JP4879790B2 - Method for producing antibacterial suede-like artificial leather - Google Patents

Description

  The present invention relates to a method for producing an antibacterial suede-like artificial leather having stable antibacterial performance, and having a good texture and appearance.

  In fabric products used in daily life, there are an increasing number of cases in which certain antibacterial properties are required for hygiene reasons, and in recent years, there is an increasing need for antibacterial artificial leather in the artificial leather field. For this reason, various antibacterial agents such as organic antibacterial agents such as quaternary ammonium salts and inorganic antibacterial agents typified by silver ions are used as antibacterial agents. It is supposed that the cationic component comes into contact with the target bacteria and destroys the target bacteria. Therefore, in general, in order to impart antibacterial performance to fabric products, natural leather products or fabric products are impregnated in a treatment solution in which an antibacterial agent and, if necessary, a binder resin are dissolved or dispersed in water or a solvent. The method of making it adhere is common (for example, refer patent documents 1 and 2).

However, when the above method is applied to suede-like artificial leather dyed with a metal complex hydrochloric acid dye, the antibacterial effect varies depending on the metal complex hydrochloric acid dye used, especially black, dark blue, dark tea using a large amount of dye. There are cases where the effect is not manifested in products dyed in the colors of the system.
Also, depending on the structure of the metal complex hydrochloric acid dye, there are some which have a large interaction with the antibacterial agent, and even when the amount of the dye used is small, there may be a case where a sufficient antibacterial effect is not exhibited. In such a case, it can be solved by increasing the concentration of the antibacterial agent to be used, but if the concentration of the antibacterial agent is increased, the texture of the obtained antibacterial suede-like artificial leather and the touch deteriorate, When using an expensive antibacterial agent, increasing the concentration leads to an increase in cost, which is not a preferable method.

Japanese Patent Laid-Open No. 7-10715 Patent No.3052296

  The present invention was made in view of the current situation as described above, and even if it is a suede-like artificial leather dyed with a metal complex hydrochloric acid dye, it has a stable antibacterial performance regardless of the dye used, and has a texture and appearance. The present invention provides a method for producing a good antibacterial suede-like artificial leather.

  In order to achieve the above object, the present inventors have made extensive studies. As a result, in providing antibacterial performance to a suede-like artificial leather dyed with a metal complex hydrochloric acid dye, the above-mentioned problems can be solved by applying an antibacterial agent after pretreatment with a cationic drug after dyeing. And the present invention was completed based on this finding.

That is, the present invention
(1) A method for producing an antibacterial suede-like artificial leather by imparting antibacterial properties to a suede-like artificial leather dyed with a metal complex hydrochloric acid dye, the step of dyeing the suede-like artificial leather with a metal complex hydrochloric acid dye, A method for producing an antibacterial suede-like artificial leather comprising a step of pretreating a suede-like artificial leather obtained in a dyeing step with a cationic agent, and a step of applying an antibacterial agent to the pretreated suede-like artificial leather;
(2) The method for producing an antibacterial suede-like artificial leather according to (1), wherein the cationic drug is an organic quaternary ammonium salt,
(3) The method for producing an antibacterial suede-like artificial leather according to (1), wherein the antibacterial agent is an antibacterial agent containing an organic quaternary ammonium salt;
It is.

  According to the present invention, even a suede-like artificial leather dyed with a metal complex hydrochloric acid dye has an antibacterial suede-like artificial leather having a stable antibacterial performance regardless of the dyed color, and having a good texture and appearance. The manufacturing method of can be provided.

Hereinafter, the present invention will be described in detail.
Examples of the raw fiber used in the present invention include ordinary fibers such as fibers that can be dyed with a metal complex hydrochloric acid dye, for example, synthetic fibers made of synthetic resin represented by polyamide, natural fibers such as silk and wool, and the like. . In the case of synthetic fibers, not only fibers made of a single polymer, but also synthetic fibers obtained by mixing or spinning two or more polymers may be used. For example, a polyamide fiber alone or a fiber obtained by mixing and spinning a polyamide fiber and a synthetic fiber such as polyester, polyacrylonitrile, polyolefin (polyethylene, polypropylene, etc.), polyvinyl alcohol, or the like can be given.
In the case of using mixed-spun fibers or composite-spun fibers, an optional step of producing a leather-like sheet from at least one of the two or more polymers constituting the fibers in a later step. In this method, the fiber is made into a fine hollow fiber or a porous hollow fiber having a large number of hollows inside by adopting a method of extracting or decomposing in a method of dividing or dividing into each polymer component constituting the fiber. preferable.

