KR20020041858A - A process for the preparation of leather having far infrared radiation characteristic, antibacterial property and deodorizing property - Google Patents

Abstract

PURPOSE: Provided is a process for producing yellow soil treated leather having a far infrared ray emitting property, an antimicrobial property, and a deodorizing property, the produced leather can be used for making shoes. CONSTITUTION: The process comprises the steps of: impregnating a leather with a mixture comprising 10-15wt% of yellow soil having a particle size of 100-300 mesh and a vegetable natural retanning agent under the pH of 4.3-5.0 at 25-35deg.C; treating the obtained retanned leather with 8-15wt% of an acryl resin to prevent the yellow soil from eluting; treating the leather with 10-15wt% of the yellow soil and a branching agent and additionally treating with 8-15wt% of the acryl resin to prevent the yellow soil from eluting; additionally, treating the obtained leather with 8-15wt% of the acryl resin to prevent the yellow soil from eluting; fixing the yellow soil to the leather by using formic acid and a cationic branching agent as a binder. The vegetable natural retanning agent is selected from the group consisting of mimosa, quebracho, mangrove bark, pine bark, hemlock bark, and etc. And the acryl resin is sodium polyacrylate.

Description

A process for the preparation of leather having far infrared radiation characteristic, antibacterial property and deodorizing property}

The present invention relates to a method for producing leather having far-infrared radiation, antibacterial and deodorizing properties, and to an ocher treated leather product obtained by the method. More specifically, the present invention is to treat the leather in the retanning process and the eggplant process with a predetermined amount of loess having a specific particle size in the conventional manufacturing process of leather, far-infrared radiation characteristics, antibacterial characteristics and deodorizing characteristics It relates to a method for producing this excellent leather and to an ocher treated leather product obtained by the method.

Far-infrared ray is a kind of electromagnetic radiation having a wavelength range of about 4 to 100 μm. The far-infrared ray has the longest wavelength in the ultraviolet region, and stretches or scavenges interatomic or intermolecular bonds formed in the molecule. energy properties to activate in the form of scissoring).

Generally, minerals, including biotite, elvan, ceramics, ocher, and the like, are known to emit far infrared rays. In recent years, taking advantage of the fact that these minerals radiate far-infrared rays to provide a number of beneficial effects on health, synthetic fibers, nonwovens, health products (e.g. beds, mattresses, pillows, etc.), sauna baths, saunas and the like containing them Is being developed.

On the other hand, in the field of tanning, various processing agents have been treated to raw hides and have attempted to obtain leather having a beneficial effect on human health. The prior art in this field of tanning is listed as an example.

Sogabe Japanese Unexamined Patent Application Publication No. 8-27500 discloses leather exhibiting sterilizing power and deodorizing effect by adsorbing wood vinegar solution to leather.

Japanese Unexamined Patent Application Publication No. 5-171572, such as Kato et al., Discloses the formula Ag _0.005 Li _0.995 Zr ₂ (PO ₄ ) ₃ , Ag _0.1 (NH ₄ ) _1.9 Ti (PO ₄ ) ₂ .4H ₂ O. The antimicrobial leather which carried antimicrobial phosphate, etc. is described.

Japanese Laid-Open Patent Publication No. 8-27499 to Ishikawa discloses 2 to 4 leathers having a freeness of 700 ml or more and a colloidal content of 1.0% by weight or less of the leather fibers of the leather reticular layer. A method for producing antimicrobial leather by impregnating with an antimicrobial treatment liquid containing any one of an antimicrobial metal salt, an antimicrobial inorganic fine powder and an organic preservative as an active ingredient is described.

Japanese Patent Laid-Open No. 7-10715 to Nakano discloses a method of producing antimicrobial leather by spraying leather with an antimicrobial agent consisting of chlorhexidine.

U.S. Patent No. 3,991,238 to Topfl et al. Discloses epoxides containing two or more epoxide groups per molecule, fatty amines having 12 to 24 carbon atoms and dicarboxylic acids of the formula HOOC (CH ₂ ) _y-1 COOH. A dressing method is described for treating a reaction product to leather.

