WO2007129862A1

WO2007129862A1 - Antioxidant fermenting microorganism agent reducing smell and volatile organic compounds from leathers, leathers comprising the same, and method for preparation thereof

Info

Publication number: WO2007129862A1
Application number: PCT/KR2007/002269
Authority: WO
Inventors: Taek Lim; Jae Yong Ko; Eun Ju Lee; In Sung Kim; Chang Hong Lee
Original assignee: Dymos Inc.; Seoul National University Industry Foundation
Priority date: 2006-05-10
Filing date: 2007-05-09
Publication date: 2007-11-15
Also published as: KR100789594B1; KR20070109278A

Abstract

Disclosed is an antioxidant fermenting microorganism agent, leather including the antioxidant fermenting microorganism agent, and a method of producing the leather. The antioxidant fermenting microorganism agent is used to reduce an odor and a volatile organic compound generated from leather so that humans are protected from noxious substances generated from leather. Leather is used as a seat for vehicles or a material for the interior of a vehicle.

Description

ANTIOXIDANT FERMENTING MICROORGANISM AGENT

REDUCING SMELL AND VOLATILE ORGANIC COMPOUNDS

FROM LEATHERS, LEATHERS COMPRISING THE SAME,

AND METHOD FOR PREPARATION THEREOF Technical Field

[1] The present invention relates to an antioxidant fermenting microorganism agent that is used to reduce an odor and a volatile organic compound generated from processed leather, leather including the antioxidant fermenting microorganism agent, and a method of producing the leather. Background Art

[2] From old times, leather and fur have been frequently used to make clothes or household goods. Currently, leather is commonly used to make clothes. In accordance with advances in processing of leather, the leather is used to produce various types of household goods as well as clothes, and leather products are frequently used daily.

[3] It is necessary to perform various steps of processes during the processing of leather. Particularly, in order to improve physical and chemical properties of leather, various types of organic and inorganic compounds may be added and physical processing may be performed. Accordingly, various types of volatile organic compounds are detected from leather goods. The volatile organic compounds cause chronic damage to humans.

[4] In respects to noxiousness of many volatile organic compounds that may cause a sick house syndrome, a sick car syndrome, and the like, there are various types of regulations all over the world. However, no specific research to examine specific symptoms caused by the volatile organic compounds has been performed nor to reduce the volatile organic compounds.

[5] Recently, photocatalysts, nanosilver, and various types of chemical substances have been used to reduce an odor and a volatile organic compound generated from leather, but do not answer the desired purpose and are not considered as critical technology for removing an odor due to a very high treatment cost. Disclosure of Invention Technical Problem

[6] It is an object of the present invention to provide an antioxidant fermenting microorganism agent that is used to radically reduce an odor and a volatile organic compound generated from leather at low cost, leather including the antioxidant fermenting microorganism agent, and a method of producing the leather.

[7] It is another object of the present invention to provide seats for vehicles, material for the interior of a vehicle, and leather parts made using the leather. Technical Solution

[8] The present invention provides an antioxidant fermenting microorganism agent to reduce a volatile organic compound generated from a polyurethane foam, wherein said agent includes a microorganism mixture, water, an organic carbon source, and a natural salt at a weight ratio of 3 to 7 : 50 to 150 : 3 to 7 : 0.5 to 1.5 and wherein the microorganism mixture contains photosynthetic bacteria, yeast, actinomyces, and lac- tobacillus at a germ number ratio of 50 to 150 : 0.5 to 1.5 : 0.5 to 1.5 : 3 to 7.

[9] Furthermore, the present invention provides leather having the antioxidant fermenting microorganism agent and a method of producing leather.

Advantageous Effects

[10] An antioxidant fermenting microorganism agent according to the present invention is added during the processing of leather to reduce odor and an amount of volatile organic compounds generated from the processed leather, thereby radically removing the cause of the odor and the volatile organic compound. In addition, the antioxidant fermenting microorganism agent generates an antimicrobial substance such as benzoic acid to induce an antimicrobial action on the leather.

