TW201945617A - Napped artificial leather and method for manufacturing same - Google Patents

Abstract

Provided is a napped artificial leather including a non-woven fabric that is an entangled body of a fiber bundle including a single fiber of filaments that have a single-fiber fineness of 0.05-1 dtex, and a first polymer elastic body added to the non-woven fabric, the napped artificial leather being configured so that: in a thickness-direction cross section, there are provided a napped fiber layer that has a thickness of 100 [mu]m or greater and includes a napped single fiber, a first layer that is a 120-[mu]m-thick region continuous to the napped fiber layer, and a second layer that is continuous to the first layer; and a bundled-fiber-bundle proportion that is the ratio of the number of bundled fiber bundles to the total number of fiber bundles included in the first layer and the second layer is greater in the first layer than in the second layer. Also provided is a method for manufacturing the napped artificial leather.

Description

   Down artificial leather and manufacturing method thereof   

The present invention relates to fluff artificial leather which can be suitably used as a surface material of clothing, shoes, furniture, car seats, and miscellaneous goods.

The suede-like artificial leather of fluffy artificial leather has a fluffed surface by raising the surface of a fibrous base material containing a non-woven fabric impregnated with a polymer elastomer. For fluff artificial leather, abrasion resistance is required. In addition, since fluff artificial leather is usually colored, it is also required to have a fastness to rubbing that does not easily shift color to other materials due to friction.

Regarding the abrasion resistance of suede-like artificial leather, for example, the following Patent Document 1 is disclosed in an imitation leather sheet made of an ultrafine fiber and a polymer elastomer, and after the application of the polymer elastomer, the mixed fiber is extracted A method for producing a suede-like artificial leather obtained by adding a polymer elastomer to a polymer component again. Regarding the friction fastness of suede-like artificial leather, the following Patent Document 2 discloses a tangled nonwoven fabric composed of ultrafine fibers having an average single fineness of 0.1 denier or less, and a polyurethane contained therein. A suede-like artificial leather composed of a main polymer, which imparts a dye and a specific copolymer to the suede-like artificial leather. Further, regarding the rubbing fastness of nubuck-like artificial leather whose fluff is shorter than suede-like artificial leather, the following Patent Document 3 discloses a nubuck-like artificial leather sheet which is characterized in that The fiber fineness is 0.0001 to 0.5 dtex, and the apparent density is 0.300 to 0.700 g / cm3, which is composed of a short-fiber non-woven fabric. The fluff length is 1 to 500 μm, and a film system composed of an elastic polymer does not exist.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Application Laid-Open No. 51-75178

Patent Document 2: Japanese Patent Application Laid-Open No. 11-217773

Patent Document 3: Japanese Patent Application Laid-Open No. 2006-241620

Although the suede-like artificial leather obtained by the technique disclosed in Patent Document 1 has improved abrasion resistance, the polymer elastic body directly grasps the ultrafine fibers, so the hand feels hard. In addition, the suede-like artificial leather obtained by the technique disclosed in Patent Document 2 is considered to be hard on the surface because it is provided with a copolymer after forming a fiber fluff surface. Furthermore, the nubuck-like leather-like sheet-like article obtained by the technique disclosed in Patent Document 3 has low abrasion resistance.

In addition, with regard to the colored fluff artificial leather, the fastness to rubbing and fading (friction and fading) that does not fade when rubbed against other fabrics is required. In the past, in order to improve the friction and decoloring resistance of the colored fluff artificial leather, a coloring method with less color loss was reviewed. However, when only the coloring method is reviewed, it is difficult to sufficiently improve the friction and decoloring resistance.

An object of the present invention is to provide a fluff artificial leather which is excellent in friction and decoloring characteristics to solve the above-mentioned problems, and which suppresses the fiber from falling off when rubbed with other fabrics.

The present inventors intensively reviewed in order to improve the friction and decoloring resistance of the colored fluff artificial leather. Further, it was found that when the surface layer of the fluff artificial leather rubs against other fabrics and the fluff fibers fall off, the fastness to rubbing decoloration is reduced because the colored fluff fibers adhere to the fabric. Based on this knowledge, the present inventors conducted a review in order to suppress the loss of fibers when the down artificial leather rubs against the fabric. As a result, the following knowledge and insights were obtained: When the fluff artificial leather rubbed with the fabric, when the pile length of the fluffed fiber was short, the root of the fluff contacted the fabric and friction, and it broke due to abrasion, and the broken fiber system was collected to form The fabric is in the yarn, and the fabric is contaminated. Then, it was found that by fixing the root of the fluff fiber with resin and increasing the length of the fluff fiber, the fluff layer was thickened. The fluff layer became a buffer, and the root of the fluff fiber became difficult to contact the fabric. At the same time, the root of the fluff fiber was fixed. However, the fiber becomes difficult to break, and a fluff artificial leather with suppressed fiber fall-off when rubbing with other fabrics is obtained. Finally, the present invention was devised.

That is, one aspect of the present invention is a fleece artificial leather, which is a fleece artificial leather including a non-woven fabric and a first polymer elastomer imparted to the non-woven fabric. The non-woven fabric is a single fiber including a single fiber fineness of 0.05 to 1 dtex. The tangled body of the fiber bundle includes, in a cross section in the thickness direction, a fluff fiber layer having a thickness of 100 μm or more including a surface layer of fluffed single fibers, and a first region having a thickness of 120 μm connected to the fluff fiber layer. Layer, and the second layer, which is a region connected to the first layer, in each of the first and second layers, a bundle fiber bundle that is a ratio of the number of bundle fiber bundles to the total fiber bundle number The ratio is higher in the first layer than in the second layer. With such a fluff artificial leather, when rubbed against a fabric, a fluff fiber layer having a thickness of 100 μm or more becomes a buffer, which can suppress the fluff fibers from rubbing the fabric and abrasion. In addition, since the fiber bundles in the first layer forming the roots of the fluff fibers form the bundle fiber bundles at a higher ratio than the fiber bundles in the second layer, the soft hand feel is not impaired, and the roots of the fluff fibers are not easily worn away. Suppress fibers from falling out and falling off. As a result, with such a fluff artificial leather, the fibers can be prevented from falling off when rubbed against other fabrics. Furthermore, it is preferable that the void ratio of the bundled fiber bundle system is less than 7% from the viewpoint of sufficiently suppressing the abrasion of the fluff fibers.

In addition, the proportion of the number of bundled fiber bundles in the first layer of fluff artificial leather is 50% or more, and the proportion of the number of bundled fiber bundles in the second layer is 20% or less. It is more preferable from the viewpoint of excellent balance.

In addition, if the lightness L ^* value in the color coordinate space (L ^* a ^* b ^* color space) of the surface on the side of the fluff fiber layer is 50 or less, it is preferable from the standpoint that the effect of improving the anti-bleaching decoloring characteristic becomes significant .