  These mixed-spun fibers and composite-spun fibers are used as a web, and the web is entangled by needle punching or high-speed fluid flow to obtain a nonwoven fabric. It can also be a knitted fabric. Furthermore, it can also be set as the laminated body of a nonwoven fabric and a knitted fabric. Next, these nonwoven fabrics, woven or knitted fabrics or laminates thereof (hereinafter, these may be collectively referred to as fiber aggregates) are impregnated with an elastic polymer solution or dispersion liquid. Prior to the impregnation treatment with the dispersion, it is preferable to smooth the surface of the fiber assembly by a method such as hot pressing, if necessary. In addition, in order to prevent the rupture of the fiber aggregate that is likely to occur during the impregnation / coagulation of the solution or dispersion of the elastic polymer or the extraction of the fiber constituent polymer, the surface of the fiber aggregate is heated and pressed between the constituent fibers. A method of partially fusing or a method of impregnating and drying the fiber aggregate with a water-soluble resin typified by polyvinyl alcohol and fixing between the fibers by glue may be used. The thickness of the fiber assembly is preferably 1 to 3 mm.

  The elastic polymer impregnated in the fiber assembly of the present invention is at least one selected from the group of elastic polymers such as polyurethane, acrylic polymers, acrylonitrile / butadiene copolymers, styrene / butadiene copolymers and the like. The elastic polymer can be mentioned. Polyurethane is particularly preferable from the viewpoints of texture, durability, and adhesive strength with the surface layer. The polyurethane includes at least one diol selected from polymer diols having a number average molecular weight of 500 to 2500, such as polyester diol, polyether diol, polyester ether diol, polycaprolactone diol, polycarbonate diol, and the like, and organic polyisocyanate. For example, at least one organic polyisocyanate selected from the group of aromatic diisocyanate, aromatic triisocyanate, alicyclic diisocyanate, aliphatic diisocyanate having a cyclic group, triphenylmethane-4,4,4-triisocyanate, etc. Isocyanate and a low molecular weight compound having a molecular weight of 300 or less having at least two active hydrogen atoms, such as low molecular diol, low molecular diamine, hydrazine and dicarboxylic acid dihydrazide Yu low molecular weight compound is a polyurethane elastomer obtained by reacting a chain extender.

  The raw material composition of these polyurethanes should be appropriately selected so as to satisfy various physical properties such as texture, deterioration resistance, yellowing resistance, and dyeability according to the application field of the antibacterial suede-like artificial leather finally obtained. Can do. If necessary, other polymers, various stabilizers, colorants, coagulation regulators and the like are added to these elastic polymers. As described above, the elastic polymer is impregnated into the fiber assembly in the state of a solution or a dispersion and solidified. As the coagulation method, a wet coagulation method is preferable in terms of texture. By using the wet coagulation method, the elastic polymer becomes porous and a natural leather-like texture can be obtained. The amount of the elastic polymer impregnated into the fiber aggregate is 100 parts by mass with respect to 100 mass parts of the fiber aggregate (when one component in the fiber is removed by extraction or the like). 10 to 60 parts by mass is preferable.

  When the fiber assembly is composed of mixed spun fibers or composite spun fibers composed of two or more kinds of polymers, these fibers are composed before or after impregnating the elastic polymer into the fiber assembly. It is preferable to use a method in which at least one component of the polymer is dissolved or decomposed and removed to leave at least one component. For example, when the mixed spun fiber or composite spun fiber is a fiber having a sea-island cross section, when the sea component is dissolved or decomposed and removed, the island component remains and the fiber becomes an ultrafine fiber bundle, while the island component is dissolved and removed. The sea component remains and becomes a porous hollow fiber having many hollow portions in the fiber. In addition, when the fiber is a composite spun fiber in which a plurality of polymers are bonded in the length direction, a method of dividing the fiber physically or chemically to form an ultrafine fiber bundle may be used. . The thickness of the ultrafine fiber is preferably 0.0001 to 0.5 dtex, particularly preferably 0.001 to 0.2 dtex.

