JP2008196080A - Method for producing napped leather-like sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a dyed napped leather like sheet excellent in color-developing property, dyed color stability and fastness by stably performing the reduction cleaning of the leather like sheet consisting mainly of a polyester-based fiber after dyed with a disperse dye. <P>SOLUTION: In the method for producing a dyed napped leather like sheet, the process of dyeing the leather like sheet includes dyeing a non-woven fabric consisting of polyester-based very fine fibers having a single fiber fineness of ≤0.5 decitex and an elastic polymer contained therein, at least on one side surface of the leather like sheet with the disperse dye in a dyeing machine, before or after performing a napping treatment, performing the reduction cleaning, and performing an oxidation treatment, wherein the reductive cleaning treatment satisfies all of the followings; (1) to perform the reduction cleaning treatment in the same dyeing machine used in the dyeing treatment, (2) to use a reduction cleaning liquid containing an alkaline substance, a reducing agent, and a surfactant, (3) to perform the cleaning under an atmosphere having a volume content of oxygen of <5%, and (4) to perform the cleaning at ≥60°C reduction cleaning liquid temperature. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a dyed standing fur leather-like sheet. More specifically, the present invention provides a smooth and smooth dyed fur leather-like sheet that is excellent in color development, leveling, and dyeing fastness by carrying out a reduction washing treatment after dyeing with a disperse dye. And a standing fur leather-like sheet obtained thereby.

  Polyester ultrafine fiber nonwoven fabric containing an elastic polymer inside the fiber aggregate, and a sheet with napped surfaces on one or both sides, has an appearance, texture, and feel that are expressed by the length of the napped fibers and the fineness of the texture. Since it is similar to natural leather suede or nubuck, it has been produced in large quantities as a suede-like or nubuck-like standing fur leather-like sheet in recent years. In particular, a standing fur leather-like sheet in which napped fibers are formed from ultrafine fibers is treated as a luxury product because it is very close to natural leather. Such standing fur leather-like sheets have high dyeing fastness, so that in terms of applications, elements such as clothing, interiors, car seats, shoes, bags, etc. are increasing. Along with this, a dyed standing fur leather-like sheet that has good color development, no dyeing spots, has a stable color tone, and is excellent in washing fastness, dry cleaning fastness, dyeing friction fastness, sweat fastness, etc. Is strongly demanded.

  In the standing fur leather-like sheet, the fibers forming the raised hair are extremely important elements for determining the quality of the standing fur leather-like sheet, such as appearance, texture, and touch. As fibers that form napped fibers, polyamide fibers, polyester fibers, acrylic fibers, and the like are generally used in many cases. Among them, the ultra-fine fibers made of polyester are excellent in color development and dyeing fastness, so that they are widely used as the fibers that make up nappings in standing fur leather-like sheets, especially as interior materials for vehicles and interior materials represented by car seats. in use. Since napped fibers made of polyester ultrafine fibers have poor color developability due to the ultrafine fibers, dyeing using a large amount of dye is usually performed to improve color developability. However, when a large amount of dye is used, the color developability itself can be secured, but the extra dye adheres and remains on the standing fur leather-like sheet, so the dyeing fastness is low, and friction, washing, dry cleaning, sweat It is easy to cause the problem of color fading. In order to overcome the above problems and to improve the fastness of dyeing, various dyeing methods have been adopted or proposed.

  For example, a suede-like artificial leather made of polyurethane consisting of polyester microfiber and polyamide microfiber is dyed with a disperse dye at a dye concentration of 1 to 35% in the space, and then a reducing agent, a reducing aid and an alkali. There is a known method for improving dyeing fastness and color stability by performing reduction cleaning treatment in the presence of an agent and regulating the release of dye before and after reduction cleaning treatment in polyurethane (Patent Document) 1). However, when this method is used, the fastness to dyeing is improved, but the reducing agent is oxidized by the air contained in the reducing bath or the air present in the dyeing machine at the time of washing with the reducing agent during dyeing, and the reducing ability becomes unstable. Along with this, there is a problem that the stability at the time of dyeing becomes insufficient, and the dyed suede-like artificial leather tends to cause hue blur and color spots, and there is room for improvement.

  In addition, in a suede-like artificial leather dyed with disperse dyes using polyester microfibers, a yellow pigment, a red pigment and a blue pigment are contained in polyurethane in order to obtain high light fastness, and then reduced and washed. It is known that disperse dyes in polyurethane are decomposed and decolorized by treatment (see Patent Document 2). Also known is a suede-like artificial leather comprising a polyurethane colored with a pigment having a reduction washing drop-off rate of 20% or less and an infrared reflectance at 850 nm of 60% or more and a fiber entanglement including polyester fine fibers. (See Patent Document 3). However, even when using these methods, the reducing ability becomes unstable at the time of washing with the reducing agent, and accordingly, the stability at the time of dyeing becomes insufficient, and the hue and blurring of the dyed suede-like artificial leather are likely to occur. There was room for further improvement.

JP 2005-133256 A JP 2004-52120 A JP 2003-253572 A

  An object of the present invention is to dye a non-woven fabric composed of polyester-based ultrafine fibers and a leather-like sheet composed of an elastic polymer contained therein with a disperse dye before or after the raising treatment, followed by a reduction washing treatment. In producing a dyed standing fur leather-like sheet having nappings mainly composed of polyester-based ultrafine fibers on the surface, dyeing spots, variation in hue between dyeing batches, polyester fiber constituting the standing fur leather-like sheet and elastic weight Suppressed the difference in dyeing state and hue difference between the coalesced, and did not lose color due to friction, washing, dry cleaning, sweat, etc., dyed with excellent dyeing fastness and good dyeing stability It is to provide a method for producing a standing fur leather-like sheet.

  In order to solve the above problems, the present inventors have repeatedly studied. As a result, a non-woven fabric made of polyester-based ultrafine fibers and a leather-like sheet made of an elastic polymer contained therein are dyed with a disperse dye before or after the raising treatment, followed by alkaline substances, reducing agents, and surface activity. Specifying the oxygen content in the atmosphere surrounding the reducing cleaning liquid containing the agent, that is, reducing the oxygen concentration in the atmosphere to a specific range or lower and performing a reduction cleaning treatment at a high temperature of 60 ° C. or higher, Oxidation treatment reduces the oxidative degradation of the reducing agent with oxygen in the air and maintains the reducing ability to be uniform and stable. The polyester forms dyed spots, hue variations between dyeing batches, and leather-like sheets. It has been found that there is no color difference between the ultrafine fiber and the elastic polymer, the dyeing stability is improved, and the reducing agent can be significantly reduced from the conventional amount used. .

  In addition, the present inventors obtained dyed raised fur leather-like sheets mainly having raised fibers mainly composed of polyester-based ultrafine fibers are free from discoloration due to friction, washing, dry cleaning, sweat, etc. I found it excellent.

That is, the present invention
(1) The leather-like sheet is formed before or after at least one surface of a non-woven fabric made of a polyester-based ultrafine fiber having a single fineness of 0.5 dtex or less and a leather-like sheet made of an elastic polymer contained therein is brushed, In the method of dyeing the leather-like sheet by dyeing with a disperse dye in a dyeing machine and performing a reduction washing treatment followed by an oxidation treatment, the reduction washing treatment satisfies both 1) to 4) below. A method for producing a dyed standing fur leather-like sheet.
1) Perform in the same dyeing machine as the dyeing process,
2) Use a reducing cleaning solution containing an alkaline substance, a reducing agent and a surfactant,
3) Performing in an atmosphere having a volume content of oxygen of less than 5%,
4) Perform the reducing cleaning solution temperature at 60 ° C. or higher,

(2) The method for producing a standing fur leather-like sheet according to (1), wherein the elastic polymer is polyurethane.
(3) The method for producing a standing fur leather-like sheet according to (1) or (2), wherein the elastic polymer content is 5% by mass or more of the standing fur leather-like sheet.
(4) The elastic polymer comprises a polyurethane soluble in dimethylformamide and a polyurethane insoluble in dimethylformamide, and the polyurethane insoluble in the dimethylformamide is unevenly distributed on the raised surface side. A method for producing any of the standing fur leather-like sheets.
(5) The manufacturing method of the standing fur leather-like sheet | seat in any one of said (1)-(4) which performs a soaping process after an oxidation process.
(6) The method for producing a standing fur leather-like sheet according to any one of (1) to (5), wherein the brushing treatment is performed after the oxidation treatment or the soaping treatment.