Korean Patent Publication No. 199595-0000075 describes a method for sterilizing and sterilizing leather, characterized in that the leather is treated with a treatment bath containing at least one salt of lanthanum or cerium.

Korean Patent Publication No. 10-0262351 describes a method of dyeing cotton fibers using ocher powder.

Korean Unexamined Patent Publication No. 2000-0033653 describes a leather paper containing a nephrite powder, a manufacturing method thereof, and a use thereof.

Korean Patent Laid-Open Publication No. 1999-0064591 discloses a method for producing an antimicrobial synthetic leather product by dispersing zeolite in a polyurethane resin.

Korean Unexamined Patent Publication No. 2000-0026558 discloses a method of manufacturing artificial leather resin by molding a particulate material composed of germanium, elvan, and loess or jade together with a synthetic resin raw material.

Korean Patent Laid-Open Publication No. 1999-0070829 discloses an antibacterial and deodorizing synthetic leather in which a coating layer made of a polyurethane resin and titanium dioxide is provided as a front surface or a back surface of a fabric layer.

Korean Laid-Open Patent Publication No. 1992-020010 describes a method of producing bio-ceramic artificial leather by adding bio-ceramic powder and filler to a PVC having a polymerization degree of 1000 or more, and foaming it with a low-temperature blowing agent.

Korean Unexamined Patent Publication No. 1993-000752 discloses a method for producing a polyurethane artificial leather that contains a bio ceramic in a polyurethane artificial leather and emits far infrared rays.

In general, the leather manufacturing industry has a problem of generating a large amount of dye wastewater and causing environmental pollution. Therefore, if a dye amount less than that used in the dyeing process can be used in the dyeing process, it helps to solve this problem. Could be.

On the other hand, ocher has been used in various fields in view of its own characteristics of emitting far infrared rays and exhibiting antibacterial and deodorizing properties [Reference: Korean Patent Publication No. 2000-0007050, Korean Patent Publication No. 2000 -18929, Republic of Korea Patent Publication No. 2000-0013562, Republic of Korea Patent Publication No. 10-0231059, etc.], as mentioned in the above prior art, far-infrared radiation material such as ocher, inorganic silicate, bio-ceramic Artificial leather which has been treated with artificial leather or the like and has been known for its antimicrobial properties is known [Reference: Republic of Korea Patent Publication No. 1999-0064591, Republic of Korea Patent Publication No. 2000-0026558, etc., mentioned above]. By using loess together with acid dyes, which were considered almost impossible to treat directly, It is not known how to cope with environmental problems by using less than the amount used in the leather dyeing process and at the same time achieve the coloring effect as well as the far infrared radiation characteristics, the antibacterial and the deodorizing characteristics.

Accordingly, it is an object of the present invention to provide a method for producing leather having excellent far-infrared radiation characteristics, antibacterial properties and deodorizing properties by treating the leather with loess, which was considered almost impossible to be directly treated with leather.

1A and 1B are photographs showing the results of antimicrobial tests on E. coli, which were treated with loess, according to the method of the present invention at 0 and 24 hours.

Figures 2a and 2b is a photograph showing the results of the antimicrobial test of Pseudomonas aeruginosa in 0 hours and 24 hours leather treated in accordance with the method of the present invention.

Figure 3 is a graph showing the results of the test on the deodorizing properties of the loess treated leather according to the method of the present invention.

4 is a graph showing far-infrared emissivity and radiation energy of loess treated leather according to the method of the present invention.

The present invention uses acid dyes, which cause environmental problems related to dye wastewater, together with loess, so that the amount of acid dyes is less than the amount used in the existing leather dyeing process to actively cope with environmental problems, and is generally direct to leather. The present invention provides a method of producing leather having excellent far-infrared radiation properties, antibacterial properties, and deodorizing properties by treating the loess, which was considered to be almost impossible, to the leather and further treating the loess by acryl-based resin.