  The above-mentioned fiber aggregate is impregnated and solidified with an elastic polymer, and the surface of the leather-like sheet obtained by ultrafineening as necessary is buffed to adjust the napping, thereby obtaining undyed suede-like artificial leather.

(1) Dyeing process using a metal complex hydrochloric acid dye When the fiber aggregate for undyed suede-like artificial leather obtained as described above is mainly composed of fibers of a polyamide-based resin, the metal complex hydrochloric acid is then used. Dyeing with dye is performed. Examples of the dyeing machine to be used include a Wins dyeing machine, a dash line dyeing machine, and a circular dyeing machine, and any of these can be used preferably. As dyeing conditions, the dye concentration is preferably 0.01% by mass or more and 20% by mass or less, particularly 2 to 20% by mass with respect to the mass of the suede-like artificial leather. The temperature of the dyeing treatment is preferably 60 ° C. or higher, more preferably 70 to 90 ° C., and the dyeing time is preferably 10 minutes or longer, more preferably about 30 to 60 minutes. You may use auxiliary agents, such as leveling agent, as needed.
As metal complex hydrochloric acid dyes used, Irgaran Yellow GRL, Isolan Olive 2S-BGL, PM Red 531, Irgaran Red 2GL, Ranacron Olive SG, Kayakaran Black 2RL, Irgaran Gray GLN, Vitanil Navy KM, Irgaran Blue 3GL, Lanaron Blue PM Brown GF, Ranacron Red Brown SR and the like can be mentioned, and in particular, Kayakaran Black 2RL, Irgaran Gray GLN, etc. as black dyes, Vitanil Navy KM, Irgaran Blue 3GL, etc. as dark blue dyes, Examples of tea-based dyes include Ranacron Brown SGR, PM, Brown GF, and Ranacron Red Brown SR.

(2) Pre-treatment step with cationic agent When antibacterial agent is directly applied to the dyed suede-like artificial leather obtained as described above, the antibacterial performance varies depending on the dye used. There is. This is due to the fact that the anion component derived from the dye remaining in the dyed suede-like artificial leather, especially the elastic polymer component, binds to the cationic component of the antibacterial agent and inhibits the contact between the antibacterial component and the bacteria. It was found that it was caused by deactivating. Therefore, in the present invention, first, a pretreatment with a cationic drug is performed, and a pretreatment is performed in which the cationic drug is ion-bonded to an anion component (mainly sulfonic acid residue) derived from a dye and immobilized. As a pretreatment method, a dye containing suede-like artificial leather is dispersed on the entire surface of the dyed suede-like artificial leather by gravure treatment or the like. Any method such as a coating method and a method of processing in a dyeing pot following the dyeing step can be used, but padding is preferably used from the viewpoint of securing an effective concentration of processing and from the viewpoint of processing efficiency.
The temperature of the pretreatment with the cationic drug is preferably about room temperature to 60 ° C, more preferably 25 to 40 ° C. The treatment time is preferably about 1 minute to 1 hour.
The solvent or dispersion medium used for the preparation of the liquid containing the cationic drug is not particularly limited as long as it can dissolve or disperse the cationic drug, preferably water, methanol, ethanol, isopropyl alcohol, toluene, Examples thereof include methyl ethyl ketone or a mixed solvent thereof.

  The amount of cationic agent applied depends on the anion group concentration estimated to remain after dyeing, depending on the type of dye used, the dyeing concentration, etc., and the effect of immobilizing anion groups depending on the type of cationic agent used for pretreatment However, it cannot be set uniformly, but can be set as appropriate based on the antibacterial effect of the preliminary test. Preferably, the process which provides 1-30 mol cationic chemical | medical agent with respect to 1 mol of residual anionic groups is preferable.