(7) A dyed standing fur-leather-like sheet obtained by the method for producing a standing fur-leather-like sheet according to any one of (1) to (6) above,
(8) Apparel, interior materials, vehicle interior materials, shoes or bags using the standing fur leather-like sheet of (7) above.

  The standing fur leather-like sheet obtained by the production method of the present invention is free from the occurrence of stained spots due to washing spots due to reduction washing, and a standing fur leather-like sheet having uniform dyeability and excellent fastness can be obtained.

The present invention is described in detail below.
The base of the standing fur leather-like sheet used in the present invention has a constitution in which polyurethane is contained in a non-woven fabric made of polyester microfibers of 0.5 dtex or less. Known polyester can be used as the polyester constituting the fiber. Then, polyethylene terephthalate, polybutylene terephthalate, and a modifier for imparting a generally known cationic dyeing property such as 5-sulfosodium-isophthalate are copolymerized or blended, either alone or What blended 2 or more types is used preferably. Moreover, it is preferable at the point which is excellent in the external appearance, surface touch, and texture of the standing fur leather-like sheet | seat from which the said polyester ultrafine fiber is obtained as an ultrafine fiber bundle.
Furthermore, the polyester ultrafine fiber of the present invention is also preferably colored with a pigment typified by carbon black or the like in that the amount of dye attached can be reduced at the time of dyeing the standing fur leather-like sheet. One.

  A polyester microfiber bundle having a single fineness of 0.5 dtex or less is produced by a conventionally known method. For example, in the fiber cross section, the polyester is an island component, and the sea component polymer is dissolved or dissolved from a sea-island type polyester ultrafine fiber generating fiber in which at least one kind of polymer having a small or no compatibility with the polyester is a sea component. By decomposing and removing, or a bonded polyester ultrafine fiber-generating fiber having a cross-sectional shape in which one or more kinds of polymers incompatible with the polyester are bonded together at a two-component interface by mechanical or chemical treatment It can be obtained by peeling. In order to set the single fineness of the ultrafine fiber constituting the bundle of the obtained polyester ultrafine fibers to 0.5 decitex or less, particularly 0.2 decitex or less, the fiber cross section is smaller than that of using the bonded ultrafine fiber generating fiber. It is advantageous in terms of the process to use a sea-island type ultrafine fiber generating fiber having a sea-island structure. Moreover, you may use the method of manufacturing an ultrafine fiber directly like a melt blown.

  The component dissolved or decomposed and removed in the polyester microfiber-generating fiber is a polymer that is different in solubility or decomposability in the polyester microfiber component and solvent or decomposing agent and has low compatibility with the polyester microfiber component. And a polymer having a lower melt viscosity or a lower surface tension than the polyester ultrafine fiber component under spinning conditions, for example, at least one kind selected from polymers such as polyethylene, polystyrene, polyethylene-propylene copolymer, and polyvinyl alcohol It is a polymer.

The polyester microfiber-generating fiber is defibrated with a card and formed into a web through a webber. The obtained web is laminated to a desired weight and thickness, and then known, such as a needle punch, high-speed water flow, etc. The entanglement process is performed by the method to obtain a nonwoven fabric composed of polyester ultrafine fiber generating fibers. It is preferable that a woven or knitted fabric or the like is laminated on the web as needed from the viewpoint that the mechanical properties are stable and a texture with a sense of fulfillment can be easily achieved. The nonwoven fabric is finally subjected to ultrafine treatment, and the surface is fluffed to form a raised surface. Therefore, the nonwoven fabric surface must be composed of ultrafine fiber-generating fibers or ultrafine fibers. However, when emphasizing the texture of the resulting standing fur leather-like sheet, it is preferable that the whole nonwoven fabric is made of ultrafine fiber-generating fibers or ultrafine fibers from the viewpoint of excellent flexibility. In order to make the nonwoven fabric a base layer having a smooth surface, the surface is preferably smoothed by a heat press treatment or the like before impregnation of the elastic polymer by a known method. As a fabric weight of the obtained nonwoven fabric, the range of 150-1000 g / m < ² > is preferable. If it is less than 150 g / m ² , the change in form such as elongation in the steps after the impregnation of the elastic polymer becomes large, and distortion may remain in the resulting product, resulting in poor appearance. On the other hand, if it exceeds 1000 g / m ² , it is impractical because the ultrafine fiber formation rate becomes slow as represented by the steps of impregnation and solidification of the elastic polymer and extraction of the sea component in the ultrafine fiber generation type fiber. . Moreover, as preferable thickness after a heat press process, the range of 1.0-3.0 mm is preferable. When the thickness is less than 1.0 mm, the shape change such as elongation becomes large in the steps after the impregnation of the elastic polymer, and distortion may remain in the obtained product, resulting in poor appearance. When the thickness exceeds 3.0 mm, the thickness of the resulting nonwoven fabric is so thick that the surface of the nonwoven fabric is easily folded and wrinkled.

The elastic polymer contained in the nonwoven fabric of the present invention may be any known elastic polymer, such as natural rubber, SBR, NBR, polychloroprene, polyisoprene, chlorosulfonated polyethylene, polyisobutylene, Examples include isobutylene isoprene rubber, acrylic rubber, polyurethane elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polystyrene-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, polydiene-based thermoplastic elastomer, and chlorine-based thermoplastic elastomer. 1 type, or 2 or more types of these can be used.
Among them, polyurethane elastomers (polyurethanes) are used as elastic polymers in terms of the texture, dyeability, abrasion resistance, mechanical properties such as tensile strength, and wrinkle resistance of the dyed standing fur leather-like sheet that is finally obtained. ) Is preferably used.

  As the polyurethane, any polyurethane resin having elasticity can be used. Particularly, a high molecular diol having a number average molecular weight of 500 to 5000 is used as a soft segment component, an organic diisocyanate is used as a hard segment component, and a low molecular chain together with these components. A segmented polyurethane obtained by reacting an extender is preferably used.

  Examples of the above-mentioned polymer diol used for the production of segmented polyurethane include polyester diol, polylactone diol, polycarbonate diol, polyester polycarbonate diol, polyether diol, etc. obtained by reaction of a dicarboxylic acid component and a diol component. One or two or more of these polymer diols can be used. If the number average molecular weight of the polymer diol used in the production of the segmented polyurethane is less than 500, the soft segment is too short and the polyurethane lacks flexibility, making it difficult to obtain a natural leather-like standing fur leather-like sheet. May be. On the other hand, when the number average molecular weight of the polymer diol exceeds 5,000, the ratio of urethane bonds in the polyurethane is relatively reduced, which decreases durability, heat resistance, hydrolysis resistance, and the like. It becomes difficult to obtain a dyed standing fur leather-like sheet having physical properties.

As the organic diisocyanate used in the production of the segmented polyurethane, any of the organic diisocyanates conventionally used in the production of polyurethane can be used. Aromatic diisocyanates such as isocyanate, isophorone diisocyanate and 1,5-naphthylene diisocyanate; Aliphatic diisocyanates such as hexamethylene diisocyanate; Alicyclic diisocyanates such as 4,4′-dicyclohexylmethane diisocyanate and hydrogenated xylylene diisocyanate be able to.
One or more of the above-mentioned organic diisocyanates can be used.