The single fiber forming the bundled fiber bundle is preferably fixed by a second polymer elastomer that penetrates into the internal voids of the bundled fiber bundle. Also, it is preferable that the fluff artificial leather is in a plane direction and contains a second polymer elastomer of 0.5 to 3.0 g / m ² from the viewpoint that the ratio of the number of bundled fiber bundles in the first layer can be sufficiently increased.

In addition, those in which at least one of the fluff fiber layer and the first layer contains polysiloxane are preferable because the fluff fibers are prone to grow, and it is easy to form a fluff fiber layer having a thickness of 100 μm or more.

In addition, a single fiber containing a cationic dyeable PET dyed with a cationic dye or a pigment dyed PET is preferable from the viewpoint of suppressing the reduction in the friction and decoloring resistance caused by the fading of the dye. Moreover, since these fibers are easy to wear, it is preferable from the point that the improvement effect of abrasion resistance and a discoloration characteristic becomes remarkable.

Also, another aspect of the present invention is a method for manufacturing fluffy artificial leather, which includes a step of preparing an artificial leather grey fabric including a non-woven fabric and a first polymer elastomer provided with voids to the non-woven fabric. Entangled body of single-fiber bundles of long fibers with a fiber fineness of 0.05 to 1 dtex; a step of imparting a second polymer elastomer and a polysiloxane to at least one side of the artificial leather grey fabric; and the polishing treatment has imparted a second high Steps on the side of molecular elastomers and polysiloxanes. With such a manufacturing method, the aforementioned fluff artificial leather can be easily obtained.

Moreover, in the said manufacturing method, it is preferable to include the process of dyeing | staining with a cationic dye after a grinding process.

According to the present invention, a fluff artificial leather can be obtained, which suppresses the fiber from falling off when it is rubbed against other fabrics, which reduces the friction and decoloration resistance.

FIG. 1 is an example of a scanning electron microscope (SEM) photograph of a cross section in the thickness direction of the suede-like artificial leather of Example 1 taken at 300 times.

FIG. 2 is an example of a SEM photograph of the bundled fiber bundles observed in the first layer of the suede-like artificial leather of Example 1 at 1500 times.

FIG. 3 is an example of an SEM photograph of the fiber bundles observed in the second layer of the suede-like artificial leather of Example 1 taken at 1500 times.

FIG. 4 is a diagram for explaining a method for measuring the thickness of a fluff fiber layer, and is an example of a SEM photograph of a cross section in the thickness direction of the suede-like artificial leather of Example 1 taken at 100 times.

    [Form of Implementing Invention]    

First, the outline of the fluff artificial leather of this embodiment is demonstrated with reference to the photograph instead of a figure. FIG. 1 is an example of a scanning electron microscope (SEM) photograph of a cross section in the thickness direction of a suede-like artificial leather 10 having a total thickness of 500 μm at 300 times. The suede-like artificial leather 10 includes a non-woven fabric and The polymer elastic body 2 to the voids of the non-woven fabric is a entangled body of fiber bundles 1 consisting of 12 long fibers of single fibers 1a having an average single fiber fineness of 0.2 dtex. Part of the polymer elastomer 2 exists outside the fiber bundle as the first polymer elastomer 2a, and part of the polymer elastomer 2 exists inside the fiber bundle as the second polymer elastomer 2b, and is fixed to the single fiber 1a and bundled. In FIG. 1, 5 is a fluff fiber layer including the surface layer of the fluffed single fiber 1a, 6 is a first layer including the fiber bundle 1 connected to the fluff fiber layer 5, and 7 is a connection including the first layer The second layer of the fiber bundle 1 of 6.

In the suede-like artificial leather 10, as shown in FIG. 1, the fluff fiber layer 5 is a surface layer having a thickness of 100 μm or more in which fluff exists. The first layer 6 is a layer having a thickness of 120 μm from the boundary with the fluff fiber layer 5, that is, from the boundary between the fiber bundle 1 and the single fiber. The second layer 7 is a layer having a depth of 120 μm and lower from the boundary with the fluff fiber layer 5. The pile fiber layer 5 contains piled single fibers 1a. The first layer 6 and the second layer 7 include a plurality of fiber bundles 1 formed of twelve single fibers 1 a surrounded by a circle as shown in FIG. 1. The fiber bundle 1 includes a bundled fiber bundle to be described later in which single fibers are bundled. In each of the first layer 6 and the second layer 7, the ratio of the number of bundled fiber bundles to the ratio of the number of bundled fiber bundles to the number of all fiber bundles 1 is the ratio of the first layer 6 to the second. Layer 7 is higher. In other words, the ratio of the fiber bundles 1 included in the second layer 7 to the single fiber 1 a bundle is lower than that of the fiber bundles 1 included in the first layer 6, and the proportion of the opened fiber bundles is higher.

FIG. 2 is an example of an SEM photograph of the bundled fiber bundles observed in the first layer 6 at 1500 times. In addition, FIG. 3 is an example of an SEM photograph of the opened fiber bundle observed in the second layer 7 at 1500 times. The so-called bundled fiber bundle means a state in which, as shown in FIG. 2, most of the single fibers are fixed and there are few voids in the fiber bundle. On the other hand, the so-called open fiber bundle means a state in which, as shown in FIG. 3, most of the single fibers are unfixed and scattered, and there are many fiber bundles in the fiber bundle. More specifically, for example, the ratio of the porosity in the bundled fiber bundle-based fiber bundle is less than 7%, and the opened fiber bundle can also be said to be in a state where the ratio of the porosity in the fiber bundle exceeds 7%, for example. In addition, the porosity of the fiber bundle can be adjusted by trimming the fiber bundle facing the front side in the SEM photograph of the thickness direction cross section of the suede-like artificial leather taken at 300 times, that is, the fiber bundle of the side is almost invisible. The outer contour was obtained by binarizing the void portion and the non-void portion of the fiber bundle using image processing software. In FIGS. 1 to 3, the outer circumference of a fiber bundle composed of 12 single fibers with a cross section facing the front is surrounded by a circle. Further, in FIG. 1, 28 fiber bundles with a cross-section facing the front are observed in the first layer, and 27 fiber bundles with a cross-section facing the front in the second layer are observed.

Furthermore, in the suede-like artificial leather 10, the ratio of the number of bundled fiber bundles in the ratio of the number of bundled fiber bundles to the total number of fiber bundles in each of the first layer 6 and the second layer 7 is The first layer 6 is higher than the second layer 7. Further, in the suede-like artificial leather of this embodiment, the number ratio of the fiber bundle system bundle fiber bundles whose cross-section faces the front surface in the first layer is preferably 50% or more, more preferably 60% or more, and particularly preferably More than 80%. On the other hand, the number ratio of the fiber bundle-based bundle fiber bundles whose cross-section faces the front surface existing in the second layer is preferably 20% or less, and more preferably 10% or less. In such a case, a suede-like artificial leather can be obtained, which can maintain the soft feel while suppressing the loss of fibers during friction with other fabrics.