  As the cationic drug to be used, an organic drug is preferable from the viewpoint that the remaining anion group can be immobilized, and among them, a quaternary ammonium salt having a formula weight of 200 to 2000 having an antibacterial effect is optimal. Examples of such agents include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide, trimethyl ammonium halides such as stearyl trimethyl ammonium chloride, dimethyl didecyl ammonium chloride, N-decyl-N-iso chloride. Benzyls such as nonyldimethylammonium chloride, dioctyldimethylammonium chloride, dicetyldimethylammonium chloride, dimethyldistearylammonium chloride, didimethylammonium chloride, benzalkonium chloride, myristyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, benzethonium chloride Luconium-type quaternary ammonium salts; chlorides such as laurylpyridinium chloride and cetylpyridinium chloride Rijiniumu like; tri chloride (polyoxyethylene) stearyl methyl ammonium, chloride and the like tri (polyoxyethylene) oleyl methyl ammonium; or compounds of these quaternary ammonium salts and silicones.

(3) Application process of antibacterial agent Next, an antibacterial agent is applied to the dyed suede-like artificial leather after the pretreatment. The antibacterial agent to be applied and the applied amount can be appropriately selected according to the target antibacterial standard. For example, it is preferable that it is 1-15 mass parts with respect to 100 mass parts of antibacterial suede-like artificial leather. When a powdery antibacterial agent is applied, a resin binder may be used in combination as long as the texture and napping are not impaired.
As the antibacterial agent to be used, those conventionally used can be used. Specifically, for example, benzalkonium chloride, hexamethylene bigamide hydrochloride, polyhexamethylene bigamide hydrochloride, organic silicone And quaternary ammonium salts.
The solvent or dispersion medium used for the preparation of the liquid containing the antibacterial agent is not particularly limited as long as it can dissolve or disperse the antibacterial agent, and preferably water, methanol, ethanol, isopropyl alcohol, toluene, methyl ethyl ketone. Or these mixed solvents etc. can be mentioned.
If necessary, for example, an additive such as a penetrating agent and a light fastening agent, for example, Takurel NS-170 (manufactured by Nichido Chemical Co., Ltd.) can be added as a penetrating agent to the liquid containing the antibacterial agent. The addition amount is about 50 to 200 parts by mass per 100 parts by mass of the antibacterial agent.
As the method for applying the antibacterial agent, the dye suede is treated by, for example, padding a liquid containing the antibacterial agent with respect to the pretreated dyed suede-like artificial leather in the same manner as the method of treating with a cationic drug in the pretreatment step. Any method such as a method of dispersing the whole artificial leather, a method of applying to the surface of the dyed suede artificial leather by gravure treatment, etc. can be used, but from the viewpoint of securing the effective concentration of the treatment and from the viewpoint of treatment efficiency The padding process is preferably used.
The application time is preferably about 1 minute to 1 hour, and the temperature is preferably about room temperature to 40 ° C.

  The antibacterial suede-like artificial leather obtained in the present invention has a stable antibacterial performance, has a good texture and appearance, and is used for clothing, shoes, gloves or interiors such as sofas. It is suitable as a material for product use in direct contact with skin, clothes, etc., or for product use used in combination with other materials.

  Next, although execution of the present invention is concretely explained with an example, the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% described in an Example are a mass part and mass%. The average fineness of the ultrafine fibers and the antibacterial properties of the obtained antibacterial suede-like artificial leather were evaluated by the following methods.

(1) Average fineness of ultrafine fiber It calculated | required by calculation from the density of the polymer used for formation of ultrafine fiber, and the cross-sectional area of ultrafine fiber. The cross-sectional area was obtained by observing at a magnification of several hundred to several thousand times using a scanning electron microscope.
(2) Evaluation of antibacterial properties The antibacterial properties were evaluated by the following experimental method.
Test method: ASTM E 2149 Antibacterial and deodorant processed product test manual Shake flask method, a predetermined bacterial solution and sample were shaken for 1 hour with a wrist action shaker, and a sterilization rate of 70% or more was passed.
Test bacteria: Klebsiella pneumoniae / Klebsiella pneumoniae ATCC 4352