  As the low molecular chain extender used in the production of the segmented polyurethane, any of low molecular chain extenders conventionally used in the production of polyurethane, particularly low molecular chain extenders having a molecular weight of 400 or less can be used. , Ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, N-methyldiethanolamine, 1,4-cyclohexanediol, bis- Diols such as (β-hydroxyethyl) terephthalate, xylylene glycol, 1,4-bis (β-hydroxyethoxy) benzene; hydrazine, ethylenediamine, propylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine Diamines such as ethylene, xylylenediamine, adipic acid dihydrazide, isophthalic acid dihydrazide, hexamethylenediamine, 4,4'-diaminophenylmethane, 4,4'-dicyclohexylmethanediamine; amino such as aminoethyl alcohol and aminopropyl alcohol Alcohols etc. can be mentioned, These 1 type (s) or 2 or more types can be used.

In the production of the segmented polyurethane, the equivalent ratio of [total isocyanate groups] / [total functional groups that react with isocyanate groups such as hydroxyl groups and amino groups] is in the range of 0.9 to 1.1. The above-described polymer diol, organic diisocyanate, and low molecular chain extender are preferably reacted from the viewpoint of obtaining a dyed standing fur leather-like sheet having high tear strength.
In addition, for the purpose of improving the solvent resistance, heat resistance, hot water resistance, etc. of polyurethane, it is crosslinked in the polyurethane by reacting with trifunctional or higher polyols such as trimethylolpropane or trifunctional amines as necessary. You may give a structure.

  The elastic polymer constituting the standing fur leather-like sheet of the present invention comprises a polyurethane soluble in dimethylformamide and a polyurethane insoluble in dimethylformamide, and the polyurethane insoluble in dimethylformamide is unevenly distributed on the napped surface side. However, a small amount of polyurethane resin can exhibit an anti-pilling effect, which is preferable in terms of texture. The polyurethane soluble in dimethylformamide referred to here is generally a polyurethane having a non-dense crosslinked structure, and is preferably a chain-like polyurethane. The polyurethane insoluble in dimethylformamide generally refers to a polyurethane having a dense cross-linked structure (having a three-dimensional network structure). The method of unevenly distributing polyurethane insoluble in dimethylformamide on the napped surface side is not particularly limited, but the method of impregnating a nonwoven fabric as an aqueous dispersion and unevenly distributing using migration, the napped surface with a coating machine represented by gravure, etc. A method of selectively imparting to the side to be used is preferably used.

  In the standing fur leather-like sheet used in the present invention, the content of the elastic polymer is preferably 5% by mass or more of the standing fur leather-like sheet, and the upper limit is 70% or less from the viewpoint that a natural leather-like soft texture can be obtained. It is preferable that it is in the range of 15-60 mass%. If the proportion of the elastic polymer exceeds 70% based on the weight of the standing fur leather-like sheet, a rubber-like texture tends to be obtained. On the other hand, when the proportion of the elastic polymer is less than 5% by mass based on the mass of the raised fur leather-like sheet, the falling of the raised hair formed by the raising treatment and the anti-pill property are reduced.

The method for producing the leather-like sheet before the raising treatment is not particularly limited, and can be produced using a known method. For example, it can be produced by the following methods (a) to (c).
(A) One or two or more polyesters and one or two or more other polymers having different solubility or decomposability from the polyesters by a mixed spinning method, a sea-island type composite spinning method, a split type composite spinning method, etc. After producing a non-woven fabric and other fiber aggregates using the ultrafine fiber-generating fiber obtained by spinning, solidifying by containing an elastic polymer, other polymer components in the ultrafine fiber-generating fiber are removed. To make ultrafine fibers, or to divide ultrafine fiber-generating fibers into ultrafine fibers.
(B) After producing a non-woven fabric or other fiber assembly using the ultra-fine fiber-generating fiber composed of one or more types of polyester and one or more types of other polymers, generation of the ultra-fine fiber A method in which other polymer components in the mold fiber are removed or the ultrafine fiber-generating fiber is divided into ultrafine fibers, which are then solidified by containing an elastic polymer.
(C) A method in which a non-woven fabric or other fiber aggregate is produced using ultrafine fibers mainly composed of polyester obtained directly by a melt blow method or the like and then solidified by containing an elastic polymer.

  Other polymers used with the polyester in the method (a) or (b) include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer; polystyrene, styrene-acrylic Examples thereof include styrene polymers such as styrene monomer copolymers and styrene-ethylene copolymers, and polyvinyl alcohol polymers, and one or more of these can be used.

  In the above methods (a) to (c), when the elastic polymer is contained in the fiber assembly mainly composed of polyester-based ultrafine fibers, a solution or dispersion containing one or more elastic polymers is used. Generally, a method of impregnating or coating the fiber assembly by a conventionally known method and solidifying the elastic polymer into a porous state or a non-porous state by a dry method or a wet method is generally employed.

In the case of producing a leather-like sheet containing an elastic polymer in a fiber assembly composed of a nonwoven fabric mainly composed of polyester-based ultrafine fibers by the method (a), more specifically, for example, It can be produced by a series of steps (i) to (iv).
(I) An ultra-fine fiber-generating fiber composed of polyester and another polymer is subjected to treatments such as drawing, crimping, and cutting to form a cotton-like form (staples, etc.). Or use a cross-wrap webber. Or it extends as it is and it is set as the web which consists of a long fiber. Then, if necessary, the web is laminated so as to have a desired basis weight. The basis weight of the web varies depending on the use of the dyed standing fur leather-like sheet finally obtained, but is generally preferably 100 to 3000 g / m ² .
(Ii) Next, a nonwoven fabric is manufactured by performing an entanglement treatment using a known means such as a needle punching method or a high-pressure water flow method. The number of punches during needle punching may vary depending on the shape of the needle, the thickness of the web, and the like, but is generally preferably 200 to 2500 punches / cm ² . In addition, by adjusting the elongation strength of the dyed standing fur leather-like sheet finally obtained, adjusting the basis weight and thickness, and other purposes, at any stage from the web formation to the completion of the entanglement process, Sheet-like materials such as nonwoven fabrics and films of different fibers may be laminated and integrated on the nonwoven fabric.
(Iii) Subsequently, the nonwoven fabric obtained in the above (ii) is made to contain an elastic polymer. The method for applying the elastic polymer is not particularly limited, but from the viewpoint of the balance of the texture, a method in which the nonwoven fabric is impregnated with the elastic polymer solution or dispersion and then solidified (solidified) by a wet method or a dry method is preferably employed. . If necessary, a colorant such as a pigment or a dye, a coagulation modifier, a flammability modifier, or the like can be added to the elastic polymer solution or dispersion.
(Iv) Next, the nonwoven fabric containing the elastic polymer is treated with a liquid that selectively acts as a solubilizer or a decomposing agent on one or more components of the ultrafine fiber-generating fiber to generate ultrafine fibers. The mold fiber is modified into an ultrafine fiber bundle to form a sheet-like material in which an elastic polymer is contained in a nonwoven fabric mainly composed of a polyester ultrafine fiber bundle.

  When producing a leather-like sheet containing an elastic polymer in a fiber assembly composed of a nonwoven fabric mainly composed of polyester-based ultrafine fibers by the series of steps (i) to (iv) above, an ultrafine fiber generation type When the island component is made of ultra-fine fibers using the sea-island structure fiber as the polyester island component as the fiber, the polyester ultra-fine fiber (bundle) and the elastic polymer are not substantially bonded to each other. Since it is not restrained by the elastic polymer, the degree of freedom of movement in the structure is increased, so that a leather-like sheet that is more excellent in natural leather-like flexibility can be obtained.

Even when a fiber assembly made of a nonwoven fabric is produced using polyester fibers that have already been made ultrafine and an elastic polymer is contained therein [when the method (c) above is employed], the elastic polymer applied to the nonwoven fabric Impregnation can be performed in the same manner as in the method (a). In the above method (b) or (c), a water aggregate is preliminarily applied to the fiber aggregate before impregnating the fiber aggregate mainly composed of polyester fiber with the elastic polymer to solidify the elastic aggregate. If the water-soluble resin is dissolved and removed with water after impregnation and coagulation of the coalescence, the adhesion between the polyester fibers constituting the fiber assembly and the elastic polymer is prevented or reduced, and the freedom of movement of the fibers is increased. Thus, a leather-like sheet with improved flexibility can be obtained.
Also in the above method (a), a water-soluble resin is applied to the fiber assembly before the fiber assembly mainly composed of polyester fibers is impregnated with the elastic polymer and solidified. A method of dissolving and removing the water-soluble resin with water after impregnation and coagulation may be used, thereby further improving the flexibility of the leather-like sheet obtained.