In addition, in the suede-like artificial leather 10, a pile fiber layer having a thickness of 100 μm or more including a surface layer of the raised single fibers is formed. The thickness of the pile fiber layer on the pile surface of the suede-like artificial leather is 100 μm or more. Therefore, when rubbing against the fabric, the fluff fiber layer serves as a buffer, and the fluff fibers can be prevented from rubbing against the fabric and abraded. The thickness of the fluff fiber layer is not particularly limited as long as it is 100 μm or more, but in terms of appearance uniformity, it is preferably 100 to 140 μm, and more preferably 100 to 120 μm.

In the above, to illustrate the suede-like artificial leather 10, the fluff artificial leather of the present embodiment includes a non-woven fabric and a first polymer elastomer imparted to the non-woven fabric. The non-woven fabric is a single fiber containing a single fiber fineness of 0.05 to 1 dtex. Entangled body of fiber bundles. In addition, the fluff artificial leather has a cross section in the thickness direction, and includes a fluff fiber layer having a thickness of 100 μm or more including a surface layer of fluffed single fibers, a first layer having a thickness of 120 μm connected to the fluff fiber layer, The second layer is a region connected to the first layer, and each of the first layer and the second layer includes a plurality of fiber bundles. In addition, part of their fiber bundles are bundled fiber bundles composed of single fibers, and the remaining fiber bundles are open fiber bundles that are not bundled with single fibers. The bundles included in each of the first and second layers The ratio of the number of bundled fiber bundles to the number of all fiber bundles has a form in which the first layer is higher than the second layer. With such a fluff artificial leather, while maintaining a soft feel, when rubbing against other fabrics, a fluff fiber layer having a thickness of 100 μm or more becomes a buffer, which suppresses the fluff fibers from rubbing against other fabrics and causing abrasion.

Hereinafter, the fluff artificial leather of this embodiment will be described in more detail while describing an example of a manufacturing method thereof.

The fluff artificial leather is produced, for example, by a manufacturing method including the following steps: a step of preparing an artificial leather grey fabric including a non-woven fabric and a first polymer elastomer provided with voids to the non-woven fabric, the non-woven fabric including a single fiber fineness of 0.05 to 1dtex single fiber long fiber fiber bundle entangled body; at least one side of artificial leather grey cloth, a step of imparting a second polymer elastomer and a polysiloxane; and a sanding treatment has been imparted to the second polymer elastomer and Polysilicone side step.

The procedure for preparing an artificial leather grey fabric is described. The artificial leather grey fabric includes a nonwoven fabric and a first polymer elastomer provided with a gap to the nonwoven fabric. The nonwoven fabric is a fiber bundle of single-fiber long fibers of 0.05 to 1 dtex. Tangled body.

The artificial leather grey cloth can be produced by melt-spinning a sea-island type composite fiber to produce a web, entangle the treated web, and apply fiber shrinkage by a heat shrinkage treatment such as water vapor or hot water or dry heat. The nonwoven fabric of the sea-island type composite fiber is processed, and the nonwoven fabric of the sea-island type composite fiber is impregnated with a first polymer elastomer, and the sea component is produced by removing the sea component from the sea-island-type composite fiber. Hereinafter, each step will be described in order.

As a method for producing a web by melt-spinning sea-island type composite fibers, sea-island-type composite fibers that are long fibers spun through a spinning bonding method and the like are collected on a web without being cut. (net) to form a long fiber web. In addition, a welding process may be applied to the formed net in order to give the form stability.

In addition, the so-called long fibers mean continuous fibers, not short fibers that are intentionally cut after spinning. More specifically, it means, for example, filaments or continuous fibers, not short fibers intentionally cut so that the fiber length becomes about 3 to 80 mm. The fiber length of the sea-island composite fiber before ultra-fibrillation is preferably 100 mm or more. As long as it can be technically manufactured and there is no unavoidable cutting in the manufacturing process, it can also be several meters, hundreds of meters, several kilometers or more. Fiber length.

In the sea-island type composite fiber, the type of the resin of the island component is not particularly limited. Specific examples include modified PET such as polyethylene terephthalate (PET), modified isophthalic acid PET, modified sulfoisophthalic acid PET, cationic dyeable PET, poly Aromatic polyesters such as polybutylene terephthalate, polyhexamethylene terephthalate, etc .; polylactic acid, polybutylene succinate, polybutylene succinate, polybutylene succinate Aliphatic polyesters such as diesters, polyhydroxybutyrate-polyvalerate resins; nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, nylon 6-12, etc .; polypropylene, polyethylene , Polybutene, Polymethylpentene, Polyolefins, etc. The fluff artificial leather of this embodiment is usually colored and used. Therefore, for the purpose of improving the rubbing fastness and suppressing the decrease in rubbing fastness due to the color shift of the coloring material, when a cationic dye is used as the dye, a cationic dyeable PET is preferably used.

In addition, as the resin of the sea component, a polymer having a higher solubility in a solvent or a decomposability due to a decomposing agent than the resin of the island component is selected. In addition, the polymers with low affinity to the island component polymer and having a lower melt viscosity and / or surface tension than the island component polymer under spinning conditions are derived from the point that the sea island type composite fiber has excellent spinning stability. Look better. Specific examples of such a sea-component resin include, for example, a water-soluble polyvinyl alcohol resin (water-soluble PVA), polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, and ethylene-vinyl acetate. Copolymers, styrene-ethylene copolymers, styrene-acrylic copolymers, and the like. Among these, water-soluble PVA does not use an organic solvent and can be dissolved and removed by an aqueous medium, which is preferable from the viewpoint of low environmental load.

The average fineness of the sea-island type composite fiber is not particularly limited. In addition, the average area of the sea component and the island component in the cross section of the sea-island composite fiber is preferably 5/95 to 70/30, and more preferably 10/90 to 50/50. The number of domains of the island components in the cross-section of the sea-island type composite fiber is not particularly limited, but from the viewpoint of industrial productivity, it is preferably 5 to 1,000, more preferably 10 to About 300.

The entanglement treatment system may include using a cross-laying machine, etc., after laminating a plurality of long fiber webs in the thickness direction, and under the condition that at least one hook is penetrated, simultaneously or alternately needling treatment or high pressure is performed from both sides thereof. Water entanglement processing method. In addition, an oil agent or an antistatic agent may be added to the long-fiber web at any stage from the spinning step of the sea-island type composite fiber to the entanglement treatment.