[11] Furthermore, the antioxidant fermenting microorganism agent produces an action against the wastewater generated during the processing of leather foam, which allows various types of compounds contained in the wastewater to biodegrade, thus increasing treatment efficiency of the wastewater. Brief Description of the Drawings

[12] FIG. 1 is a GC-mass graph of known leather that does not contain an antioxidant fermenting microorganism agent; and

[13] FIG. 2 is a GC-mass graph of leather that contains an antioxidant fermenting microorganism agent of the present invention. Best Mode for Carrying Out the Invention

[14] The present invention will be described in detail hereinafter.

[15] The term "an antioxidant fermenting microorganism" in the present invention means a combination of effective microorganism groups that coexist and live sym- biotically and are capable of creating an antioxidant substance such as inositol, ubiquinone, and polyphenol using an organic carbon source and natural salts as raw materials through a fermentation process.

[16] The antioxidant fermenting microorganism agent of the present invention contains various types of microorganism species including photosynthetic bacteria, yeast, actinomyces, lactobacillus, and the like, and is an environmentally safe material which has been used in fermenting traditional foods.

[17] The antioxidant fermenting microorganism agent according to the present invention is added during the process for producing leather to prevent various types of chemical agents from remaining and to decompose the remaining chemical agents, thereby reducing the amount of volatile organic compounds that are generated from the produced leather.

[18] The antioxidant fermenting microorganism agent according to the present invention contains a microorganism mixture including photosynthetic bacteria, yeast, actinomyces, and lactobacillus that are mixed with each other at a germ number ratio of 50 to 150 : 0.5 to 1.5 : 0.5 to 1.5 : 3 to 7, thereby reducing the amount of volatile organic compounds. It is most preferable that the mixing ratio of photosynthetic bacteria, yeast, actinomyces, and lactobacillus be 100 : 1 : 1 : 5.

[19] Examples of photosynthetic bacteria which are contained in the antioxidant fermenting microorganism agent according to the present invention include Rhodopseudomonas palustris, examples of yeast include Saccharomyces cerevisiae, examples of actinomyces include Streptomyces albus, and examples of lactobacillus include Lactobacillus plantarum.

[20] The above-mentioned germs that act as the matrices are appropriately mixed with each other, water, organic carbon sources, and natural salts are added at a weight ratio of 50 to 150 : 3 to 7 : 0.5 to 1.5 in a fermentation culture fluid form, and fermentation is completely performed in an anaerobic state at 20 to 3O⁰C for 7 to 10 days to produce the antioxidant fermenting microorganism according to the present invention. Preferably, the fermentation culture fluid contains water, the organic carbon sources, and the natural salts at a weight ratio of 100 : 5 : 1.

[21] The organic carbon source is a typical carbon nutritive element and preferable examples thereof include syrup, and preferable examples of the natural salts include deep-sea natural salts that are not contaminated.

[22] Natural salts that are used in the present invention is uncontaminated natural sea salts which was fermented with the microorganism agent according to the present invention for 7 days.

[23] In addition, the present invention provides leather that contains the antioxidant fermenting microorganism agent and a method of producing the leather.

[24] The term "leather" used in the present invention encompasses untanned fresh hides and tanned hides. The general term "skin" means the skin (raw hide) that is stripped from animals, and the tanned hide is the general name for products from which fur is removed and which are subjected to tanning (the tanning is the general term for processes of treating the skin). Products having different physical properties may be obtained according to the type of raw hide and the type of process such as tanning and finishing.

[25] Chemical substances are added during the course of performing the tanning, and various types of chemical substances generated from the leather when the processed leather is used are noxious to humans.

[26] For example, carbon disulfide (CS₂) is a sort of a volatile organic compound and is emitted from the processed leather. Carbon disulfide is called sulfurated carbon, and is colorless or has a light yellow color. Carbon disulfide has a strong unpleasant odor and is a volatile liquid having a boiling point of 46⁰C.

[27] In the case of when a carbon disulfide vapor is inhaled, or a carbon disulfide liquid comes into contact with the skin or mucous membrane for a long period of time or is swallowed, a disorder in the nervous system occurs.

[28] Therefore, in the present invention, the antioxidant fermenting microorganism agent that contains various types of microorganism species having photosynthetic bacteria, yeast, actinomyces, lactobacillus, or the like as a matrix is added at a predetermined step during a process of producing leather to prevent chemicals from remaining during the processing of leather while natural properties of the leather are not reduced.