In the present invention, the above-mentioned leather-like sheet comprising a fiber aggregate mainly composed of polyester fibers and the elastic polymer contained therein is subjected to raising treatment before dyeing treatment or after dyeing treatment, Napped fur is formed on one or both sides of the sheet to form a raised leather-like sheet.
The raising treatment for forming napping may be performed by any conventionally known method. For example, a leather-like sheet is cut (sliced) into a plurality of sheets in the thickness direction as necessary, and one or both of them are then cut. The surface of the surface is raised by buffing with sandpaper or the like, or by raising a needle cloth to form napped.

  In the present invention, the single filament fineness mainly composed of polyester-based ultrafine fibers formed on one side or both sides of the leather-like sheet is the appearance, feel, texture, lighting effect, etc. of the dyed raised fur-like sheet that is finally obtained. From this point, it is necessary to be 0.5 dtex or less, preferably 0.4 dtex or less, and more preferably 0.0001 to 0.1 dtex. If the fineness of the fibers forming the napped fibers is greater than 0.5 decitex, the color developability will be good when dyed, but the texture and feel of the raised fur-like sheet itself will be impaired, especially as a fashion material It tends to be unsuitable. On the other hand, if the thickness of the fibers forming the nap is less than 0.0001 dtex, the appearance becomes fine and the tactile sensation is good, but the color developability is extremely deteriorated when dyed because it is too thin. Thus, it cannot be dyed in vivid or deep colors, and is particularly unsuitable as a fashion material.

Further, the length of napped fur (napped length) in the raised fur leather-like sheet obtained by the raising treatment can be adjusted according to the use of the raised fur leather-like sheet. A thickness of 2 mm, particularly 0.05 to 1 mm is preferable from the viewpoints of anti-pill property, touch, and lighting effect. Further, the napped density in the raised fur leather-like sheet is preferably 10,000 / cm ² or more.
The nap length in the standing fur leather-like sheet may be the same over the entire surface or may not be uniform. When the raised hair lengths are uneven, they may be uneven in a random state, or may be uneven with a predetermined regularity so as to appear in a pattern or the like. Further, when napping is formed on both sides of the raised fur leather-like sheet, the napping length of the napping on both sides may be the same, or the napping length may be different on one side and the other side. . By selecting various treatment conditions for raising treatment, the raised state of the raised fur-like sheet can be appropriately adjusted, and the appearance and feel of the raised fur-like sheet can be adjusted, for example, suede, nubuck, raised A uniform state where the lengths are uniform, a rough state where the napped lengths and / or napped densities are uneven, and the like can be achieved.

  In the present invention, for the purpose of fixing nap on the surface of the leather-like sheet, if necessary, a treatment liquid containing an elastic polymer solvent constituting the leather-like sheet, and a fiber assembly constituting the leather-like sheet are formed. A treatment liquid containing any fiber swelling agent or solvent may be applied to the surface of the leather-like sheet before or after the raising treatment. Further, the elastic polymer solution or dispersion may be applied to the leather-like sheet as a napping fixative before or after the raising treatment. Further, a brushing process may be performed at any stage after the raising process to adjust the appearance or feel of the standing fur leather-like sheet.

  The above-mentioned napping treatment is applied to the leather-like sheet to form napping on one or both sides and then dyed to obtain a dyed nap-fur leather-like sheet, or the above-mentioned napping treatment is performed after dyeing the leather-like sheet. Then, napping is formed on one side or both sides to form a dyed standing fur leather-like sheet. In addition, in the order of the steps of the raising treatment and the dyeing treatment referred to here, the dyeing treatment is a general term for a series of treatments including dyeing, reduction washing, water washing and oxidation treatment.

  Thickness of leather-like sheet before raising treatment or raising-furnished leather-like sheet subjected to raising treatment (thickness of body part not including napped length in raised-fur leather-like sheet with napping) Is preferably 0.1 to 3 mm, particularly preferably 0.2 to 2.0 mm. If the thickness of the leather-like sheet or standing fur leather-like sheet (main part) is less than 0.1 mm, the leather-like sheet or standing fur leather-like sheet itself may not be strong enough to withstand the dyeing process. It will be unsuitable as a fashion material. On the other hand, if the thickness of the leather-like sheet or the standing fur leather-like sheet (main part) exceeds 3 mm, it becomes difficult to pass through the nozzle of a dyeing apparatus such as a liquid dyeing machine in a stable state, and the process during dyeing Passability tends to be poor.

  The dyeing treatment of the leather-like sheet before raising treatment or the raised fur leather-like sheet subjected to raising treatment may be performed directly without performing preliminary treatment, but before the dyeing treatment, the leather-like sheet or standing fur leather-like sheet is used. It is highly desirable to perform the dyeing process after previously performing a process for making the water fully acclimatized by, for example, putting it into water. The leather-like sheet before brushing or the raised fur-leather-like sheet that has been brushed is well-familiar with water before dyeing, so that the degree of dye penetration is uniform and dyeing spots are prevented. Further, it is possible to prevent the leather-like sheet or the standing fur leather-like sheet from being damaged by twisting in the dyeing machine, and to prevent the occurrence of wrinkles that lower the commercial value.

  Although the water temperature at the time of performing the treatment to adjust to water is effective even at room temperature, it is preferably 60 ° C. or higher, more preferably 70 to 100 ° C. Further, the time for acclimatization to water may be shorter if the leather-like sheet before raising treatment or the raised fur-like sheet subjected to raising treatment is thin, and may be about 5 minutes, preferably 10 minutes or more More preferably, by performing the treatment for about 30 to 60 minutes, the effect of the water acclimation treatment can be exhibited more. The treatment for habituation to water may be performed using a device different from the dyeing machine used for dyeing, but the treatment for habituation to water using a dyeing machine used for dyeing-dyeing-reduction washing treatment- It is more efficient to perform the oxidation treatment sequentially and sequentially. Taking the case of using the above-mentioned liquid dyeing machine as an example, as a specific method for acclimatizing to water, before filling the dyeing machine with a predetermined amount of water, during or after filling, The leather-like sheet before raising treatment or the raised fur leather-like sheet subjected to raising treatment is put into the dyeing machine, and after raising the water temperature to the above temperature, the leather-like sheet is flown at 10 m / min during the treatment time. The method of performing the process which adjusts to water, moving the inside of a dyeing machine at a flow rate of 50 to 300 m / min, more preferably at least 50 minutes.

  The leather-like sheet or the standing fur-leather-like sheet is dyed with a disperse dye directly as it is or after the above-described treatment for making it acclimatized with water.

  The method for dyeing the leather-like sheet of the present invention with a disperse dye is not particularly limited, and a known method can be used. That is, a known disperse dye can be used. For example, any dye may be used as long as it is a disperse dye that is sparingly soluble in water and used for dyeing hydrophobic fibers when dispersed in water, and dyes used for dyeing polyester fibers and the like can be used as appropriate. Specifically, benzeneazo (monoazo, disazo, etc.), heterocyclic azo (thiazole azo, benzothiazole azo, quinoline azo, pyridine azo, imidazole azo, thiophenazo, etc.), anthraquinone, condensed (quinophthaline, styryl, coumarin, etc.) ) Etc. can be used arbitrarily. These can be used alone or in combination. Moreover, a well-known method can be used also about the method of dyeing | staining. As dyeing conditions, specifically, the dyeing temperature is 110 to 160 ° C, preferably 120 to 150 ° C. If it is less than 110 degreeC, there exists a tendency for the dyeing | staining of the whole polyester microfiber to become inadequate, the dyeing reproducibility of dyeing finish is bad, and it becomes easy to generate | occur | produce a spot. On the other hand, when it exceeds 160 ° C., thermal degradation of the polyester fiber and the elastic polymer is likely to occur. The dyeing time is preferably 10 to 120 minutes. In dyeing, the dyeing bath may be stirred or permeated by a dyeing machine described later so that the dyeing bath sufficiently penetrates into the leather-like sheet, and further, the dyeing bath or the leather-like sheet is circulated. It is preferable in terms of uniformly dyeing the leather-like sheet.