Then, for the entangled long-fiber web, the entangled state of the long-fiber web can be adjusted or smoothed by performing a fiber shrinkage treatment such as a heat shrinkage treatment such as water vapor or hot water or dry heat, or a heat-pressing treatment. State, a non-woven fabric of sea-island type composite fibers can be obtained.

The nonwoven fabric of the sea-island type composite fiber is impregnated with a resin solution containing a first polymer elastomer, and the first polymer elastomer is cured. Specific examples of the first polymer elastomer include polyurethane, acrylonitrile elastomer, olefin elastomer, polyester elastomer, polyamide elastomer, and acrylic elastomer. Among these, polyurethane is preferable. The resin liquid of the first polymer elastomer may be an emulsion or a solution. In addition, in the polymer elastomer, a coloring agent such as carbon black or a dye, a coagulation regulator, an antioxidant, an ultraviolet absorber, a fluorescent agent, a mold inhibitor, a penetrating agent, an antifoaming agent, Lubricants, water repellents, oil repellents, thickeners, extenders, hardening accelerators, foaming agents, water-soluble polymer compounds such as polyvinyl alcohol or carboxymethyl cellulose, inorganic particles, conductive agents, etc. .

唑啉系交聯劑、氮

系交聯劑等交聯劑，而形成交聯構造。 In addition, as the first polymer elastomer, it is particularly preferred to use an emulsion containing a crosslinkable polyurethane and impregnated and crosslinked the polyurethane. In the subsequent step, the crosslinked polyurethane is difficult to dissolve or swell even if a solution of the second polymer elastomer polyurethane which has been dissolved in the solvent is applied. More appropriate. Examples of the crosslinkable polyurethane include a polyurethane having a functional group such as a carboxyl group or a sulfonic acid group capable of forming a crosslinked structure, or a functional group such as a hydroxyl group. Crosslinkable functional urethane. Specifically, for example, as a monomer unit which forms a polyurethane chain, the side chain of a polyurethane chain contains the acid group, such as a carboxyl group or a sulfonic acid group, and activity, such as a hydroxyl group or an amine group, is mentioned. A functional group of hydrogen, or a polyurethane of a polyfunctional monomer unit such as a functional group that maintains self-crosslinkability. In the formation of the crosslinked structure, a carbodiimide-based crosslinking agent, an epoxy-based crosslinking agent,

Oxazoline crosslinking agent, nitrogen

It is a crosslinking agent such as a crosslinking agent to form a crosslinked structure.

The content rate of the first polymer elastomer contained in the down artificial leather is not particularly limited, but it is preferably 5 to 50% by mass, and more preferably 8 to 45% by mass. When the content rate of the first polymer elastomer is too high, the softness tends to decrease. When the content of the polymer elastomer is too low, abrasion resistance tends to decrease.

Furthermore, by removing the sea component from the sea-island type composite fiber of the sea-island type composite fiber, an artificial leather grey fabric containing a non-woven fabric and a first polymer elastomer having voids provided to the non-woven fabric is produced. A tangled body of single-fiber bundles of long fibers with a fiber fineness of 0.05 to 1 dtex. As a method for removing the sea component from the sea-island type composite fiber, a method of treating the non-woven fabric of the sea-island type composite fiber with a solvent or a decomposing agent capable of selectively removing only the sea component may be mentioned. Then, the artificial leather grey fabric may be cut in the thickness direction to adjust the thickness as necessary, and processed into an artificial leather grey fabric having a predetermined thickness.

The artificial leather grey fabric thus obtained includes a nonwoven fabric and a first polymer elastic body provided with voids to the nonwoven fabric. The nonwoven fabric is an entangled body of fiber bundles of single fibers including long fibers having a single fiber fineness of 0.05 to 1 dtex.

Then, in the artificial leather grey cloth thus obtained, a second polymer elastomer and a polysiloxane are provided on at least one side where the fluff is formed in a subsequent step.

In the manufacturing method of the present embodiment, before the sanding process is performed to form fluff on the fluff-forming surface of the artificial leather gray fabric, the resin liquid containing the second polymer elastomer is dried and dried to increase the second height. The molecular elastomer is cured. With this treatment, in the fluff-forming surface of the artificial leather gray fabric, the gap between the fiber bundles of the single fibers including the long fibers in the surface layer portion is impregnated by the capillary phenomenon and the resin liquid system containing the second polymer elastomer is impregnated. . Then, the resin liquid which has penetrated the space of the fiber bundle is dried, and the dispersed single fiber system forming the fiber bundle is bundled and fixed by the second polymer elastomer. By such a treatment, a bundled fiber bundle including bundled single fibers as shown in FIGS. 1 and 2 is formed. After forming a bundle of fiber bundles in the surface layer at a high ratio, the root layer of the fluff fiber is firmly fixed by sanding the surface layer. Even when rubbing with other fabrics, the root of the fluff fiber becomes difficult to wear, and the fiber dispersal is also suppressed. .

The second polymer elastomer provided on the fleece-forming surface of the artificial leather grey fabric may be the same as or different from the first polymer elastomer. Specific examples include polyurethane, acrylonitrile elastomer, olefin elastomer, polyester elastomer, polyamide elastomer, acrylic elastomer, and the like. Among these, polyurethane is preferable.

In addition, as the second polymer elastomer, in particular, from the viewpoint of easily penetrating the voids in the fiber bundle, it is preferable to apply a polyurethane solution, for example, which is contained in N, N-dimethylformate. Solvent-type polyurethane which is dissolved in a solvent of a well-known polyurethane such as fluorenamine (DMF) or cyclohexanone.

The amount of the second macromolecular elastomer provided on the fluff-forming surface of the artificial leather grey fabric is preferably 0.5 to 3.0 g / m ^{2 in} the plane direction of the fluff artificial leather, and more preferably 0.75 to 2.0 g / m ² . When the amount of the second polymer elastomer is within this range, the fluff surface formed later is not too hard, and it is easy to form a bundle fiber bundle near the root of the fiber at a high ratio, and it is easy to form a moderate content by polishing. The length of the fluffed single fiber having a thickness of 100 μm or more is preferred from the viewpoint of a fluff fiber layer. When the amount of the second polymer elastomer is too small, it tends to become impossible to form a bundled fiber bundle at a high ratio. In addition, when the amount of the second polymer elastomer is too large, it becomes difficult to form a fluff fiber layer having a thickness of 100 μm or more including a single fiber having a moderate length by polishing.

In addition, it is preferable that the surface of the artificial leather grey fabric to be formed with a pile is preferably coated with a solution or an emulsion containing a polysiloxane before being subjected to a sanding process for forming the pile, and then the polysiloxane is provided by drying. With this treatment, the gap between the fiber bundles of the single fibers including the long fibers in the surface layer portion is permeated by the capillary phenomenon, and similar to the second polymer elastomer, polysiloxane is also penetrated. The polysiloxane provided in this way functions as a sliding material, and it is easy to form a fluff having a length capable of forming a fluff fiber layer having a thickness of 100 μm or more by subsequent polishing. In detail, when the surface layer containing the bundled fiber bundles in a high proportion is sanded with sandpaper or emery paper, as described later, the friction with the single fibers is reduced, and the single fibers can be prevented from being cut excessively. Excessively short.

