KR101312940B1 - Method for manufacture of horse skin dyed with natural dye and the horse skin obtained thereby - Google Patents

Abstract

The present invention provides a method for producing a skin stained with a natural dye and a skin obtained by the method. The present invention is characterized by the use of lac dyes, paprika dyes, cacao dyes or safflower sulfur dyes as natural dyes, and the dyed with natural dyes obtained according to the method of the present invention has high fastness and physical properties are also dyed with synthetic dyes. Compared to Marfi is inferior characteristics.

Description

Method for manufacture of horse skin dyed with natural dye and the horse skin obtained thereby

The present invention relates to a method for producing a coat dyed with a natural dye and a coat obtained by the method.

Synthetic dyes used in the processing and manufacturing of leather, including horse skin, may cause human risks such as skin rashes, allergies and atopic dermatitis, and environmental hazards by raising BOD, COD, TN, and TP. In fact, the human and environmental risks of synthetic dyes have been continuously reported.

Due to the side effects of synthetic dyes, interest in natural dyes is now emerging. However, in the case of natural dyes, low color fastness has always been pointed out as a problem, whether it is textile or leather.

The present invention discloses a technique using a natural dye that is higher in color fastness compared to the case of using a synthetic dye in the dyeing of the skin and inferior to the case of using a synthetic dye in physical properties such as tensile strength and tear strength.

It is an object of the present invention to provide a method for producing a coat dyed with a natural dye.

Another object of the present invention is to provide a coat dyed with a natural dye obtained by the above production method.

The present inventors, as confirmed in the following Examples and Experimental Examples, using a total of about 20 natural dyes, such as lac dye, paprika dye, cacao dye or safflower sulfur dyes to dye the tan after the tanning process and neutralization process In the case of lacies dyed with lac dyes, paprika dyes, cacao dyes or safflower dyes, acid red 97 (Alizarine Chrome Red G, Color index: 22890, CAS RN: 10169-02-5) is a red synthetic dye. Compared with the case of using, without being inferior in physical properties such as tensile strength, tear strength, the fastness (friction fastness and washing fastness) was found to be rather high compared to the case using a synthetic dye.

The present invention is provided based on these experimental results.

In one aspect, the present invention relates to a method for producing a coat dyed with a natural dye, and more particularly, to a method for producing a coat dyed with a lac dye, paprika dye, cacao dye or safflower sulfur dyes of natural dyes.

Specifically, the method for producing a skin dyed with natural dyes of the present invention is (a) pretreatment step for removing unnecessary components contained in the skin, (b) pre-treatment of the collagen fibrous tissue on the skin after the pre-treatment step, An oily step to impart heat resistance and flexibility, (c) a dyeing step to color the finish after the oily step, and (d) a finishing step to impart flexibility and smoothness to the dyeing step. The dyeing step of (c) is characterized in that it comprises the step of mixing and stirring the oil after the oily step, natural dye and water selected from the group consisting of lac dye, paprika dye, cacao dye and safflower dye.

Among the natural dyes used in the method of the present invention, "lac dye" refers to a reddish-dark reddish brown dye obtained by removing the resin component by extracting the resinous material secreted by the oil layer of Lacifer lacca KERR. Coccidae with water. .

Among the natural dyes used in the method of the present invention, "paprika dye" is a pigment obtained by extracting paprika fruit with a non-polar organic solvent such as n-hexane, and orange, yellow or red dye is obtained depending on the type of fruit used. Can lose.

In the natural dyes used in the method of the present invention, "cacao dye" refers to a dark reddish brown pigment obtained by fermenting and roasting cacao seeds with a polyphenolic colorant and then extracting with water.

In the natural dyes used in the method of the present invention, "safflower sulfur dye" refers to a yellow pigment obtained by extracting the ornamental flower of safflower (safflower) with water.

The pigments used in the method of the present invention may be prepared and used directly, but since all of them are distributed in the market, an appropriate one may be purchased and used in the market.

In the method of the present invention, the natural dye may be used in the range of 2 to 10 parts by weight, preferably 3 to 7 parts by weight, based on 100 parts by weight of raw skin and 80 to 150 parts by weight of water, and an appropriate amount of natural dyes is used. It may be determined in consideration of the degree of purification of the silver dye, the moisture content of the dye, the intensity of the intended color, and the like. In addition, it is preferable that the internal temperature of the drum is maintained at 50 to 60 ° C. such that the natural dye sufficiently penetrates and binds to the leather, and is preferably performed by rotating the drum at least 60 minutes at 9 to 12 rpm.

