.
Dye: Ranil Blue BW (Sumitomo Chemical) 1.2%
Leveling agent: 1%
After dyeing, it was soaped, washed with water and dried. The following dye solution was applied to the obtained uniformly dyed fiber napping sheet using a print roll in a staggered pattern <Dye Solution>
Dye: Irgaran Yellow GRN 5%
Solvent: water / isopropyl alcohol = 70/30
After applying the dye, it was dyed in hot water at 90 ° C., washed with water, dried and hair-stabilized, and a suede-like artificial leather having a pattern was obtained without impairing the napping of the entire surface. This suede-like artificial leather has the entire surface covered with ultrafine fiber napping, and the napped fibers are not glued and fixed together with a binder, and it has the lighting effect and soft touch that are the characteristics of suede, and it is clear with different colors It had a graceful appearance born from a sense of pattern.
[0032]
Example 4
Using a printing roll on the entire surface of the napped sheet obtained by buffing in Example 1, the dye solution including the lattice pattern was continuously applied in two portions, and dyed in hot water. A suede-like artificial leather having
Lattice pattern <dye solution>
Dye: Ilgaran Red 2GL 3%
Solvent: water / isopropyl alcohol = 70/30
Other parts <dye solution>
Dye: Ilgaran Yellow GRN 3%
Solvent: water / isopropyl alcohol = 70/30
<Dyeing>
Hot water temperature: 90 ° C
Immersion time: 10 minutes This suede-like artificial leather has the entire surface covered with ultrafine fiber napping, and the napped fibers are bonded and fixed together with a binder, and has the lighting effect and soft touch that are characteristic of suede, Furthermore, it had an elegant appearance brought about by vivid patterns with different colors. However, compared with the pattern patterns of Examples 1 to 3, the pattern pattern was slightly deep and slightly inferior in terms of luxury.
[0033]
Comparative Example 1
In Example 1, the napped fibrous substrate was dyed uniformly in red, and then a blue solution composed of a pigment and a PU binder was applied and dried by a gravure machine having a lattice pattern, in the same manner as in Example 1. Implementation, a suede-like artificial leather with a pattern was obtained.
Although this pattern has a pattern, the pattern portion to which the pigment liquid was applied had fuzz fixed with a binder, and the suede feeling was lost, the lighting effect was poor, and the tactile sensation was also impaired.
[0034]
Comparative Example 2
The surface of the artificial leather substrate in Example 1 was not buffed, and a polyurethane resin solution containing a red pigment was coated and dried to obtain a coating layer having a film thickness of 50 microns. This coating layer was pressed with a heating roll and smoothed.
Subsequently, a plate having a polka dot projection was placed on the back side of the substrate, and the coating layer of the projection was removed by buffing from the surface to obtain napped. As a result, an artificial leather having a contrast between a white polka dot raised portion and other silver-attached portions was obtained.
This one had a pattern and an interesting appearance, but was not suede.

Claims (5)

  The surface of the substrate composed of a three-dimensional entangled nonwoven fabric composed mainly of ultrafine fibers of 0.3 denier or less and a polymer elastic body is covered with the raised fibers made of the ultrafine fibers, and the raised fibers are substantially bonded to each other. A suede-like artificial leather characterized by having a patterned pattern formed by two or more colors of the same hue, which are not converged, or the same hue. A method for producing a suede-like artificial leather, comprising sequentially performing the following steps (1) to (9):
(1) A step of forming a web by curling staples mainly composed of ultrafine fiber-generating fibers that generate ultrafine fibers of 0.3 denier or less, (2) a step of laminating the web and needle punching to form a nonwoven fabric , (3) a step of pressing a needle punched nonwoven fabric, (4) a step of impregnating a polymer elastic body solution or dispersion and solidifying the polymer elastic body, (5) generating ultrafine fibers from ultrafine fiber generating fibers A step of obtaining an artificial leather substrate, (6) a step of buffing the surface of the obtained substrate with sandpaper to form napped on the surface, (7) a step of applying a dye solution in a pattern , (8) A step of fixing the applied dye, and a step of dyeing the entire substrate surface using the dye by the dip dyeing method. A method for producing a suede-like artificial leather, comprising sequentially performing the following steps (7) to (9) after the steps (1) to (6) according to claim 2 .
(7) a step of dyeing the entire surface of the substrate using a dye by a dip dyeing method , (8) a step of applying a dye solution in a pattern, (9) a step of fixing the applied dye, A method for producing a suede-like artificial leather, wherein the following steps (7) and (8) are sequentially performed after the steps (1) to (6) according to claim 2.
(7) A step of applying the dye solution to the napped surface in a pattern and a step of continuously applying the dye to the entire napped surface in two steps,
(8) a step of fixing the applied dye; The method of any one of Claims 2-4 WHEREIN: The manufacturing method of the suede tone artificial leather which reverses the order of a process (4) and a process (5).