As the polysiloxane provided on the fluff-forming surface of such an artificial leather grey fabric, various polysiloxanes having film-forming properties are more preferably used, and more specifically, amine-modified polysiloxanes.

The amount of polysiloxane provided on the fluff-forming surface of the artificial leather grey fabric is not particularly limited, but is preferably 0.05 to 0.7 g / m ² , and more preferably 0.09 to 0.5 g / m ² . When the amount of the polysiloxane is in such a range, it becomes easy to form a fluff fiber layer having a thickness of 100 μm or more including a single fiber having a moderate length by grinding by polishing. When the amount of polysiloxane is too small, the length of the fluff becomes short, and it becomes difficult to form a fluff fiber layer of 100 μm or more. When the amount of polysiloxane is too large, there is a tendency that the fluff becomes too long or it becomes difficult to form fluff.

The second polymer elastomer and polysiloxane provided on the fleece-forming surface of the artificial leather gray cloth are dried by applying a solution or emulsion containing them, for example, by a coating method such as gravure coating and the like. And given. At this time, for example, if a method such as gravure coating is applied while pressing an artificial leather gray fabric with a nip roller, it is preferable to allow the second polymer elastomer and polysiloxane to penetrate the fibers of the surface layer more effectively. bundle. The second polymer elastomer and the polysiloxane may be applied simultaneously or may be applied in separate steps. In addition, after applying either of the solution containing the second polymer elastomer or the polysiloxane, another solution may be applied before drying, or the other solution may be applied after the previously applied solution is dried.

Then, the suede-like artificial leather having a fluff fiber layer of 100 μm or more can be obtained by sanding the surface of the artificial leather gray cloth provided with the second polymer elastomer and the polysiloxane. Examples of the sanding method include a method of using sandpaper or emery paper, which preferably has a number of 120 to 600, and more preferably 240 to 600. In this way, a suede-like artificial leather can be obtained which has a napped surface in which napped fibers are present on one or both sides.

For fluff artificial leather, shrinkage processing or kneading softening treatment to impart softness to adjust the feel can be further applied, or anti-seal combing treatment, antifouling treatment, hydrophilization treatment, lubricant treatment, softness Agent treatment, antioxidant treatment, ultraviolet absorbent treatment, fluorescent agent treatment, flame retardant treatment and other processing.

Down artificial leather is usually colored. Examples of the coloring method include a method in which a single fiber formed of a non-woven fabric is mixed with a pigment and colored (a dope dyeing method), or a method in which fluff artificial leather that is not dyed with a dope is dyed.

The dye system for dyeing fluff artificial leather is appropriately selected depending on the type of the fiber. For example, when the fiber is formed from a polyester resin, it is preferably dyed with a cationic dye or a disperse dye.

系陽離子染料；C.I.鹼性藍54、C.I.鹼性藍159、C.I.鹼性紅29、C.I.鹼性紅46等之偶氮系陽離子染料；C.I.鹼性黃40等之香豆素系陽離子染料；C.I.鹼性黃21等之次甲基系陽離子染料；C.I.鹼性黃28等之次甲基偶氮系陽離子染料；C.I.鹼性紫11等之呫噸系紫色陽離子染料等。此等係可單獨使用，也可組合2種以上而使用。 Specific examples of the cationic dye include CI Basic Blue 3, CI Basic Blue 6, CI Basic Blue 10, CI Basic Blue 12, CI Basic Blue 75, CI Basic Blue 96, and the like.

Cationic dyes; CI basic blue 54, CI basic blue 159, CI basic red 29, CI basic red 46 and other azo cationic dyes; CI basic yellow 40 and other coumarin cationic dyes; CI Methylene cation dyes such as Basic Yellow 21; methine azo cationic dyes such as CI Basic Yellow 28; xanthene purple cationic dyes such as CI Basic Yellow 11. These systems can be used alone or in combination of two or more.

Specific examples of the disperse dye include benzoazo dyes (monoazo, disazo, etc.), and heterocyclic azo dyes (thiazoleazo, benzothiazoleazo, and quinolineazo). , Pyridine azo, imidazole azo, thiophene azo, etc.), anthraquinone-based dyes, condensation dyes (quinophthaloline, styryl, coumarin, etc.) and the like. These systems can be used alone or in combination of two or more.

As the dyeing method, a dyeing method such as a high-pressure liquid flow dyeing method, a roll dyeing method, a hot-melt continuous dyeing machine method, and a sublimation printing method can be used without particular limitation.

The purpose of the fluffed artificial leather of this embodiment is to improve the friction and decolorization resistance of non-color shifting to other fabrics when rubbing with other fabrics. Therefore, as a coloring method, from the viewpoint of obtaining fuzz artificial leather with excellent rubbing fastness, it is particularly preferable to use a dope dyeing method in which a single fiber formed of a non-woven fabric is mixed with a pigment and colored, or a cationic dye that is not easily faded. The method of dyeing, or a combination of them.

In addition, the fluff artificial leather of this embodiment exhibits a remarkable effect particularly when dyed to a dark color. In detail, when the fluff artificial leather is colored dark, when the fluff artificial leather rubs against other fabrics, not only the dye itself moves to other fabrics, but also the colored fluff fibers that fall off due to abrasion will adhere to other fabrics. Cloth and pollution. The fluffed artificial leather of this embodiment is particularly difficult to cause the fibers to fall off due to abrasion. Therefore, it is possible to suppress the fibers that are colored to a dark color from falling off and attach to other fabrics. From such a point of view, the value of the lightness L ^{* in} the color coordinate space (L ^* a ^* b ^* color space) of the surface of the fluff fiber layer of the fluff artificial leather is 50 or less, especially 40 or less The darker ones are more suitable in that when they are rubbed against other fabrics, the effect of suppressing the staining of other fabrics due to the detachment of the colored fibers becomes significant.

The average fineness of the single fibers forming the fiber bundle as described above is preferably 0.05 to 1 dtex, more preferably 0.1 to 0.5 dtex, and particularly preferably 0.1 to 0.3 dtex. When the average fineness of the single fibers forming the fiber bundle is less than 0.05 dtex, the fibers become easily abraded and fall off when rubbed against other fabrics. When the average fineness of the single fibers forming the fiber bundle exceeds 1.0 dtex, there is a tendency that the fluff fibers become hard, or the soft feel of the fluff artificial leather tends to decrease.