The method of the present invention is a method for producing a conventional dyed leather, by using one of the natural dyes of the dye, lac dye, paprika dye, cacao dye, safflower dye, tensile strength, tear strength, etc. Because the fastness is rather high without falling out of the physical properties of, the manufacturing process of the other dyeing leather except the dyeing step of the method of the present invention can be applied as it is known in the art.

The manufacturing process of dyed leather is described in "Bibliothek des Leders", Volume 3 (tanning).

agents, tanning and retanning) (1985), Volume 4 (defatting, fatliquoring and hydrophobicization in leather manufacture) (1987) & Volume 5 (the dyeing of leather) (1987) Umschau Verlag, "Leather Technicians Handbook", 1983 , by JH Sharphouse, published by Leather Producers Association, "Fundamentals of Leather Manufacturing", 1983, by E. Heidenmann, published by Eduard Roether KG, which are described in detail below. Reference may be made to the descriptions of these documents for the processes described hereinbefore and for the descriptions omitted, and therefore the descriptions of the documents are considered as part of this specification.

The manufacturing process of dyed leather generally comprises a pre-treating process, a tanning process, a dyeing process and a finishing process, and the process of the present invention also comprises these steps. Include by default.

In the method of the present invention, the pre-treating process of step (a) is performed to remove animal components such as proteins, dirt, salt, etc. from raw hides, and to proceed to the oily step, which is a processing step of the subsequent leather. Step.

The pretreatment step preferably comprises a soaking process, a lime process, a fleshing process and a sorting process.

The soaking process is a process for removing animal components such as proteins, salts, and dirt from salted raw skins for storage, and absorbing moisture into the raw skins shrunk by salting to reduce the raw materials.

In the soaking process, salted raw materials are immersed in water at 25 to 30 ° C. for about 20 to 30 hours to remove salts and impurities. In this case, water solubility aids, surfactants, and the like may be used to efficiently remove salts and impurities. Can be. Sodium carbonate, sodium sulfide, sodium hydroxide, and the like can be exemplified as the water aid, which may be used, and it is preferable to use 0.1 to 0.5 parts by weight based on 100 parts by weight of raw skin. The surfactant may be used in an amount of 0.1 to 0.3 parts by weight based on 100 parts by weight of the raw material, and nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants may be used. In the soaking process, preferably, proteolytic enzymes can be additionally used so that the material used in the lime process can be uniformly and effectively penetrated into the skin, and the preferred amount of proteolytic enzyme is in the range of 100 parts by weight to 0.3 to 2 parts by weight. .

After removing salts, impurities, etc. through the soaking process, it is preferable to carry out the lime process for the purpose of relaxing and swelling the collagen fibers in order to remove unnecessary proteins and fats and to efficiently carry out the oily step, which is a subsequent step. Do. Lime process is to immerse the raw material in the composition containing alkaline substances to induce the swelling and activation of the raw material and to remove the unnecessary protein and fat attached to the raw material, the surfactant is added to remove the unnecessary protein and fat more efficiently Can be used. As the alkaline material for performing the lime process, sodium hydrogen sulfide, lime, sodium sulfide and the like may be used, and may be used in the range of 1 to 10 parts by weight based on 100 parts by weight of raw skin.

After the lime process, a fleshing process is performed to physically remove the fat from the subcutaneous subcutaneous tissue, and after the fleshing process, a sorting process is performed to sort the raw material and to flatten the leather according to the purpose of the leather. Done. In the sorting process, a process of adjusting the thickness (thickness) of the raw skin according to the use of the leather using a band knife or the like may be added.

As such, after the pretreatment step through the water, lime, meat removal and sorting steps, the collagen fibers of the leather are fixed and stabilized to perform oily steps for imparting water resistance, heat resistance and flexibility.

The planetary step is preferably carried out through a deliming process, a bating process, a pickling process and a tanning process.

The deliming process is a process for removing the lime components remaining in the leather after the lime process.The process is used to recover the loosened and swollen fibers in the lime operation and to soften the leather by removing the lime components by using a deoxidizing agent such as an acid or an acid salt. The softening process is a process for additionally removing unnecessary protein components contained in the leather using proteolytic enzymes and imparting flexibility and elongation to the fibrous tissue.

As the deliming agent that can be used in the deliming process, nitrogen-based deliming agents such as ammonium chloride and ammonium sulfate, and non-nitrogen deliming agents such as propylene carbonate and polyvalent aromatic acids can be used, and the range of 1 to 5 parts by weight based on 100 parts by weight of raw skin It is preferable to use as.