[29] Additionally, the agent according to the present invention is used to decompose or remove unreacted remaining chemicals to reduce the odor and the volatile organic compound generated from the processed leather and the material for the interior and seat products manufactured using the leather, thus protecting humans from the volatile organic compounds.

[30] A method of producing the leather containing the antioxidant fermenting microorganism agent will be described in detail hereinafter.

[31] A typical process of producing the leather includes a preparation process, a tanning process, a dyeing process, and a finishing process. Details of steps constituting the processes will be given below. The steps and the purpose for the steps will be given below. Treatment conditions in the steps are extensively known in the art to which the present invention belongs. The order of some steps may be reversed, a portion of steps may be omitted or performed in conjunction with other steps.

[32] 1) Preparation process

[33] A) Soaking: The main aim of the soaking is to remove salts used for storage and pollutants from the raw hide so that the raw hide is restored. In this connection, moisture content of the raw hide is recovered so that the contents are increased from 35 to 45% to about 64%.

[34] B) Fleshing: Any remaining oiliness such as fat, flesh (meat pieces), and connective tissues is removed from a flesh side of the skin. [35] C) Liming: The raw hide is immersed in a saturated solution of a lime to easily remove the fur, relax and swell the tissue by using alkali, and remove any remaining protein such as fur from the raw hide and an epithelium layer.

[36] D) Rinsing : Cleaning is performed for a subsequent process.

[37] E) Splitting: The thickness is primarily determined and controlled according to the type and the grade of raw hide and the type of products.

[38] F) Reliming: The liming process is performed again to completely remove any fur or pollutants from the raw hide so that a subsequent process can be desirably performed to make the leather smooth.

[39] 2) Tanning process

[40] A) Deliming: Neutralization is performed by using an alkali, and a globular protein is removed to increase softness of the skin and desirably perform a subsequent process.

[41] B) Bating: Unclean protein is removed, grades are made fine, and the large peyong is obtained.

[42] C) Pickling: In order to prevent the propagation of bacteria before the tanning is performed to ensure permanency of the skin, a pelt is subjected to acidification so that the tanning is desirably performed. Leather before pickling is finished is called a pelt.

[43] D) Tanning: Protein is converted into a substance that will not decay. Tanning is performed by using chromium, aluminum, vegetable oil, and a mimosa to form the skin.

[44] E) Samming: Water is removed from the skin that is subjected to tanning and aging to precisely control the thickness during shaving. Dehydration is performed so that the moisture content is controlled to be in the range of 30 to 45%.

[45] F) Shaving or grading: The thickness that is primarily controlled during splitting is precisely recontrolled.

[46] G) Neutralization: The pH is controlled depending on the type of dyeing and fat liquoring (oiling).

[47] H) Re tanning: The skin that is subjected to only tanning may be used to obtain products through the subsequent process. However, since nonuniform tanning that occurs due to shaving after chromium tanning is performed causes uneven dye (dyeing is not uniformly performed due to a dyeing rejection reaction) and a difference in quality of portions. In order to avoid this and provide desirable properties according to the purpose of goods, and to ensure that the skin has desirable softness and appearance, that is, a sophisticated skin, tanning is additionally performed.

[48] 3) Dyeing process

[49] A) Dyeing: Dyeing of leather is performed by using the following process. The skin is mixed with a water-soluble dye in a cage that is capable of being maintained at the same temperature and subjected to a physical operation so as to be uniformly colored, such that various colors can be ensured.

[50] B) Fat liquoring: since the drying of the dyed skin render the skin too hard, it is difficult to be used. Accordingly, an oiling agent fills spaces between fibers to reduce friction and act as a lubricant. In addition, fat liquoring is performed to preserve softness, increase yield, produce a desirable skin, and protect the skin (provision of waterproofing).

[51] 4) Finishing process

[52] A) Drying: Air is repeatedly recycled to evaporate water contained in the fibers of the skin. Drying may be classified into natural drying and artificial drying, and moisture content after drying is in the range of 8 to 14%.