  Further, the concentration of the disperse dye in the water bath (dye bath) is preferably 0.01 to 50 owf%, particularly preferably 0.1 to 30 owf% in terms of fastness to dyeing.

  When dyeing the leather-like sheet before raising or raising the raised fur-like sheet, if necessary, for example, dyeing aids such as glucose, sodium sulfate, salt, antioxidants, chelating agents, and antifoaming Agents, penetrants, etc. may be used in combination.

  As the dyeing machine used for the dyeing process, any known dyeing machine can be used, and examples thereof include a jigger dyeing machine, a Wins dyeing machine, a dash line dyeing machine, a circular dyeing machine, and a rotary washer dyeing machine. In the present invention, since it is necessary to maintain the oxygen content in the reducing cleaning treatment atmosphere at less than 5%, the dyeing machine has good airtightness that can maintain the oxygen content at less than 5%. A machine is preferably used. Examples of dyeing machines with good sealing properties include liquid dyeing machines such as circular dyeing machines, rotary washer dyeing machines, etc. Among them, circular dyeing machines that have excellent sealing properties and are capable of high-pressure dyeing. A liquid dyeing machine such as is more preferably used.

In the present invention, after the dyeing treatment with the disperse dye, the reduction cleaning treatment (hereinafter sometimes simply referred to as “reduction cleaning”) needs to be performed in an atmosphere having a volume content of oxygen of less than 5%. The lower the oxygen content in the atmosphere when performing the reduction cleaning treatment, the more preferable. From this point, the oxygen volume content in the atmosphere is preferably 2% or less, preferably 1% or less. More preferably, 0% or closer to it is even more preferable.
During the reduction treatment, when the volume content of oxygen in the atmosphere is 5% or more, the reduction in the reducing cleaning solution is hindered or suppressed by oxygen, and the disperse dye is dissolved uniformly and smoothly in the water bath. The dyeing / reducing agent concentration in the reducing cleaning solution is non-uniform, changes with time, lacks in concentration, etc., making it difficult to dye in a uniform color without sufficient cleaning, and lacking in dyeing stability. Become.

Here, the “volume content of oxygen” in the present specification refers to the volume content of oxygen in the gas space surrounding the reduction cleaning bath when performing the reduction cleaning treatment, and dyes the reduction cleaning treatment. When carried out in the machine, it means the volume content of oxygen in the gas space in the dyeing machine.
At that time, the “volume content of oxygen in the atmosphere (gas space)” can be measured by directly inserting the sensor unit of the oxygen concentration measuring device into the atmosphere (gas space) for dyeing treatment, The details are as described in the Examples section below.

  Air (atmosphere) usually contains around 21% oxygen. If reduction cleaning is performed directly in air (in the atmosphere), the oxygen contained in a large amount in the air is excessive in the reduction cleaning liquid. This prevents the disperse dye from being reduced and solubilized in water, so that the reduction cleaning treatment is not performed smoothly and the dyeing stability is lowered. On the other hand, in the present invention, the reduction cleaning treatment to the leather-like sheet is carried out in an atmosphere having a volume content of oxygen of less than 5%, thereby suppressing the deactivation of the reducing agent and reducing the disperse dye smoothly and It can be sufficiently solubilized in water. Moreover, since the dye that has been made water-soluble by the reduction treatment can be prevented from being oxidized and rendered water-insoluble again, the leather-like sheet before or after the raising treatment does not cause dye washing spots and is excellently dyed. It can be dyed uniformly and vividly while maintaining stability.

In order to keep the volume content of oxygen in the atmosphere at less than 5% during the reduction cleaning process and the leather-like sheet cleaning process, the atmosphere is inert such as nitrogen gas, argon gas, helium gas and carbon dioxide gas. A method of replacing with gas is preferably employed. Among them, although not limited, industrially, a method of substitution using nitrogen gas is more preferable from the viewpoints of handleability and cost.
The timing for replacing the gas in the atmosphere with an inert gas is preferably performed at an arbitrary stage at any point in time after completion of dyeing and before performing reduction cleaning. In addition, it is preferable to perform substitution with an inert gas at any stage from the time when the dyeing process is completed and the time after washing is completed until before any of the reducing agent and the surfactant is added. Furthermore, when another processing step such as adjustment of the amount of water bath to adjust the leather-like sheet to water is necessary, any one of the alkali, reducing agent, and surfactant when the other processing step is completed. It is preferable to perform replacement with an inert gas at an arbitrary stage between the time point until the subsequent charging.

After the volume content of oxygen in the atmosphere in which the reduction cleaning treatment is performed is less than 5%, an alkaline substance, a reducing agent, and a surfactant are put into a water bath (treatment bath). A well-known processing agent can be used for the alkaline substance, reducing agent, and surfactant which perform the reduction washing process said here, It is preferable to use caustic soda or the alkaline agent for fiber dyeing as an alkaline agent. As the reducing agent, for example, hydrosulfite, thiourea dioxide or the like is preferably used. The surfactant is preferably an anionic or nonionic surfactant or a chelating agent. There are no particular restrictions on the method of charging these chemicals, and any method should be employed depending on the type and concentration of the dye used, the dyeing bath ratio, the mass ratio of the polyester fiber in the leather-like sheet to be dyed, etc. For example, a batch charging method in which all of the drugs are mixed in advance and charged at a time, a sequential charging method in which each drug is sequentially charged one by one without mixing, one or two kinds of the drugs There can be mentioned, for example, a divided charging method in which the above is divided into a plurality of times, but is not particularly limited.
In addition, alkaline substances and reducing agents removed from each chemical container etc. should be left in the air for a short time, and as quickly as possible in a water bath (dyeing bath) in a treatment atmosphere substituted with an inert gas. It is desirable to add them from the viewpoint of preventing oxidation of these drugs.

  When the alkaline substance, the reducing agent and the surfactant, and the auxiliary agent are added to the water bath (reduction treatment bath), the leather-like sheet to be subjected to the reduction cleaning treatment is moved while moving in the treatment bath. The liquid is agitated, and these agents are mixed uniformly, which is preferable because there is a merit that a reduction effect can be obtained. In this case, the moving speed of the leather-like sheet in the treatment bath is preferably 10 m / min or more, particularly 50 to 300 m / min, from the viewpoint of the stirring action and the leveling effect.

  The reduction cleaning treatment in a water bath containing an alkaline substance, a reducing agent and a surfactant needs to be performed while maintaining the temperature of the treatment bath (water bath, dye bath) at 60 ° C. or higher, and is 70 to 95 ° C. It is preferable to carry out while maintaining the above. When the bath temperature during the reduction cleaning treatment is less than 60 ° C., the leather-like sheet is not sufficiently subjected to reduction cleaning, resulting in low fastness. When the bath temperature exceeds 95 ° C., the disperse dye inside the fiber is reduced and washed, and the color developability is deteriorated, which easily causes dyeing spots.

  The reductive cleaning time is not particularly limited, but generally 10 to 120 minutes is preferable, and 30 to 60 minutes is more preferable. When the reduction cleaning time is less than 10 minutes, the reduction cleaning to the leather-like sheet is not sufficient, and a large amount of the dye in the elastic polymer of the leather-like sheet remains, and the appearance and fastness are reduced. To do. On the other hand, even when the reduction cleaning treatment time exceeds 120 minutes, no essential problem occurs, and the disperse dye dissolution and removal has reached saturation and the fastness is not further improved. It is preferable to make it less than minutes. Further, the number of reduction washings needs to be taken out from the dyeing machine, and depending on the amount of dye concentration used, it may be better to carry out the reduction washings twice or more depending on necessity.