The softening process uses proteolytic enzymes such as pepsin, trypsin, chymotrypsin, and elastase, and additionally uses lipolytic enzymes such as lipase to remove fat components that may remain in the skin. Can be. The proteolytic enzyme may be used in the range of 0.5 to 5 parts by weight based on 100 parts by weight of the raw skin, and a dispersant may be further used to improve the contact and reaction of the proteolytic enzyme to the raw skin surface. In addition, pH adjusting agents may be further used so that proteolytic enzymes exhibit optimal activity. Surfactant can be used as a dispersing agent, and surfactant can use any of a nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant. The preferred amount of dispersant is in the range of 0.1 to 0.7 parts by weight based on 100 parts by weight of raw hide. The pH adjusting agent may be used an organic acid such as lactic acid, formic acid, acetic acid, butyric acid, propionic acid, inorganic acids such as sodium bisulfite, sodium hydroxide, ammonium hydroxide, and the like, and may be used in the range of 0.1 to 0.7 parts by weight based on 100 parts by weight of raw skin. .

After the deliming process and the softening process, a pickling process is performed to prepare a tanning process, which is a subsequent step. Since the leather after the deliming and softening process has an alkaline pH of about 8 to 9, uniform tanning of the surface and the inside of the raw material may not be achieved without the pickling process. Therefore, it is necessary to adjust to an acid state suitable for a subsequent tanning process through the pickling process.

Pickling process may be carried out in a temperature range of 20 ~ 30 ℃, it is carried out by adding the acid component in the range of 0.1 to 3 parts by weight based on 100 parts by weight of leather, wherein the water is usually 100 to 150 based on 100 parts by weight of leather It is preferable to add in a range by weight. As the acid component, weak acids such as formic acid, lactic acid, acetic acid, butyric acid, propionic acid, and strong acids such as nitric acid and sulfuric acid can be used. In the pickling process, the raw acid in the alkaline state may swell due to the sudden administration of the acid component. In order to prevent this, it is preferable to add the weak acid component first and then add the strong acid component to gradually increase the acidity.

After the pickling process, the tanning process is performed using tanning agent. The tanning process is to fix and stabilize the collagen fibers so that the raw materials do not decay. Through this process, the raw materials have water resistance, abrasion resistance, chemical resistance, heat resistance, Properties such as elasticity and flexibility are improved and added.

As tanning agents, in addition to inorganic tanning agents such as chromium salts, aluminum salts, and zirconium salts, as organic tanning agents, tanning agents extracted from plants such as quebracho, wattle, sumac, hemlock, and spruce, and synthetic tanning agents (phosphate charcoal) Ning agent, sulfate tanning agent, etc.) etc. can be used. Although chromium salt is mainly used as a tanning agent, it is preferable to use a mixture of one or more tanning agents except for chromium salt due to human health and environmental hazards of the chromium salt.

When the oiliness process is finished through the tanning process, Yuseong Hyuk is obtained, and before proceeding to the dyeing step, a dehydration process, a sorting process, and a shaving process may be performed. The dehydration process is to adjust the moisture content of the leather to 40 ~ 50% by mechanical pressure. The sorting process is based on the grade of the leather in consideration of the purpose and use of the leather, the value of the product, and the wound of the leather surface. It is a process of classifying grades, and a shaving process is a process of re-adjusting the thickness (thickness) of the leather in consideration of the purpose of use.

After the oil process, the dyeing step is performed through the dehydration process as described above.

The dyeing step may preferably comprise a retanning process, a neutralization process, a coloring process and a branching process, or preferably may further comprise a fixing process.

The retanning process, the neutralizing process, the coloring process, the eggplant process, and the like constituting the dyeing step may be sequentially performed in the drum but may be performed in one step.

Tanned leather may have a non-uniform fibrous structure pattern in the epidermis due to inconsistent tanning effect. The retanning process converts the non-uniform fibrous structure pattern into a uniform fibrous structure pattern, thereby achieving both aesthetic and physical properties. It is a process for improving. Due to the retanning process, flexibility, elasticity, and the like are improved, and also stability against water or sweat is improved.

The retanning process can be carried out using tanning agents, preferably vegetable tanning agents and synthetic tanning agents, with the preferred range of tanning agents being in the range of 1.5 to 5.0 parts by weight based on 100 parts by weight of leather.

After the retanning process, it is desirable to carry out a neutralization process to prevent the rapid reaction of the dye in the coloring process with the eggplant in the eggplant process. Eggplants can cause pigmentation and eggplant unevenness due to rapid reaction when dyes and eggplants are added.