The thickness of the fluff artificial leather is not particularly limited, but it is preferably 0.3 to 1.5 mm, and more preferably 0.4 to 1.0 mm. The weight per unit area of the fluffed artificial leather is not particularly limited, but it is preferably 150 to 600 g / m ² , and more preferably 200 to 500 / m ² .

In addition, the apparent density of fluff artificial leather is not particularly limited, but it is preferably 0.4 to 0.7 g / cm ³ , and more preferably 0.45 to 0.6 g / cm ^3. From this, an excellent balance between fullness and soft feel can be obtained. From the point of fluff artificial leather, it is more suitable.

As described above, the fluff artificial leather of this embodiment can obtain a suede-like artificial leather, which suppresses the loss of fibers during friction with other fabrics, which reduces the friction and decoloring resistance. Preferably, when the lightness L ^* value in the color coordinate space (L ^* a ^* b ^* color space) of the surface of the fluff fiber layer is 50 or less, and when the color is darker than 40, it is determined as described later. The fastness to abrasion and discoloration is preferably 4 or more when dry, and 3 or more when wet.

    [Example]    

Hereinafter, the present invention will be described more specifically with reference to examples. The scope of the present invention is not limited at all by the examples.

    [Example 1]    

The sea-island type composite long fiber is entangled in three dimensions to prepare a sea-island type composite long-fiber non-woven fabric, which contains ethylene-modified polyvinyl alcohol as a sea-based thermoplastic resin, and is modified by tetrabutylphosphonium salt of sulfoisophthalic acid. High quality polyethylene terephthalate (cationically dyeable PET) is used as the thermoplastic resin for the island component, and the mass ratio of the sea component to the island component is sea component / island component = 25/75.

Then, the first polyurethane is imparted to the nonwoven fabric of the sea-island type composite long fiber by impregnating the polyurethane emulsion with a 150 ° C drying oven. In addition, as the polyurethane emulsion, an emulsion is used which contains a self-emulsifying polyurethane having a crosslinked structure formed by a crosslinking agent after drying, and is blended with a carbodiimide-based crosslinking agent.联 剂。 Union agent. Then, the sea-island type composite long-fiber nonwoven fabric to which the first polyurethane is given is immersed in hot water at 95 ° C for 20 minutes, and dip-nip is dipped to remove the sea-islands. The non-woven fabric containing the first polyurethane and impregnated polyester fibers with impregnated polyester fibers was dried in a drying oven at 120 ° C to obtain a non-woven fabric containing cationic dyeable polyester fibers and the first polymer. Raw material of urethane artificial leather grey cloth. Then, the nonwoven fabric provided with the first polyurethane was cut in the thickness direction and divided into two parts to obtain an artificial leather grey fabric. The obtained artificial leather grey fabric includes a nonwoven fabric and a first polyurethane having a gap provided to the nonwoven fabric, and the nonwoven fabric is an entangled body of a single fiber fiber bundle including a cationic dyeable PET fiber having a single fiber fineness of 0.2 dtex. The content ratio of the first polyurethane is 10% by mass and the thickness is 0.65mm.

Next, a second polyurethane is applied to the artificial leather grey cloth. Specifically, on one side of the artificial leather grey cloth, a DMF solution (solid content: 5%) of polyurethane was passed between a 55-mesh gravure roll and a support roll to perform gravure coating, and dried. The coating amount was 2.00 g / m ² when dried. In addition, the first polyurethane is not dissolved or swelled by coating the polyurethane with a DMF solution.

Then, on one side of the artificial leather grey cloth provided with the second polyurethane, a solution of polysiloxane (amino-modified polysiloxane, solid content: 27.0%) was passed through a 150-mesh gravure roll and a support roll Gravure coating was performed at one time and then dried. The coating amount is an amount of 0.14 g / m ² of amine-modified polysiloxane when dried.

Then, using # 240, # 400, and # 600 sandpaper, the surface imparted with the second polyurethane and polysiloxane was polished at a speed of 3.0 m / min to obtain a suede made of fluffed artificial leather. Artificial leather. Then, in a dye solution at 90 ° C containing Nichilon Red-GL (manufactured by Nissin Kasei Co., Ltd.) at 9.4% owf as a cationic dye and 90% acetic acid as 1 g / L as a dyeing aid, a bath ratio of 1:30 , Dipping suede-like artificial leather for 40 minutes, and dyed red. Then, in the same dyeing bath, using a hot water bath containing Soldine R 2g / L as an anionic surfactant, the soaping step was repeated twice at 70 ° C. Then, after soaping, dyed suede-like artificial leather was obtained by drying. 1 to 4 are SEM photographs of a cross section of the obtained suede-like artificial leather.

Then, the obtained suede-like artificial leather was evaluated according to the following evaluation method.

<Determination of Thickness of Fluff Fiber Layer>

Using a scanning electron microscope, an arbitrary cross section parallel to the thickness direction of the suede-like artificial leather was taken at 100 times to obtain an SEM photograph. Then, the obtained SEM photograph was enlarged to A4 size. Then, as shown in FIG. 4, in the SEM photograph enlarged to A4 size, curve A is drawn along the boundary with the first layer connected to the fluff fiber layer. A curve B is drawn along the boundary connecting the apexes of the fluff fibers forming the fluff fiber layer. The straight line B is drawn so that the vertices of the fluff fibers are aligned along the focus existing in the cross section of the suede-like artificial leather. Then, along the curve A and the curve B, a plurality of straight lines Pn (P ₁ , P ₂ , P ₃ ‧‧‧ P ₁₂ ) parallel to the thickness direction are drawn at intervals of 100 μm. Then, the lengths of the line segments from the curve A to the curve B on the straight line Pn are measured. Then, the lengths of the line segments on each of the 12 different straight lines Pn are obtained, and their average values are obtained. In five SEM photographs, the average value was measured in the same manner, and the average value of each average value was taken as the thickness of the fluff fiber layer.

<Measurement of the ratio of the number of bundled fiber bundles in the first layer>

Using a scanning electron microscope, an arbitrary cross section parallel to the thickness direction of the suede-like artificial leather was taken at 300 times, and an SEM photograph was obtained. Then, in the SEM photograph taken at 300 times, from the boundary line between the fluff fiber and the fiber bundle as shown in FIG. 1, the cross section existing in the first layer defining a 120 μm-thick area faces the fiber bundle on the front side. Then, the image processing software image-proplus was used to determine the porosity of each fiber bundle. Then, among the porosity of each fiber bundle, the number of fiber bundles having a porosity of the fiber bundle bundle less than 7% was counted. Then, the ratio of the number of fiber bundles with a porosity of less than 7% to the number of defined fiber bundles was obtained. In the five SEM photographs, the ratio of the number of fiber bundles with a porosity of less than 7% was similarly calculated, and the averaged values were taken as the ratio of the number of bundle fiber bundles in the first layer.