[53] B) Conditioning: Water is provided into the fiber structure while the fiber structure of the skin is shrunk and made hard after drying to reduce friction during milling and restore the fiber of the skin into an original state while the skin pores are not destroyed, thereby ensuring desirable softness. After conditioning, moisture content is in the range of 18 to 22%.

[54] C) Milling: The fiber structure that is made hard due to the evaporation of water is relaxed, desirable softness of the skin is ensured, and the closed skin pores are opened to easily perform treatment using chemicals and a subsequent process.

[55] D) Toggling: The surface of the skin is made refined and flat to increase the yield of goods and prevent leather goods from expanding when the leather goods are made.

[56] E) Spraying: A dye, a pigment, and a polishing agent are applied.

[57] F) Pressing and embossing: Physical properties are improved and the surface is made smooth and flat.

[58] G) Measuring: The quantity is obtained.

[59] In the method of producing leather according to the present invention, 0.05 to 0.15 wt% of antioxidant fermenting microorganism agent is added to a typical process of producing leather, which includes the preparation process, the tanning process, the dyeing process, and the finishing process, based on the amount of chemicals added during the dyeing process.

[60] In the case of when the amount of antioxidant fermenting microorganism agent is less than 0.05 wt% based on the amount of added chemicals, there is a problem in that efficiency is reduced. In the case of when the amount is more than 0.15 wt%, there is a problem in that another odor is generated due to fermentation of the microorganism agent.

[61] Examples of the dye that is added during the dyeing process include an acidic dye, a basic dye, and a metal dye, and an acidic dye may be used in the present process. Additionally, examples of a fat liquoring agent include sulfur oxides, sulfurous oxides, phosphorus oxides, and synthetic series, and they may be combined with each other by using various types of methods.

[62] Furthermore, in the method of producing leather according to the present invention,

0.03 to 0.07 wt% of antioxidant fermenting microorganism agent is added based on the amount of leather coating agent that is added during the spraying step of the finishing process. In the case of when the amount of antioxidant fermenting microorganism agent is less than 0.03 wt% based on the amount of added leather coating agent, the removal efficiency of odor is reduced. In the case of when the amount is more than 0.07 wt%, there is a problem in that another odor is generated due to fermentation of the microorganism agent. An acryl base and a polyurethane base are used as the leather coating agent, and it is preferable to use a water-soluble type coating agent.

[63] Moreover, in the method of producing leather according to the present invention,

0.05 to 0.15 wt% of antioxidant fermenting microorganism agent is added based on the amount of chemicals that are added during the dyeing process and 0.03 to 0.07 wt% of antioxidant fermenting microorganism agent is added based on the amount of coating agent that is added during the spraying step of the finishing process.

[64] The present invention also provides leather that is produced by using the above- mentioned production method.

[65] The leather according to the present invention may be used as seats for vehicles, the material for the interior of a vehicle, and leather parts. Meanwhile, the antioxidant fermenting microorganism agent according to the present invention is uniformly sprayed on the entire surface of the seats for vehicles, the material for the interior of a vehicle, leather parts, or the like, which is produced by using leather processed to perform the application, and then left at normal temperature for 24 hours to decompose and remove the odor and the volatile organic compounds from the processed leather.

[66] As described above, in the present invention, the antioxidant fermenting microorganism agent is added in the course of producing leather or sprayed on the leather, thereby providing the following effect.

[67] Unlike a known process in which an odor and a volatile organic compound are reduced from leather by a simple procedure, in the present invention, the antioxidant fermenting microorganism agent is added during the processing of the skin or the antioxidant fermenting microorganism is sprayed on the processed leather to remove factors such as an odor and a volatile organic compound which are noxious to humans.

[68] Furthermore, the antioxidant fermenting microorganism agent is added to wastewater that is generated during the processing of the leather to allow various types of compounds contained in the wastewater to biodegrade, thereby increasing treatment efficiency of the wastewater.

[69] Additionally, in the present invention, since a biological material is used to remove the odor from leather, a change in natural properties of leather is minimized. In the case of when a skin seat produced by using leather according to the present invention is used, a sick house syndrome and a sick car syndrome that are generated from known leather may be reduced.