After the neutralization process is completed, a dye is added to perform a coloring process. In the method of the present invention, the coloring process is performed using a natural dye, and the amount of natural dye, the internal temperature of the drum, and the degree of stirring As described above.

After the coloring process, the eggplant process is carried out to impart oil to the leather to impart flexibility and to impart washing resistance, water resistance, and the like. The branching agent may use any known branching agent. For example anionics such as oil sulfate, oil sulfite, oil sulfonate, soap, oil phosphate, cationics such as aliphatic amine based oils, amphoterics such as aminocarboxylic acid based oils, nonionics such as polyethylene oxide derivatives, Vegetable or animal fats, such as olive oil and iron oil, can be used. Such a branching agent may be added in a range of 4 to 15 parts by weight based on 100 parts by weight of leather, and water may be used in a range of 80 to 150 parts by weight based on 100 parts by weight of leather. Preferred stirring conditions of the eggplant process are 40 to 50 DEG C inside the drum, 8 to 15 rpm rotation speed of the drum, 60 to 180 minutes stirring time.

After the coloring and eggplant process, a fixing process may be added. The fixing process is a process for stabilizing the binding of the dye to the branched leather and inducing further binding of the dye to the branched leather by acidifying the leather which has been subjected to the coloring and branching process using an acid component, in particular formic acid. For the fixing process, the acid component, preferably formic acid, is used to adjust the pH to a value of 3.5 or higher, and the fixing aid can be used to improve the degree of fixation, wherein the fixing aid usually uses a cationic polymer.

Fixing process may be used in the range of 0.5 to 3 parts by weight based on 100 parts by weight of leather in consideration of the type of branching agent used, the amount of branching agent used, water is used in the range of 80 to 150 parts by weight based on 100 parts by weight of leather. Can be. Preferred stirring conditions of the fixing step are 40 to 50 ° C. in the drum, 8 to 15 rpm, and 60 to 180 minutes for the stirring time.

After the dyeing step including the fixing process, the finishing process is performed. If the steps prior to the finishing process are processes under wet conditions, the finishing process is process steps under dry conditions, including a saming process for removing moisture and a setting out process for imparting smoothness to the leather. process conditions for each process, including drying, conditioning, staking, milling, buffing, togling, and finishing , Methods of carrying out the process, and the like are known in the art and reference may be made to the literature as described above.

In another aspect, the present invention relates to a skin dyed with a natural dye obtained by the method for producing a skin dyed with a natural dye as described above.

Mapi dyed with natural dyes of the present invention can be understood as a natural dye dye as a lac dye, paprika dyes, cacao dyes or safflower dyes, more specifically having the fastness and physical properties of the following [Table 1] Can be understood as a mopi.

As described above, it is possible to provide a method for producing a naturally dyed coat using a lac dye, paprika dye, cacao dye, or safflower dye as a natural dye, and a coat obtained by the method, which is obtained according to the method of the present invention. Natural dyed skin has a high fastness and exhibits properties such as tensile strength and tear strength that do not jump compared to the skin using synthetic dyes.

1 is a photograph of the surface color of a mop stained with lac dye, paprika dye, cacao dye and safflower dye.
2 is an evaluation result of physical properties and fastnesses such as tensile strength, tear strength, and the like of lacy dye, paprika dye, cacao dye and safflower dye.

Hereinafter, the present invention will be described with reference to Examples and Experimental Examples. However, the scope of the present invention is not limited to these examples and experimental examples.

< Example > Dyed with natural dyes Mafi  Produce

Example 1 Preparation of Mares Dyed with Rock Dye

100 parts by weight of the natural dye solution (100 parts by weight of the dye liquid mixed with 5 parts by weight of powdery lac dye) was mixed with 100 parts by weight of the skin after the tanning process and the neutralization process, and the mixture was placed on a drum. After keeping the internal temperature of the drum at 50 ° C, the drum was rotated at 10 rpm for about 60 minutes to allow the lac dye to be dyed on the skin. Next, sulfuric acid oil, which is an anionic branching agent, was put into the drum at 12 parts by weight based on 100 parts by weight of the mop, and the drum was rotated at 10 rpm for about 120 minutes while maintaining the internal temperature of the drum at 50 ° C to induce the binding of the lac dye, the moist and the eggplant. It was. Then, 1 part by weight of formic acid, a fixing agent based on 100 parts by weight of distilled water, was diluted with 10 times the weight of water and placed in a drum. Similarly, the drum was rotated at 10 rpm for 60 minutes while maintaining the internal temperature of the drum at 50 ° C. By inducing further binding of the skin stained with the lac dye was prepared. The color of the mop prepared with the lac dye can be seen in [FIG. 1].