<Measurement of the ratio of the number of bundled fiber bundles in the second layer>

In the lower layer portion of the area below the first layer as shown in FIG. 1, similar to the “measurement of the ratio of the number of bundled fiber bundles in the first layer”, the porosity was found to be less than The ratio of the number of fiber bundles of 7%, and their average values are taken as the ratio of the number of bundle fiber bundles in the second layer.

<Fastness to rubbing and discoloration>

The ATLAS abrasion fastness tester CM-5 (manufactured by ATLAS ELECTRIC DEVICES CO) was used to measure the fastness to abrasion and discoloration when dry and wet. In the case of fastness to rubbing and decoloring during drying, a dry cotton white cloth is mounted on a friction member made of glass, and a suede-like artificial leather is formed on the surface with a pile fiber layer, so that the cotton mounted on the friction member The white cloth was contacted under a load of 900g, and returned 10 times. Then, the cotton cloth was removed, and a scotch tape (Cellotape, registered trademark) was attached to the contaminated part. After a 1.5-pound cylindrical load was rolled back and forth once, the scotch tape was peeled from the cotton cloth. On the other hand, in the case of fastness to rubbing and decoloration when wet, a moistened cotton cloth, which is immersed in distilled water and removed from excess water, is mounted on a glass friction member. The face with the fluff fiber layer was formed, and the cotton white cloth attached to the friction member was brought into contact under a load of 900 g, and back and forth 10 times. Then, the cotton cloth was removed and dried at 60 ° C or lower. Then, a transparent tape was affixed to the contaminated part, and a 1.5-lb. Cylindrical load was rolled back and forth once, and then the transparent tape was peeled from the cotton cloth. Then, the gray scale for contamination (grade 5 to grade 1) was used to determine the fastness to rubbing and decoloring when dry and wet, and the color change of cotton cloth.

<Evaluation of hair loss>

On the red rubber bolt No. 20 with a diameter of 63 mm, a metal plate with a load and a polyethylene sheet with a thickness of 1 mm were sequentially laminated to form a friction member with a total weight of 400 g. Then, cover the side of the polyethylene sheet of the friction member with a white cloth (cotton-blended wide cloth (E / C = 65/35)), wind it up, and fix it with rubber bands in the state of stretched wrinkles. Then, the white cloth of the friction member was brought into contact with the surface of the suede-like artificial leather on which the fluff fiber layer was formed, and back and forth 4 times in a 25 cm interval at a speed of 4 seconds. Moreover, the load is only the weight of the friction member itself. Then, the following criteria were used to determine the adhesion of the fibers (fine hairs) that fell off after 4 round trips to the white cloth. In addition, for example, the intermediate system between 4th level and 5th level is judged to be 4.5 level.

Level 5: Fine hairs are not attached to white cloth at all, and it is a level 5 gray scale for pollution.

Level 4: Very fine hairs are sparsely attached to the white cloth, and the gray scale scale for pollution is 4-5.

Level 3: Small fine hairs are sparsely attached to white cloth, which is a level 4 gray scale for pollution.

Level 2: Small fine hairs are moderately attached to white cloth, which is a gray scale scale of 3-4 for pollution.

Level 1: Large and small fine hairs are attached to white cloth, and the gray scale scale for pollution is below level 3.

<L ^* value>

L ^* a ^* b * from the surface of the fluff fiber layer of the dyed suede-like artificial leather cut out using a spectrophotometer (Hitachi Hi-Tech Scientific Co., Ltd .: U-3010) in accordance with JIS Z 8729 Coordinate values of the color system, and obtain the lightness L ^* . The value is an average of three points measured by selecting an average position from all the test pieces.

<Lifting>

According to JIS L 1076 (Test method for lifting of woven fabrics and knitted fabrics) Method A (method using an ICI type lifting tester), evaluation of the surface of the test piece of the suede-like artificial leather with the pile fiber layer formed (Pilling). Specifically, a 100 mm × 120 mm test piece was wound outward with a pile fiber layer, and wound around a rubber tube for a lifting test. Then, the test piece wound around the rubber tube was set into four groups, and placed in 23 cm on the inner side of the ICI hoisting tester, in a cube-shaped rotating box covered with cork board, and placed in groups of four. The test piece was rotated for 10 hours or 20 hours. Then, the test piece was detached from the rubber tube, and the test piece was compared with the standard photograph of the judging judgment, and the occurrence degree of the jutting was judged on a scale of 5 (good) to 1 (poor).

<Exterior>

The fluffed surface of the obtained suede-like artificial leather was evaluated as follows, and the touch of the surface was confirmed by five reviewers, and the uniformity and roughness were judged by the following criteria.

A: Three or more persons judged that the state of the surface was uniform, and there was no rough feeling, and the appearance was good.

B: Three or more persons judged that the state of the surface was uneven and rough appearance.

<Feel>

The suede-like artificial leather obtained by bending was compared with the suede-like natural leather, and the difference in toughness or softness was judged by five reviewers using the following criteria.

A: Three or more persons judged a texture excellent in the balance between fullness and softness.

B: Three or more people judged a hard feel.

The results are shown in Table 1.

    [Example 2]    

A suede was produced in the same manner as in Example 1 except that the second polyurethane solution was applied at a coating amount of 2.00 g / m ² during drying and was coated at a coating amount of 1.25 g / m ² . Shape artificial leather for evaluation.

The results are shown in Table 1.

    [Example 3]    

A suede was produced in the same manner as in Example 1 except that the second polyurethane solution was applied at a coating amount of 2.00 g / m ² during drying, and was coated at a coating amount of 0.75 g / m ² . Shape artificial leather for evaluation. The results are shown in Table 1.

    [Example 4]    

Except in Example 1, a non-woven fabric comprising a tangled body of fiber bundles of single fibers of a cationic dyeable PET having a single fiber fineness of 0.2 dtex was formed to have a cationic dyeability of 0.1 dtex having a single fiber fineness of 0.1 dtex. The non-woven fabric of the entangled body of the fiber bundle of 6 mol% modified PET monofilament was replaced with 10% by mass of the first polyurethane, and changed to 14% by mass, instead of using A second polyurethane solution was applied at a coating amount of 2.00 g / m ² , and a suede-like artificial leather was produced in the same manner except that the coating was applied at a coating amount of 1.25 g / m ² . Then, instead of dyeing with cationic dyes, the suede-like artificial leather was dyed with disperse dyes, and fluffy artificial leather was obtained by alkali reduction, acid washing, and water washing treatments. Then, the obtained fluff-like artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

    [Example 5]    

Except in Example 1, a non-woven fabric instead of a tangled body of fiber bundles containing single fibers of cationic dyeable PET having a single fiber fineness of 0.2 dtex was formed to contain a single fiber fineness of 0.1 dtex containing 5.0% by mass of carbon black. The non-woven fabric of the entangled body of the fiber bundle of the single fiber of 6 mol% modified isophthalate is replaced by 10% by mass of the first polyurethane, and replaced by 14% by mass, instead of being dried A second polyurethane solution was applied at a coating amount of 2.00 g / m ² , and a suede-like artificial leather was produced in the same manner except that the second polyurethane solution was applied at a coating amount of 1.25 g / m ² . Then, instead of dyeing with cationic dyes, the suede-like artificial leather was dyed with disperse dyes, and fluffy artificial leather was obtained by alkali reduction, acid washing, and water washing treatments. Then, the obtained fluff-like artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

    [Example 6]    

A suede was produced in the same manner as in Example 1 except that the second polyurethane solution was applied at a coating amount of 2.00 g / m ² during drying and the coating was applied at a coating amount of 0.40 g / m ² . Shape artificial leather for evaluation. The results are shown in Table 1.