[70] In addition, the antioxidant fermenting microorganism generates secondary products that act as antimicrobials action such as benzoic acids antioxidant substances including inositol, ubiquinone, and polyphenols and by a fermentation process so that the anaerobic microorganisms are capable of enduring oxygen free radicals. The secondary products may decompose or remove a substance that causes an odor and a volatile organic compound to reduce the odor and the volatile organic compound generated from a skin material for the inside of a vehicle and seat goods by using an environmentally friendly process. Mode for the Invention

[71] Hereinafter, the present invention will be described in detail in light of Examples and Experimental Examples. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the Examples and Experimental Examples set forth herein. Rather, these Examples and Experimental Examples are provided such that this disclosure will be thorough and complete and will fully convey the concept of the present invention to those skilled in the art.

[72] <EXAMPLE 1> Antioxidant fermenting microorganism agent

[73] Rhodopseudomonas palustris that was photosynthetic bacteria, Saccharomyces cerevisiae that was yeast, Streptomyces albus that was actinomyces, and Lactobacillus plantarum that was lactobacillus were mixed with each other at a ratio of 100 : 1 : 1 : 5. The microorganism mixture, water, the organic carbon source, and the natural salts were mixed with each other at a ratio of 5 : 100 : 5 : 1 and completely fermented in an anaerobic state at 20 to 3O⁰C for 7 to 10 days to produce an antioxidant fermenting microorganism agent. The above-mentioned germs were isolated and cultured in a natural state.

[74] <EXAMPLE 2>

[75] Shaving was performed after tanning so that physical properties were provided to the neutralized natural skin by performing retanning in a drum for various purposes. 0.1 wt% of antioxidant fermenting microorganism agent was added based on the amount of chemicals used during dyeing and fat liquoring processes to produce leather.

[76] <EXAMPLE 3>

[77] After drying was performed by using dyeing and fat liquoring processes to produce the skin, the leather coating agent was used during the spraying process to form the coat, and 0.05 wt% of antioxidant fermenting microorganism agent was applied on the hide based on the amount of coating agent, and then dried to produce leather. [78] <EXAMPLE 4>

[79] Shaving was perforaied after tanning so that physical properties were provided to the neutralized natural skin by performing retanning in a drum for various purposes. Additives and 0.1 wt% of antioxidant fermenting microorganism agent on the basis of the amount of additives were then added to perform the dyeing and fat liquoring processes. Next, the drying process was performed to produce a primary skin, a coating agent was added during the spraying process, 0.05 wt% of antioxidant fermenting microorganism agent was applied on the hide based on the amount of coating agent, and drying was performed to produce leather.

[80] EXPERIMENTAL EXAMPLE>

[81] Untreated leather (leather that did not contain the antioxidant fermenting microorganism agent according to the present invention, weight: 8.47 g and area: 120 D) and treated leather that was produced in Example 4 (weight: 8.26 g and area: 126 D) were prepared.

[82] The leather samples were put separately into the chambers for generating the volatile organic compounds (51 Pyrex chamber) and the chambers were completely sealed. The chambers for generating the volatile organic compounds in which the samples were contained were treated in a thermostat at 8O⁰C for 12 hours.

[83] The volatile organic compounds that were generated from the chambers for generating the volatile organic compounds that were treated at the constant temperature of 8O⁰C were adsorbed onto an adsorption tube (Tenax TA Thermal Desorption tube). The adsorption process included creating a vacuum after providing a moisture and air removing filter to an inlet of each of the chambers, providing the adsorption tube to an outlet of each of the chambers, and creating a vacuum by using a vacuum pump (12 to 15 D/min) for 1 min.

[84] In the case of when a vacuum was created by using the vacuum pump (12 to 15

D/min) for 1 min, since each of the chambers for generating the volatile organic compounds was produced to have the volume of 5 I, the generated volatile organic compounds were adsorbed onto media in the adsorption tube while all gases emitted from the chambers passed through the adsorption tube. The adsorption tube was treated at 38O⁰C for 3 hours before being used to maintain the desired active state.

[85] The adsorption tube was connected to GC-MSD (Agilent 6890GC/5973N MSD) to perform qualitative and quantitative analyses for 40 min, a library search was performed to confirm the components, and the results of the meaningful volatile organic compound components are described in the following Table 1. FIGS. 1 and 2 are GC-mass graphs of untreated leather and treated leather, respectively.