  The oxidation treatment after the reduction cleaning is performed after discharging the reducing agent solution from the inside of the dyeing machine, adding water, and washing with water. The method of oxidation treatment is not particularly limited, a method of oxidizing by introducing air or oxygen gas into the atmosphere of the treatment bath, a method of using an oxidant, a method of using both oxidation by air or oxygen gas and oxidation by an oxidant And so on. Among them, the method using both oxidation with air or oxygen gas and oxidation with an oxidizing agent is preferable because water insolubilization, fixation, and color development by oxidation of the disperse dye can be performed more quickly and reliably. The kind of the oxidizing agent used for the oxidation treatment is not particularly limited, and is generally used conventionally in dyeing plants such as hydrogen peroxide, potassium dichromate, excessive permanganate, perboric acid, and the like. One or more oxidizing agents can be used.

The oxidation treatment with an oxidizing agent may be performed simultaneously with neutralization of the alkaline substance using acetic acid or other neutralizing agents conventionally used in dyeing plants. In the former case, the neutralization treatment is performed after the oxidation treatment. Do.
The concentration of the oxidizing agent in the bath when oxidizing with an oxidizing agent should be adjusted as appropriate according to the type of oxidizing agent, processing conditions such as processing temperature and processing time, and the amount of disperse dye. Can do. For example, when hydrogen peroxide is used as the oxidizing agent, it is preferably used at a rate of 0.5 to 20 g / liter bath.
The treatment temperature and treatment time during the oxidation treatment using the oxidizing agent can also be adjusted as appropriate according to the type and concentration of the oxidizing agent, the type and amount of disperse dye, the type and concentration of the reducing agent, and the like. However, generally, it is preferable to carry out at 30-70 degreeC for about 10-90 minutes.

The leather-like sheet which has been subjected to the oxidation treatment as described above is directly dried and dyed. Further, the dyeing fastness of the leather-like sheet is further improved by performing the soaping process.
In the soaping process, surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants, and reducing detergents commonly used in fabric soaping processes, etc. Any of these can be used and is not particularly limited. The conditions of the soaping process are not particularly limited because the process conditions conventionally used in the soaping process for fabrics can be adopted, but the soaping bath temperature is set to 40 to 100 ° C., particularly 60 to 95 ° C., and it adheres to the leather-like sheet. It is preferable to remove the excess dye to a target level.

  It is preferable to perform a brushing treatment after the above-described oxidation treatment or soaping treatment from the viewpoint that it is easy to completely remove excess dye adhering to the surface of the leather-like sheet. The brushing treatment is more preferably performed in a wet state from the viewpoints of dye removal efficiency and hair styling. Further, it is preferable from the viewpoint of dye removal efficiency that the brushing treatment is performed in a liquid using a brush roll to which abrasive grains are attached.

By performing the above-described series of treatments using a leather-like sheet that has been raised in advance and formed napped on one or both sides, a fiber aggregate mainly composed of polyester fibers and an elastic polymer contained therein are used. Thus, the intended dyed standing fur leather-like sheet mainly composed of polyester-based ultrafine fibers on one or both sides is produced.
In addition, when the above-described series of treatments are performed using a leather-like sheet that has not been subjected to raising treatment, napping consisting of a fiber assembly mainly composed of polyester fibers and an elastic polymer contained therein is used. Since the dyed leather-like sheet is produced, the intended dyed standing fur-leather-like sheet can be produced by subjecting the leather-like sheet to the raising treatment described above.

The standing fur leather-like sheet obtained by the method of the present invention takes advantage of excellent characteristics such as stable color development, uniform hue without spots, and high dyeing fastness,
It can be suitably used as a skin material or a backing material for applications requiring a high level of dyeing fastness, such as clothing, gloves, shoes, interiors, and vehicle interior materials.

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to the following examples. In the following examples, the volume content of oxygen in the atmosphere during the reduction cleaning treatment was measured as follows.

(1) Volume content of oxygen in the atmosphere during the reduction cleaning process: in the atmosphere of the reduction cleaning machine (because the reduction cleaning process is performed with the same machine as the dyeing machine, it may be hereinafter referred to as the inside of the dyeing machine). The measurement was performed by inserting a sensor portion of an oxygen concentration meter (“XO-326AL” manufactured by Shin Cosmos Electric Co., Ltd.). The size of the insertion port was made equal to that of the sensor unit so as to prevent the inflow of air into the atmosphere in the dyeing machine as much as possible, and grommet sealing was performed during measurement.

  Further, the dyeing uniformity, washing fastness, migration and dyeing friction fastness of the dyed standing fur leather-like sheet obtained in the following examples were measured as follows.

(1) Dyeing uniformity:
The surface of the dyed standing fur leather-like sheet obtained in the following examples was visually observed and evaluated according to the following evaluation criteria.
[Evaluation criteria for dyeing uniformity]
◎: Standing fur made of polyester microfiber forming the surface of the standing fur leather-like sheet is dyed uniformly and dark, has no color spots, has a high-grade color tone, and has very good color development It is.
○: Napped fibers made of polyester microfibers forming the surface of the standing fur leather-like sheet are almost uniformly dyed, have no color spots, have a substantially uniform color tone, and have a normal color development.
(Triangle | delta): The dyeing | pulling of the nap made from the polyester extra fine fiber which makes the surface of a standing fur leather-like sheet | seat is inadequate, or is dye | stained somewhat unevenly, and color development is a little bad.
X: Napped fibers made of polyester ultrafine fibers forming the surface of the standing fur leather-like sheet are hardly dyed, are extremely light colors, and have a poor color tone without any sense of quality.

(2) Fastness to washing The fastness to washing (discoloration and staining) of the dyed standing fur leather-like sheet obtained in the following examples was evaluated according to JIS L-0844-1973 A-1.
(3) Migration Evaluation was made according to JIS L-0849-1996.
The contaminated fabric was evaluated using a multi-woven fabric defined in JIS L-0803-1998.
(4) Dyeing friction fastness:
The dyeing friction fastness (dry / wet) of the dyed standing fur leather-like sheet obtained in the following examples was evaluated according to JIS L-0849-1971.
(5) Dry cleaning The wash fastness (discoloration and staining) of the dyed standing fur-leather-like sheet obtained in the following examples was evaluated according to JIS L-0860-1996 A method.

Sea-island type composite fiber with 60 parts of polyethylene terephthalate with an intrinsic viscosity of 0.65 and 40 parts of linear low-density polyethylene with MFR = 40 as the sea component (20 islands, fineness 4.0 decitex, fiber length 51 mm, 捲A non-woven fabric was prepared by performing needle punching with a thickness of 1.3 mm and a basis weight of 530 g / m ² using a 12-shrinkage / inch). The nonwoven fabric was impregnated with a 15% dimethylformamide (hereinafter abbreviated as DMF) solution of polyether polyurethane so that the solid content would be 20% by mass of the standing fur leather-like sheet, wet-coagulated with a DMF aqueous solution, and washed with water. The sea component polyethylene was extracted and removed with 85 ° C. toluene to obtain a leather-like sheet substrate having a basis weight of 480 g / m ² , a thickness of 1.0 mm, and a fineness of the polyester ultrafine fiber of 0.024 dtex.

After buffing one side of the obtained substrate with sand paper No. 180 to a thickness of 0.8 mm, a solvent mixed with 30 parts of DMF and 70 parts of acetone on the opposite side was used with a 200 mesh gravure roll. 8 g / m ^{2 was} applied and dried, and the gravure surface was buffed twice with No. 240 sandpaper and twice with No. 400 sandpaper to obtain a standing fur leather-like sheet before dyeing.