Examples 1-3, Comparative Example 1
A sea-island composite fiber consisting of 60 parts of nylon (island component) and high-fluidity low-density polyethylene (sea component) was prepared by a melt spinning method, and this was stretched 2.5 times in warm water at 70 ° C. A fiber oil agent was applied to the sea-island type composite fiber, machine crimped and dried, then cut to 51 mm to obtain 4 dtex staple fiber. Using this stable fiber, a web having a basis weight of 600 g / m ² is formed by the scrap method, then needle punching of about 500 punches / cm ² is performed alternately from both sides, and further heated to 120 ° C. with a calender roll An intertwined nonwoven fabric (fiber assembly) with a smooth surface was produced by pressing. The basis weight of the entangled nonwoven fabric was 400 g / m ² and the apparent specific gravity was 0.3. This entangled non-woven fabric is impregnated with a 13% strength polyurethane dimethylformamide (DMF) solution mainly composed of polytetramethylene ether-based polyurethane, and dipped in a mixed solution of DMF / water = 15/85 to make the polyurethane porous. After wet coagulation to a quality, the sea component in the composite fiber was eluted and removed in hot toluene to obtain an ultrafine fiber (average fiber thickness of 0.05 dtex to obtain a leather-like sheet. The obtained leather-like sheet. The thickness was 1.4 mm and the amount of polyurethane was 160 g / m ^{2. The} resulting leather-like sheet was divided into two parts, the sliced surface was buffed to a thickness of 0.55 mm, and the other surface Was brushed with sandpaper having a particle size of # 400 to obtain undyed suede-like artificial leather.

This undyed suede-like artificial leather was dyed with a 1: 2 type metal complex dye under the following conditions.
Dye preparation:
(A) PM Red 531 (manufactured by Sumitomo Chemical Co., Ltd.): 1.60 owf%
(B) Irgaran Yellow (registered trademark, manufactured by Ciba Specialty Chemicals Co., Ltd.) GRL: 5.50 owf%
(C) Ranacron Brown (registered trademark, manufactured by Ciba Specialty Chemicals) SGR: 7.50 owf%
Bath ratio: 1: 100
Temperature, time: 90 ° C., 60 minutes Dyeing machine: Wins dyeing machine Next, as a pretreatment, an impregnating solution was prepared under the conditions shown in Table 1, padded to a moisture content of 70%, and then subjected to a pin tenter. It dried at 140 degreeC. Furthermore, as the antibacterial agent, AEM5772-2 (manufactured by AEGIS, (octadecylamino) (dimethyl) (trihydroxysilyl) (propyl) ammonium chloride) is used, and the water content becomes 70% by the impregnation liquid shown in Table-1. After performing the padding process as described above, the film was dried at 140 ° C. with a pin tenter. After drying, it was subjected to scouring and hair-styling treatment, and a brown antibacterial suede-like artificial leather with excellent appearance and excellent mechanical properties was obtained. Table 1 also shows the antibacterial evaluation.

Comparative Example 2
In Example 1, only antibacterial treatment was performed without performing pretreatment. Antibacterial performance did not reach the target. Table 1 also shows the antibacterial evaluation.

Comparative Example 3
In Example 1, no pretreatment was performed, and the concentration of the antibacterial agent was increased to 27%. Antibacterial performance did not reach the target. Table 1 also shows the antibacterial evaluation.

  Table 1 shows the evaluation results of the ultrafine fiber napped sheets obtained in the above examples and comparative examples.

Claims (2)

A method for producing antibacterial suede-like artificial leather by imparting antibacterial properties to a suede-like artificial leather dyed with a metal complex hydrochloric acid dye. In the process of dyeing a suede-like artificial leather with a metal complex hydrochloric acid dye, the dyeing step The resulting suede-like artificial leather was trimethylammonium halide, didimethylammonium chloride, benzalkonium-type quaternary ammonium salt, pyridinium chloride, tri (polyoxyethylene) stearylmethylammonium chloride and tri (polyoxyethylene) oleylmethyl chloride. An antibacterial suede-like artificial comprising a step of pretreating with at least one cationic agent selected from ammonium, and a step of applying an organic silicone-based quaternary ammonium salt as an antibacterial agent to the pretreated suede-like artificial leather A method of manufacturing leather.   The method for producing an antibacterial suede-like artificial leather according to claim 1, wherein the organosilicon quaternary ammonium salt is (octadecylamino) (dimethyl) (trihydroxysilyl) (propyl) ammonium chloride.