[86] Table 1

[87] As shown in the above Table 1, in respect to the total amount of volatile organic compounds that was generated from two samples, the amount was 215.1 D in the case of untreated leather and 73.8 D in the case of treated leather.

[88] When the amount of volatile organic compounds generated from untreated leather was considered 100%, the total amount of volatile organic compounds generated from treated leather was reduced to 34.3%, by about 65%, and the amount of organic compounds in respect to odor was reduced by about 80%.

[89] In the case of leather that was treated with the antioxidant fermenting microorganism agent, the amount of carbon disulfide, a chemical that is noxious to humans and stimulates the eye and the throat, was reduced by about 59%, and the amounts of 10 types of volatile substances were less than the limiting value of the analyzer. However, the volatile substances were detected in the case of untreated leather.

[90] The reason is that leather was treated with the antioxidant fermenting microorganism agent. In addition, the amount of 2-butoxy ethanol that is noxious to humans was reduced by 94% after the treatment, and n-butyl formate that causes pruritus was not detected after the treatment.

Claims

[1] An antioxidant fermenting microorganism agent comprising: a microorganism mixture that contains photosynthetic bacteria, yeast, actinomyces, and lactobacillus at a germ number ratio of 50 to 150 : 0.5 to 1.5 :

0.5 to 1.5 : 3 to 7; water; an organic carbon source; and a natural salt, wherein the microorganism mixture, water, the organic carbon source, and the natural salt are mixed at a weight ratio of 3 to 7 : 50 to 150 : 3 to 7 : 0.5 to 1.5 to reduce a volatile organic compound generated from a leather. [2] The antioxidant fermenting microorganism agent as set forth in claim 1, wherein the microorganism mixture contains photosynthetic bacteria, yeast, actinomyces, and lactobacillus mixed with each other at a germ number ratio of

100 : 1 : 1 : 5. [3] The antioxidant fermenting microorganism agent as set forth in claim 1, wherein the microorganism mixture, water, the organic carbon source, and the natural salt are mixed at a ratio of 5 : 100 : 5 : 1. [4] A leather comprising the antioxidant fermenting microorganism agent according to claim 1. [5] A leather comprising the antioxidant fermenting microorganism agent according to claim 2. [6] A leather comprising the antioxidant fermenting microorganism agent according to claim 3. [7] A method of producing a leather, the method comprising: a preparation process; a tanning process; a dyeing process; and a finishing process, wherein 0.05 to 0.15 wt% of antioxidant fermenting microorganism agent of claim 1 is added based on the amount of chemicals added during the dyeing process. [8] A method of producing a leather, the method comprising: a preparation process; a tanning process; a dyeing process; and a finishing process, wherein 0.03 to 0.07 wt% of antioxidant fermenting microorganism agent of claim 1 is added based on the amount of chemicals that are added during a spraying step of the finishing process. [9] A method of producing a leather, the method comprising: a preparation process; a tanning process; a dyeing process; and a finishing process, wherein 0.05 to 0.15 wt% of antioxidant fermenting microorganism agent of claim 1 is added based on the amount of chemicals added during the dyeing process, and

0.03 to 0.07 wt% of antioxidant fermenting microorganism agent of claim 1 is added based on the amount of chemicals that are added during a spraying step of the finishing process.

[10] A leather which is produced by using the method of claim 7.

[11] A leather which is produced by using the method of claim 8.

[12] A leather which is produced by using the method of claim 9.

[13] A seat for a vehicle or interior materials for a vehicle which is produced by using the leather of claim 4. [14] A seat for a vehicle or interior materials for a vehicle which is produced by using the leather of claim 5. [15] A seat for a vehicle or interior materials for a vehicle which is produced by using the leather of claim 6. [16] A seat for a vehicle or interior materials for a vehicle which is produced by using the leather of claim 10. [17] A seat for a vehicle or interior materials for a vehicle which is produced by using the leather of claim 11. [18] A seat for a vehicle or interior materials for a vehicle which is produced by using the leather of claim 12.