Next, this standing fur leather-like sheet was put into a circular liquid dyeing machine (“Circular Rapid Dyeing Machine CUT-RA-2L” manufactured by Nisaka Manufacturing Co., Ltd.), and a predetermined amount of water was added thereto, and the standing fur leather obtained there was obtained. After adding the sheet (bath ratio = 1: 30) and raising the water temperature to 90 ° C., the standing fur leather-like sheet is moved at the same temperature for 30 minutes at a moving speed (rotary reel speed) of 180 m / min. Then, after the standing fur leather-like sheet was sufficiently conditioned to water, the water temperature was cooled to 40 ° C. or lower and drained.
Dyeing was performed at 135 ° C. for 60 minutes with the following disperse dye composition and auxiliary composition at a bath ratio of 1:15.

dye:
Harmony Light Blue GN (Hokuriku Color Co., Ltd.) 0.17% owf
Harmony Light Blue BHL (Hokuriku Color Co., Ltd.) 0.46% owf
Harmony Light Red RHL (Hokuriku Color Co., Ltd.) 0.58% owf
Harmony Light Yellow MS6 (Hokuriku Color Co., Ltd.) 1.15% owf
Leveling agent: KP leveler AUL (aromatic sulfonate derivative, manufactured by Nippon Kayaku Co., Ltd.)
2g / L
pH adjuster: New buffer K (manufactured by Mitsima Chemical Co., Ltd.) 1.8 g / L
Metal ion sequestering agent: Skarner NT (manufactured by Takamatsu Yushi Co., Ltd.) 1.0 g / L

After dyeing, the temperature was lowered, followed by washing with water. After washing with water, water was inserted so that the bath ratio was 1:20, and after the dyeing machine was sealed, nitrogen gas was introduced using a nitrogen generator until the pressure in the dyeing machine reached 304 kPa), and then The introduction of nitrogen gas was stopped, the mixed gas of air and nitrogen gas in the dyeing machine was exhausted, and this treatment was repeated three more times. When the volume content of oxygen in the gas (atmosphere) in the dyeing machine at this time was measured by the method described above, it was 0.6%, and the atmosphere was substantially free of oxygen. Next, the following reducing agent was added.
Sodium hydroxide 6g / L
Thiourea dioxide 3g / L
H867 (manufactured by Yushi Co., Ltd., chelating agent) 1 g / L

Thereafter, the temperature was increased to 70 ° C. at a rate of temperature rise of 1 ° C./minute, washed for 30 minutes, then cooled down and washed with water, and then the above reduction washing method was repeated twice, followed by washing with water. .
After that, oxidation treatment was performed under the following conditions: Hydrogen peroxide 3g / L
Sodium carbonate 3g / L
Treatment conditions: 70 ° C x 20 minutes

  The dyed standing fur leather-like sheet had an elegant suede-like appearance in which the napped fibers made of polyester ultrafine fibers on the surface and the polyurethane visible between the napped fibers were balanced and evenly dyed. The dyeing friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated, and as shown in Table 1 below.

Example 1 except that the standing fur leather-like sheet dyed gray and washed with water by the circular dyeing machine of Example 1 was sealed with nitrogen in the same manner as in Example 1 and the concentrations of the alkaline substance and the reducing agent were conducted under the following conditions. Repeated twice under the same conditions, oxidized, washed with water and dried to obtain a gray standing fur leather-like sheet.
Sodium hydroxide 2g / L
Thiourea dioxide 1g / L
H867 (manufactured by Yushi Co., Ltd., chelating agent) 1 g / L
The standing fur leather-like sheet had an elegant suede-like appearance in which the surface polyester microfibers were uniformly dyed in color. The dyeing friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated, and as shown in Table 1 below.

A needle punching process with a basis weight of 600 g / m ² was performed in the same manner as in Example 1, and the nonwoven fabric was shrunk 22% by 26% in hot water at 90 ° C. and then dried. Thereafter, a 5% solution of polyurethane emulsion resin (Vonic 1310 made by Dainippon Ink & Chemicals, Inc., insoluble in DMF) is impregnated so that the solid fur content is 3.1% by mass of the standing fur leather-like sheet to obtain a squeeze rate of 60%. Thereafter, drying was performed at 150 ° C. The polyurethane emulsion was merged near the surface of the nonwoven fabric and unevenly distributed near the surface to obtain a filmed nonwoven fabric. This nonwoven fabric was impregnated with a 15% DMF solution of polyether polyurethane to a solid content of 20% by mass of the standing fur leather-like sheet, wet coagulated with a DMF aqueous solution, washed with water, and then seawater-containing polyethylene with 85 ° C. toluene. Upon extraction and removal, a leather-like sheet substrate having a basis weight of 675 g / m ² , a thickness of 1.5 mm, and a polyester ultrafine fiber density of 0.45 g / cm ³ and a fineness of 0.024 dtex was obtained.

The obtained substrate was sliced in the thickness direction, and the sliced surface was buffed with No. 180 sandpaper to make the thickness 0.6 mm, and then mixed on the opposite side at a ratio of 30 parts DMF and 70 parts acetone. 8g / m ² using a 200 mesh gravure roll and then dried, and the gravure surface is buffed twice with No. 240 sandpaper and twice with No. 400 sandpaper, and the standing fur leather-like sheet before dyeing Got. The polyurethane emulsion resin was unevenly distributed on the raised surface side of the obtained standing fur leather-like sheet. This suede-like raw machine was dyed in the same manner as in Example 1 under the following conditions.

dye:
Dianix Black HLA (Dystar) 15.0% owf
Dianix Red HLA (Dyster) 4.5% owf
Dianix Yellow HLA (Dystar) 6.0% owf
Leveling agent: KP leveler AUL (aromatic sulfonate derivative, manufactured by Nippon Kayaku Co., Ltd.)
1.0 g / l
pH adjuster: New buffer K (manufactured by Mitsima Chemical Co., Ltd.) 1.8 g / L
Metal ion sequestering agent: Skarner NT (manufactured by Takamatsu Yushi Co., Ltd.) 1.0 g / L
went.

  Subsequently, reduction washing, water washing, and oxidation treatment were performed in the same manner as in Example 1 and dried. The obtained dyed standing fur leather-like sheet had an elegant suede-like appearance in which the surface of the polyester ultrafine fiber was uniformly dyed black. The dyeing friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated, and as shown in Table 1 below.

Polyvinyl alcohol copolymer (manufactured by Kuraray Co., Ltd.) containing 10 mol% of isophthalic acid copolymerized polyethylene terephthalate (melting point: 234 ° C), containing 10 mol% of ethylene units, a saponification degree of 98.4 mol%, and a melting point of 210 ° C A sea island fiber having a single yarn fineness of 6 dtex was obtained by performing composite spinning of 12 islands of sea island fibers having a sea component of EXCEVAL) and a mass ratio of sea / island = 40/60. The fiber was crimped, cut to 51 mm, and carded to produce a short fiber web.
Next, after adding 84 T / m of additional yarn to 84 decitex / 36 f false twisted polyester yarn, weaving was performed at a twist density of 82/76 / inch, and a plain fabric with a basis weight of 55 g / m ² . Got.
After laminating the web and plain fabric, needle treatment was performed under the condition of 1200 punch / cm ² and dry heat shrinkage treatment was performed at 200 ° C., resulting in a basis weight of 580 g / m ² and an apparent density of 0.350 g / cm ^3. A 1.67 mm fiber entangled body was obtained.
Next, water was added to a polycarbonate-based polyurethane water emulsion (manufactured by Nikka Chemical Co., Ltd., Evaphanol, APC-28) to obtain an elastic polymer aqueous dispersion having a concentration of 10%. The thermal gelation temperature of this elastic polymer aqueous dispersion was 60 ° C.
Next, the elastic polymer liquid was impregnated with a solid content (fiber entangled fiber + woven / knitted fabric) / elastic polymer = 80/20 mass ratio. After impregnating the elastic polymer aqueous dispersion, infrared rays having a maximum energy wavelength of 2.6 μmh were irradiated at 97 V for 60 seconds, and the fiber entangled surface temperature was raised to 70 ° C. Moreover, the moisture content after infrared irradiation was 30%. Thereafter, it was heated and dried with a hot air dryer at 155 ° C. to completely heat and dry the moisture, to completely evaporate the moisture and to cure the elastic polymer, and to fix to the fiber entangled body. Thereafter, the polyvinyl alcohol copolymer was extracted and removed with hot water at 90 ° C. and dried. After that, when the opposite side of the scrim insertion is brushed with # 320 sandpaper, the surface is covered with napped fibers of about 0.2 decitex, and the unstained artificial leather with the scrim inserted on the back side A similar sheet was obtained.