The present invention

Retanning process (A) in which a homogeneous mixture of 10 to 15% by weight loess with a particle size of 100 to 300 mesh and a vegetable natural retanning agent is impregnated into leather under a pH condition of 4.3 to 5.0 and a temperature condition of 25 to 35 ° C. ,

Process (B) of treating 8-15% by weight of the acrylic resin to the retanned leather obtained in the step (A) to prevent elution of the loess,

10 to 15% by weight of loess is treated with leather obtained in step (B) together with eggplant, and 8 to 15% by weight of acrylic resin is further treated to prevent elution of loess,

Process (D) to further prevent the elution of ocher by further treating 8-15% by weight of the acrylic resin to the branched leather obtained in step (C), and

It provides a process for producing leather having excellent far-infrared radiation property, antibacterial property and deodorizing property, comprising the step (E) of fixing loess to leather by using formic acid and cationic branching agent as a fixing agent.

Hereinafter, the present invention will be described in more detail.

First, the extraction of loess will be described.

The loess should use what is easily obtained in Korea, but take as little contaminants as possible and ventilate it under sunlight. The completely dried ocher mass is crushed, sieved to remove contaminants, then calcined in a kiln for about 1.5 hours at a temperature of about 900 ° C. or more, and the calcined ocher is crushed with a ball mill to a particle size of about 100 to 200 mesh. . The ocher powder thus obtained was dissolved in water and left to stand for one night in the precipitated state, and the supernatant was decanted to obtain the precipitated ocher powder, which was then further dried in a desiccator containing magnesium sulfate. About 300 mesh of loess powder is obtained.

In the retanning process a homogeneous mixture is required for the processing of the ocher powder into the leather together with the natural vegetable retanning agent. Therefore, in order to obtain a homogeneous mixture of the loess powder and the natural vegetable retanning agent, the ocher powder and the natural vegetable retanning agent should be stirred for about 2 hours at a stirring speed of about 2500 rpm or more.

In the present invention, in the dyeing step of the leather, non-benzidine type acid dyestuffs are used among the acid dyes commonly used in consideration of the case where the processed leather is in contact with the skin of the user. It is desirable to. Such non-benzidine-based dyes include Bayenal Brown CR New from Bayer AG, Germany, and Brown O from Croda International plc, UK. ) And the like, and any type of bibenzidine-based dyes having a color similar to ocher may be used in the present invention. On the other hand, in the amount of dye used, at least 3% by weight of the dye must be used in the conventional dyeing process of the leather, but a predetermined dyeing effect can be obtained, but in the present invention, the amount is much smaller than the amount of the dye normally used. By weight%, even when using a small amount of dye, it is possible to obtain a sufficient coloring effect comparable to the coloring effect which can be obtained by using 3% by weight of dye in a conventional leather dyeing process.

Despite the fact that less dye is used in the dyeing process than the amount normally used, the reason why the actual dyeing effect is not inferior to the leather dyed with the amount of dye normally used is because of the unique coloration of the loess used together. It is believed to be due to the effect. In addition, the present invention, by using less than the amount usually used in the dyeing process, the concentration of the dyeing waste water is also lowered by that, it is possible to provide an advantage that can suppress the occurrence of environmental problems as possible.

Ocher is added in the same amount in the retanning process and the eggplant process, each of which is preferably 10 to 15% by weight, particularly preferably 10 to 12% by weight, based on the weight of the wet blue. Do.

The retanning process must meet pH conditions of 4.3 to 5.0 and temperature conditions of 25 to 35 ° C. On the other hand, in the retanning process it is preferable to put the ocher together with the vegetable natural retanning agent, so that the loess physically penetrates the raw skin. As the vegetable natural retanning agent used in the retanning process, for example, mimosa, quebracho, mangrove bark, pine bark, hemlock bark, maze Mention may be made of myrobalans, chestnuts, valonia, sumac, oak and the like. Particularly preferred vegetable natural retanning agents for use in the retanning process of the present invention are mimosa and quebracho.

After the retanning process, the acrylic resin is treated in the hide in an amount equivalent to the amount of the loess to prevent the ocher from eluting from the hide.

Subsequently, the eggplant process is further treated with the eggplant in an amount equivalent to that used in the retanning process. After the eggplant process, the same acrylic resin as used in the retanning process is treated to the eggplant treated raw material to prevent the ocher from eluting. In the present invention, since ocher is more likely to fall off the surface of the leather during processing and using the leather as a secondary product (eg shoes, handbags, purses, etc.), the present invention treats the acrylic resin after the retanning process and after the branching process. It is of great importance that the ocher powder primarily prevents the ocher powder from deviating from the surface of the leather.