Example 2 Preparation of Mare Dyed with Paprika Dye

In the same process as in <Example 1> was prepared a dye stained with a natural dye, a natural dye was prepared using a paprika dye in the same amount as the lock dye instead of the lock dye. The color of the cape prepared with paprika dye can also be seen in FIG. 1.

Example 3 Preparation of Mare Dyed with Cacao Dye

In the same process as in <Example 1> was prepared a dye stained with a natural dye, a natural dye was prepared by using a cacao dye in the same amount as the lock dye instead of the lock dye. The color of the cape prepared with cacao dye can also be seen in [Figure 2].

Example 4 Preparation of Dye Stained with Safflower Sulphate

In the same process as in <Example 1> was prepared a dye stained with a natural dye, a natural dye was prepared by using a safflower sulfur dye in the same amount as the lac dye instead of the lac dye to the dye stained with a natural dye. The color of the cape prepared with safflower sulfur dyes can also be seen in FIG.

< Comparative Example > Dyed with synthetic dyes Mafi  Produce

Acid red 97 (Alizarine Chrome Red G, Color index: 22890, CAS RN, which is a synthetic dye of red color representing red instead of a lac dye, is prepared in the same process as in <Example 1>. : 10169-02-5) was used to prepare a skin stained with a synthetic dye. The color of the mipa stained with the synthetic dye is shown in Fig. 1 together.

< Experimental Example > Dyed with natural or synthetic dyes Mafi  Properties and Fastness  evaluation

The tensile strength, tear strength, elongation, elongation, rupture strength, friction fastness and wash fastness of the skin dyed with natural dyes or synthetic dyes prepared in the above Examples and Comparative Examples by the method disclosed in FIG. It was.

The results are shown in [Figure 2] below.

The results of FIG. 2 show that the physical properties and the fastnesses of the skins dyed with natural dyes in the above example show an effect equal to or greater than the physical properties or fastnesses of the skins of Comparative Examples dyed using synthetic dyes.

Claims (6)

(a) a pretreatment step to remove unnecessary components contained in the skin,
(b) an oily step to immobilize and stabilize the collagen fibrous tissue in the pretreated step to give water, heat resistance and flexibility,
(c) a dyeing step for imparting color to the oily finishes, and
(d) comprising a finishing step to impart flexibility and smoothness to the finish after the dyeing step,
The dyeing step of (c) comprises the step of mixing and stirring the oil after the oily step, natural dye and water selected from the group consisting of lac dye, paprika dye and cacao dye,
In addition, the dyeing step of (c) is configured to further include a branching process and a fixing step simultaneously with or after the mixing and stirring step,
The eggplant process is performed using 3 to 15 parts by weight based on 100 parts by weight of sulfurous acid oil, which is an anionic branching agent,
The fixing process is a method of producing a dyed with natural dyes, characterized in that the formic acid is used as a fixing agent based on 100 parts by weight of 0.5 to 3 parts by weight.
The method of claim 1,
The mixing and stirring step is dyed with natural dyes, characterized in that the mixing is carried out by mixing and stirring 100 parts by weight of the water, 80 to 150 parts by weight of 100 parts by weight of water, 2 to 10 parts by weight of the natural dyes based on 100 parts by weight of skin Method of making a mop.
The method of claim 1,
The mixing and stirring step is dyed with natural dyes, characterized in that the mixing is carried out by mixing and stirring 100 parts by weight, 80 to 150 parts by weight of 100 parts by weight of water, 3 to 7 parts by weight of natural dyes based on 100 parts by weight of skin Method of making a mop.
The method of claim 1,
The mixing and stirring step is carried out by mixing and stirring at a temperature of 50 to 60 ℃ at 9 to 12rpm for 60 minutes or more, characterized in that the dyeing method of dyed with natural dyes.
The method of claim 1,
The eggplant process is performed by stirring at 8 to 15 rpm for 60 to 180 minutes at a temperature in the range of 40 to 50 ℃,
The fixing process is a method of producing a dyed with natural dyes, characterized in that performed by stirring at a temperature in the range of 40 to 50 ℃, 8 to 15 rpm for 60 to 180 minutes.
A coat dyed with a natural dye obtained by the process according to any one of claims 1 to 5.

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