    [Example 7]    

Except in Example 1, a non-woven fabric instead of a tangled body of fiber bundles of single fibers of cationic dyeable PET having a single fiber fineness of 0.2 dtex was formed into 6 mols of isophthalic acid containing a single fiber fineness of 1.0 dtex. The non-woven fabric of the entangled body of the fiber bundles of the single fiber of the% modified PET was obtained in the same manner as in the example to obtain a fluffy artificial leather. Then, the obtained fluff-like artificial leather was evaluated in the same manner as in Example 1. The results are shown in Table 1.

    [Comparative Example 1]    

A suede-like artificial leather was produced and evaluated in the same manner as in Example 1 except that the steps of providing the second polyurethane and polysiloxane were omitted. The results are shown in Table 1.

    [Comparative Example 2]    

In the same manner as in Example 3, instead of polishing after the step of imparting the second polyurethane and polysiloxane, and polishing before the step of imparting the second polyurethane and polysiloxane, the same procedure was performed. A suede-like artificial leather was produced and evaluated. The results are shown in Table 1.

    [Comparative Example 3]    

Except in Example 1, instead of grinding after the step of imparting the second polyurethane and polysiloxane, the grinding was performed before the step of imparting the second polyurethane, instead of 2.00 g during drying. / m ² coating amount A second polyurethane solution was applied, and the coating was changed to a coating amount of 0.40 g / m ^2. A step of applying polysiloxane was omitted, and a suede-like artificial leather was produced in the same manner and evaluated. . The results are shown in Table 1.

    [Comparative Example 4]    

A suede-like artificial leather was produced and evaluated in the same manner as in Example 4 except that the steps of applying the second polyurethane and polysiloxane were omitted. The results are shown in Table 1.

    [Comparative Example 5]    

A suede-like artificial leather was produced and evaluated in the same manner as in Example 4 except that a DMF solvent and polysiloxane were applied instead of the second polyurethane. The results are shown in Table 1.

From the results in Table 1, it can be seen that the suede-like artificial leather obtained in Examples 1 to 7 having a fluff fiber layer having a thickness of 100 μm or more and the ratio of the number of bundled fiber bundles is higher in the first layer than in the second layer, and is resistant to friction and discoloration The fastnesses are all grade 4 or higher when dry, all grades 3 or higher when wet, and the fine hair shedding evaluations are all 3.5 or higher. In addition, it has excellent lifting properties, appearance, and texture. On the other hand, compared with the suede-like artificial leather of Example 1, the suede-like artificial leather of Comparative Example 1 which omitted the step of imparting the second polyurethane and polysiloxane, has a thickness of a fluff fiber layer. It becomes thin, and the ratio of the number of bundled fiber bundles in the first layer is also low. In addition, the fastness to abrasion and discoloration was 2.5 when wet, and the fine hair shedding evaluation was 3.5. In addition, compared with the suede-like artificial leather of Example 3, the suede-like artificial leather of Comparative Example 2 was polished before the step of applying the second polyurethane and polysiloxane, and the thickness of the fluff fiber layer was determined. It becomes thin, and the ratio of the number of bundled fiber bundles in the first layer is also low. In addition, the fastness to rubbing and bleaching is grade 3 when dry, and grade 2.0 when wet, and also has poor lifting properties, appearance, and feel.

    [Industrial availability]    

The suede-like artificial leather obtained by the present invention can be suitably used as a skin material for clothing, shoes, furniture, car seats, and miscellaneous goods.

Claims (11)

    A fluff artificial leather is a tangled body of a non-woven fabric and a fluff artificial leather with a first polymer elastomer imparted to the non-woven fabric, and the non-woven fabric is a single-fiber bundle of long fibers with a single fiber fineness of 0.05 to 1 dtex. The cross section in the thickness direction includes a fluff fiber layer having a thickness of 100 μm or more including the surface layer of the fluffed single fiber, a first layer connected to the fluff fiber layer and having a thickness of 120 μm, and a first layer connected to In the second layer of the first layer region, the ratio of the number of bundled fiber bundles in the ratio of the number of bundled fiber bundles to the total number of fiber bundles in each of the first layer and the second layer, The first layer is higher than the second layer.         For example, the fluff artificial leather of claim 1, wherein the ratio of the number of bundled fiber bundles in the first layer is 50% or more, and the ratio of the number of bundled fiber bundles in the second layer is 20% or less.         For example, the pile artificial leather of claim 1, wherein the bundle fiber bundle system has a porosity of less than 7%.         For example, the fluff artificial leather of claim 1, wherein the lightness L * value in the color coordinate space (L * a * b * color space) of the surface on the side of the fluff fiber layer is 50 or less.         The fluff artificial leather according to claim 1, wherein the single fiber system forming the bundled fiber bundle is fixed by a second polymer elastomer that penetrates into the internal voids of the bundled fiber bundle.     For example, the fluff artificial leather according to claim 5, wherein the second polymer elastomer includes 0.5 to 3.0 g / m ² in a planar direction.     The fluff artificial leather of claim 1, wherein at least one of the fluff fiber layer and the first layer comprises polysiloxane.         The fluff artificial leather of claim 1, wherein the single fiber comprises a cationic dyeable PET dyed with a cationic dye.         The fluff artificial leather of claim 1, wherein the single fiber comprises PET colored with a pigment.         A method for manufacturing fluffy artificial leather, which is the method for manufacturing fluffy artificial leather according to claim 1, and includes the following steps: preparing an artificial leather grey fabric including a non-woven fabric and a first polymer elastomer having voids provided to the non-woven fabric; Step, the non-woven fabric is an entangled body of long fiber bundles of single fibers having a single fiber fineness of 0.05 to 1 dtex, and a step of imparting a second polymer elastomer and polysiloxane to at least one side of the artificial leather gray fabric, and A step of sanding the surface that has been imparted to the second polymer elastomer and the polysiloxane.         The method for manufacturing fluff artificial leather according to claim 10, further comprising a step of dyeing with a cationic dye after the sanding step.