The amount of acrylic resin to be treated in the hides after the retanning process and after the eggplant process is preferably 8 to 15% by weight, particularly preferably 10 to 12% by weight. When the amount of the acrylic resin is less than 8% by weight, the effect of preventing the separation of the ocher powder is not sufficient, whereas when the amount of the acrylic resin is more than 15% by weight, the stiffness of the finally obtained ocher-treated leather ) Becomes too large to be undesirable for processing into secondary products.

On the other hand, since treating the acrylic resin cannot completely prevent the release of the loess, it is preferable to fix the loess to the raw material using formic acid and the cationic branching agent as the fixing agent. As the cationic branching agent, mention may be made, for example, of tertiary amine salts or quaternary ammonium compounds. Cationic branching agents, such as tertiary amine salts or quaternary ammonium compounds, have excellent penetration into chromium tanning leather, and combine with other kinds of branching agents, vegetable tanning agents, and acid dyes to form precipitates. It is characteristic. Particularly preferred cationic branching agents are quaternary ammonium compounds with 18 carbon atoms. In the method of the present invention, as formic acid and cationic branching agent are simultaneously introduced, the precipitate formed by the cationic branching agent is deposited on the surface of the leather to form an oil film, thereby maintaining the loess without leaving the surface of the leather. Can be.

In addition, since the leather obtained by the method according to the present invention has a preferred use for shoemaking, instead of using no chromium tanning agent in the retanning process in consideration of the health of the end user, it is used for the shoemaking using a natural vegetable tanning agent. The primary condition for leather, sweat absorption (absorbency), was improved to make it a natural-friendly leather.

Hereinafter, the present invention will be described in more detail with reference to Examples, which are not intended to limit the present invention.

Example 1

Using a solution consisting of 200 parts by weight of water and 0.5 parts by weight of oxalic acid, 100 parts by weight of chromium leather having a thickness of 0.8 to 1.0 mm were treated at 30 ° C. for 20 minutes and drained.

The solution was continuously circulated for 30 minutes in a solution containing 30 parts by weight of water, 1.5 parts by weight of sodium formate, and 1.0 parts by weight of synthetic fatliquor, followed by an additional 3.0 parts by weight of sodium polyacrylate. Circulate for minutes and then drain.

The leather treated as above is 30 parts by weight of water, 2.0 parts by weight of mimosa, 2.0 parts by weight of Quebracho, 3.0 parts by weight of anionic phenolic retanning agent, anionic resin tanning agent (crosslinked condensation product of dicyandiamide and methylene) 2.0 parts by weight, 1.0 parts by weight of synthetic branch oil, 3.0 parts by weight of sodium polyacrylate, 1.0 part by weight of Bibenzidine-based dye, Bayern Brown Sea New, naphthalene-based synthetic tanning agent (naphthalene 2-sulfonic acid formaldehyde condensate) Circulated for 40 minutes in a solution consisting of 1.0 part by weight and 10.0 parts by weight of ocher having a particle size of 150 to 250 mesh, additionally 100 parts by weight of water at 60 ° C., and then acidified by adding 1.5 parts by weight of 85% formic acid, It is then further circulated for 20 minutes and then drained.

Finally, the mixture was circulated for 30 minutes in a solution consisting of 150 parts by weight of water at 50 ° C., 5.0 parts by weight of sulfated neats foot oil, 4.0 parts by weight of sulfonated lanolin oil, and 0.5 parts by weight of natural carpentry oil, 10.0 parts by weight is further added. 20 minutes after the addition, 1.0 parts by weight of 85% formic acid was added, circulated for 15 minutes to acidify, 1.0 parts by weight of cationic branching agent was added and circulated again, and then the leather was washed with cold water, followed by a general process. Further treatment yields ocher treated leather.