Next, this standing fur leather-like sheet is put into a circular liquid flow dyeing machine (“Circular Rapid Dyeing Machine CUT-RA-2L” manufactured by Nisaka Manufacturing Co., Ltd.), and a predetermined amount of water is added thereto, and the above-mentioned standing fur leather-like sheet is placed there. (Bath ratio = 1: 30), and after raising the water temperature to 90 ° C., move the standing fur leather-like sheet at the same temperature for 30 minutes at a moving speed (rotary reel speed) of 180 m / min. After the standing fur-leather-like sheet was sufficiently familiar with water, the water temperature was cooled to 40 ° C. or lower and drained.
Dyeing was performed at 135 ° C. for 60 minutes with the following disperse dye composition and auxiliary composition at a bath ratio of 1:15.

dye:
Dianix Black HLA (Dystar) 15.0% owf
Dianix Red HLA (Dyster) 4.5% owf
Dianix Yellow HLA (Dystar) 6.0% owf
Leveling agent: KP leveler AUL (aromatic sulfonate derivative, manufactured by Nippon Kayaku Co., Ltd.)
1.0 g / l
pH adjuster: New buffer K (manufactured by Mitsima Chemical Co., Ltd.) 1.8 g / L
Metal ion sequestering agent: Skarner NT (manufactured by Takamatsu Yushi Co., Ltd.) 1.0 g / L

After dyeing, the temperature was lowered, followed by washing with water. After water washing, after inserting water so that the bath ratio becomes 1:20, nitrogen gas was introduced using a nitrogen generator until the pressure in the dyeing machine was 304 kPa) with the dyeing machine sealed. Thereafter, the introduction of nitrogen gas was stopped, the mixed gas of air and nitrogen gas in the dyeing machine was exhausted, and this treatment was further repeated three times. When the volume content of oxygen in the gas (atmosphere) in the dyeing machine at this time was measured by the method described above, it was 0.6%, and the atmosphere was substantially free of oxygen.
Next, the following reducing agent was added.
Sodium hydroxide 2g / L
Thiourea dioxide 1g / L
H867 (manufactured by Yushi Co., Ltd., chelating agent) 1 g / L
Thereafter, the temperature was raised to 70 ° C. at a rate of temperature rise of 1 ° C./1 minute, washed for 30 minutes, then the temperature was lowered and washed with water, and then the above reduction washing method was repeated twice, followed by washing with water. .

After that, oxidation treatment was performed under the following conditions: Hydrogen peroxide 3g / L
Sodium carbonate 3g / L
Treatment conditions: 70 ° C x 20 minutes

  The dyed standing fur leather-like sheet had an elegant suede-like appearance in which the napped fibers made of polyester ultrafine fibers on the surface and the polyurethane visible between the napped fibers were balanced and evenly dyed. The dyeing friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated, and as shown in Table 1 below.

Comparative Example 1
In Example 1, reduction cleaning after dyeing was performed without performing nitrogen sealing. The obtained fur-like sheet was dyed almost gray on the entire surface. However, when observed in detail, polyurethane dyed in pale yellow-green is not colored with napped fibers made of polyester ultrafine fibers on the surface. It was seen from between, and it was in a state where greens with different hues were mixed, lacking in uniformity of hue, and lacking elegance. The dyeing friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated, and as shown in Table 1 below.

Comparative Example 2
In Example 2, reduction cleaning after dyeing was performed without performing nitrogen sealing. The resulting standing fur leather-like sheet was dyed in gray with a sharp surface, but when observed in detail, the polyurethane side was dyed in dark gray, whereas the polyester polyester fiber on the surface was dyed in bright gray. The polyurethane was visible from between the raised fibers, and the color of the surface appearance was marbling, lacking in hue uniformity and lacking elegance. The dyeing friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated, and as shown in Table 1 below.

Comparative Example 3
In Example 3, it was the reduction | restoration washing | cleaning after dyeing | staining, and performed without performing the nitrogen seal | sticker similar to Example 3. FIG. The entire surface was dyed black and the dyeability was uniform, but the color was slightly sharp. When this dyed standing fur leather-like sheet was evaluated for fastness to dyeing friction, migration, fastness to washing and fastness to dry cleaning, it was a product with low sweat fastness as shown in Table 1 below.

Comparative Example 4
In Example 4, it was the reduction | restoration washing | cleaning after dyeing | staining, and the result performed without performing the nitrogen seal | sticker similar to Example 4. FIG. The entire surface was dyed black and the dyeability was uniform, but the color was slightly sharp. Further, the dyed friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated, and as shown in Table 1, the sweat fastness was low.
Comparative Example-5
In Example 4, the reduction cleaning after dyeing was not performed with the same nitrogen sealing as in Example 4, but the reduction cleaning was repeated twice for 30 minutes at a bath temperature of 55 ° C. under the following conditions.
Sodium hydroxide 6g / L
Thiourea dioxide 3g / L
H867 (manufactured by Yushi Co., Ltd., chelating agent) 1 g / L
Other than that, the same procedure as in Example 4 was performed. As a result, the obtained standing fur leather-like sheet was dyed black on the entire surface, and the dyeability was uniform, but the color was slightly sharpened. It was. See also Table 1 below. By performing the reduction cleaning treatment of the standing fur leather-like sheet at a temperature of 55 ° C., which is lower than 60 ° C., the polyurethane is dyed darker than the napped fibers made of polyester fine fibers on the surface. The color difference from the raised fiber was large and the surface dyeing stability was poor. Further, the dyeing friction fastness, migration, fastness to washing and fastness to dry cleaning of this dyed standing fur leather-like sheet were evaluated. As shown in Table 1, the dyeing fastness was poor.

  As can be seen from the results in Table 1, in Comparative Examples 1 to 4, the reduction cleaning treatment of the standing fur leather-like sheet is performed in an atmosphere containing a lot of oxygen, so that the reducing agent is quickly decomposed and the reduction cleaning effect is small. Therefore, the effect of removing the dye dyed on the polyurethane is small, the polyurethane side is dyed in a dark color and has a marbling tone, and the dyeing fastness is low, so the commercial value is extremely low.

Claims (8)

Before or after raising at least one side of a non-woven fabric made of polyester-based ultrafine fibers having a single fineness of 0.5 dtex or less and a leather-like sheet made of an elastic polymer contained therein, the leather-like sheet is placed in a dyeing machine. In a method of dyeing the leather-like sheet by dyeing with a disperse dye and performing a reduction washing treatment followed by an oxidation treatment, the reduction washing treatment satisfies both the following 1) to 4): A method for producing a dyed standing fur-leather-like sheet.
1) Perform in the same dyeing machine as the dyeing process,
2) Use a reducing cleaning solution containing an alkaline substance, a reducing agent and a surfactant,
3) Performing in an atmosphere having a volume content of oxygen of less than 5%,
4) Perform the reducing cleaning solution temperature at 60 ° C. or higher, The method for producing a standing fur leather-like sheet according to claim 1, wherein the elastic polymer is polyurethane. The method for producing a standing fur leather-like sheet according to claim 1 or 2, wherein the content of the elastic polymer is 5% by mass or more of the standing fur leather like sheet. The elastic polymer comprises a polyurethane soluble in dimethylformamide and a polyurethane insoluble in dimethylformamide, and the polyurethane insoluble in dimethylformamide is unevenly distributed on the raised surface side. Manufacturing method of standing fur leather-like sheet. The manufacturing method of the standing fur leather-like sheet | seat of any one of Claims 1-4 which performs a soaping process after an oxidation process. The manufacturing method of the standing fur leather-like sheet | seat of any one of Claims 1-5 which performs a brushing process after an oxidation process or a soaping process. A dyed standing fur-leather-like sheet obtained by the method for producing a standing fur-leather-like sheet according to any one of claims 1 to 6. A garment, interior material, vehicle interior material, shoe or bag using the standing fur leather-like sheet according to claim 7.