The antimicrobial properties of the leathers (hereinafter referred to as ocher treated leathers) obtained by the method of the present invention are tested. [Test Institution: Korea Institute of Building Materials Testing and Research Institute, Far-Infrared Application Evaluation Center (Deodorization and Far-Infrared Radiation Characteristics) Tested at)].

1. Test Method

KICM-FIR-1002

2. Use strain

1) Escherichia coli ATCC 25922

2) Pseudomonas aeruginosa ATCC 15442

The results for the antimicrobial test are listed in Table 1 below.

Test Items Sample classification Initial concentration (CFU / mL) Concentration after 24 hours (CFU / mL) Bacterial Reduction (%) Antibacterial test by Escherichia coli Untreated leather 206 504 - Ocher treated leather 206 One 99.5 Antibacterial test by Pseudomonas aeruginosa Untreated leather 226 532 - Ocher treated leather 226 One 99.6

Note 1) CFU: Colony forming Unit

2) The number of bacteria on the medium is calculated by multiplying the dilution multiples.

From the results of Table 1 above, the ocher treated leather according to the method of the present invention shows a rapid decrease in the number of colony forming units after 24 hours to 1, which shows very high growth inhibition rate for both Escherichia coli and Pseudomonas aeruginosa You can see that it is excellent.

The deodorizing properties of the ocher treated leathers obtained by the process of the invention are then tested.

1. Test Method

KICM-FIR-1004

2. Test gas name: Ammonia

3. Gas concentration measurement: gas detector

Test results for deodorant properties are listed in Table 2 below.

Test Items Elapsed time (min) Gas concentration in ppm untreated samples (ppm) Gas concentration (ppm) of ocher treated samples Deodorization rate (%) Deodorization test 0 500 500 - 30 480 50 90 60 470 30 94 90 450 20 96 120 440 10 98

Note: The specimen size is 300 × 300 mm.

From the results of Table 2, it can be confirmed that the ocher treated leather according to the method of the present invention exhibits a high deodorization rate of 98% even after 2 hours has elapsed. This fact can also be confirmed from the attached graph of FIG. 3. That is, the gas concentration, which was 500 ppm at the start of the test, dropped sharply to 50 ppm at 30 minutes after the test, and dropped to only 10 ppm at 2 hours after the test.

The far-infrared radiation characteristics of the ocher treated leather obtained by the process of the invention are tested. The test is performed at 40 ° C. using the FT-IR spectrometer and is prepared for a blackbody.

The test results are listed in Table 3 below.

Emissivity (5 to 20 μm) Radiation energy (W / ㎡) 0.908 3.66 × 10 ²

The ocher treated leathers obtained by the process according to the invention not only show good far-infrared radiation properties but also very good antibacterial and deodorizing properties. In particular, the ocher treated leather obtained by the process according to the invention is preferred for use as shoemaking leather.

Claims (6)

Retanning process in which a homogeneous mixture of 10 to 15% by weight ocher with a particle size of 100 to 300 mesh and a natural vegetable retanning agent is impregnated into leather under a pH condition of pH 4.3 to 5.0 and a temperature condition of 25 to 35 ° C. ), Process (B) of treating 8-15% by weight of the acrylic resin to the retanned leather obtained in the step (A) to prevent elution of the loess, 10 to 15% by weight of loess is treated with leather obtained in step (B) together with eggplant, and 8 to 15% by weight of acrylic resin is further treated to prevent elution of loess, Process (D) to further prevent the elution of ocher by further treating 8-15% by weight of the acrylic resin to the branched leather obtained in step (C), and A process for producing ocher treated leather, comprising the step (E) of fixing the loess to leather using formic acid and a cationic branching agent as a fixing agent. The vegetable natural retanning agent used in the retanning process (A) is a mimosa, quebracho, mangrove bark, pine bark, hemlock foil. bark, myrobalans, chestnuts, chestnuts, valonia, sumac and oak. The method according to claim 2, wherein the vegetable natural retanning agent is mimosa or quebracho. The production method according to claim 1, wherein the acrylic resin used in the step (B), the step (C), and the step (D) is sodium polyacrylate. The process according to claim 1, wherein the cationic branching agent used in step (E) is a quaternary ammonium compound having 18 carbon atoms. A loess treated leather obtained according to the method of claim 1.