KR100596720B1 - Paint composition for urushiol-coated leather - Google Patents

Abstract

The present invention relates to a lacquer-containing lacquer coating for lacquer coating and a method for producing the lacquer skin by penetrating or coating natural leather obtained from an animal.

Specifically, the present invention relates to a coating composition and a method for producing the composition, which comprises at least 50% by weight of the natural lacquer or the natural lacquer separated by components and then directly participating in the coating composition.

Natural lacquer liquids extracted from lacquer trees without the presence of high strength coatings or penetrants containing natural or large amounts of natural materials (more than 50% by weight) that can be used in natural leather (e.g., refined coatings) Taking into consideration that it is difficult to use on a commercial scale, the inventors have invented a method for producing chilpi using a composite paint containing a lacquer component that is easy to work with.

Through the present invention, the natural properties of the lacquer, such as aesthetics, durability, antibacterial, antibacterial, antifouling, waterproof, water repellent, flame retardant, and chemical durability of the coating film itself, can be easily added to the leather, resulting in a significant improvement in workability. .

Lacquer, lacquer, leather, natural paint, composite paint

Description

Paint composition for lacquer {PAINT COMPOSITION FOR URUSHIOL-COATED LEATHER}

Chilpi is a compound word of "chil" and "pi" and refers to lacquer and lacquer, a lacquer and animal skin, and lacquered leather. Korea has also been able to easily access leather since ancient times and has been widely used in clothing, trinkets, and living containers. However, since the leather is a material which is highly vulnerable to moisture, rot or decay, the lacquer is applied to the leather in order to reinforce the weak point of the leather, and a method of manufacturing lacquer is known which has enhanced durability and strength. Such chilpi crafts can be found in China and Japan and have developed into leather crafts with excellent physical properties such as antiseptic, moisture proof, antifouling, and antibacterial properties. For example, the durability and strength were so excellent that the armor was made of chilpi (chili armor treasure 460). The chilpi armor was light and hard and could withstand swords and bows.

Natural lacquer is a sap extracted from rhus Vernicifera widely distributed in Korea, Japan and China. It has been used as a paint in China for about 5,000 years, and has excellent coating strength, durability, waterproofness, etc., and lacquerware, which is more than 2,000 years old, has good physical properties to preserve the original shape. However, the humidity and temperature must be properly maintained during drying, and it is difficult to apply variously because the application is difficult and the drying speed is also slow. Specifically, in the case of chilpi crafts, the coating was mainly performed by using the nickname 'Three' technique of applying a thin layer of natural lacquer and wiping. In some cases, the coating was formed using a brush or fiber. Shri technique has many handicraft elements and it is difficult to get out of the craft application because there are many changes depending on the state of natural lacquer. This difficulty is due to the fact that the natural lacquer has an unstable suspension of solid components such as urushiol, polysaccharides, glycoproteins, and proteins, in addition to water, and there are many changes depending on the extraction time, place, and extraction method.

Furthermore, the lacquer liquid used in the refining coating is generally subjected to a refining process of so-called `` Kurome '' method that reduces moisture to less than 3% by repeatedly applying lacquer on a wide surface. It has been used for thousands of years in China, Japan, Korea, etc., and finally, Japan has made progress by developing various additives. Recently, the refining method has been modified and developed by the homogenization and reduced pressure dehydration, or by the wiper type vacuum thin film distillation unit and the three-axis roll miller, and a new mass production technique using the bubble column reactor using the organic solvent enzyme reaction has been developed. As a result, productivity and physical properties are improved. However, its use is extremely limited due to the difficulty in application and use due to the heterogeneity of its content and the presence of components that do not directly participate in the coating film formation in natural lacquer liquid.

On the other hand, leather is rarely used immediately without any treatment on the skin of the animal, and generally goes through 20 different treatments. Among these processes, chromium, which is a heavy metal, is mainly used in a tanning process to prevent changes in leather and corruption, which has been a cause of environmental pollution. At present, a method using zirconium and aluminum as a substitute for chromium has been developed and put into practice, but a product using vegetable tanning using vegetable raw materials in the tanning process is preferred as a high value-added product.

In addition, leather can be dyed to express colors other than its own color, and commercialized chemical dyes are used for this purpose. However, in order to highlight environmental friendliness and naturalness, leathers using natural dyes such as buckwheat, marionette, and joiner are being introduced.

Lastly, the surface of leather is generally weak to moisture, heat, chemicals, etc., and is easily coated with chemical paints such as urethane. Natural coatings to do are very rare. First of all, there are natural paints and coatings based on dry oils such as soybeans and castor oils, but they mainly contain unsaturated fatty acids, which makes them difficult to use in leather due to their weakness but weak strength.

Urushiol, on the other hand, has both a phenol group and an alkyl group. The phenol group has strength and alkyl group gives flexibility and good reactivity, making it easy to use as a material of chilpi.

Therefore, the coating of leather based on urushiol and lacquer polymer to reduce the environmental pollution and to highlight the natural friendliness and naturalness is the flow of the leather industry. In this respect, by treating, dyeing and coating the leather Chilpi, which maximizes its natural and natural friendliness, can be said to be highly marketable. In addition, the preservative, antibacterial, antimicrobial, antifouling, chemical durability, water repellency and waterproofness of the lacquer is important because it is a very necessary physical property in the functional aspect.

However, the natural lacquer or purified lacquer described above requires high humidity and proper temperature, and is difficult to apply because it is difficult to apply and use and must be handled by a technician or craftsman. Therefore, we have developed lacquer mixed paints that can be easily cured at low humidity or temperature by adding paint additives or hardeners or additives used in the manufacture or drying of commercially available lacquer reactions or urushiol, mainly in Korea, Japan and China. However, they have been mainly used as functional special paints, although there are some examples applied to existing lacquer crafts or utility products, but none have been introduced into leather.

Therefore, the present inventors added a commercial curing agent to natural lacquer itself or a recombinant lacquer composition separated and recombined according to its constituents under various conditions to test whether it is possible to prepare chilpi regardless of drying humidity or temperature. A method of preparing an environmentally friendly lacquer coating composition having a weight% of 50% or more was found, and the present invention was completed based on this.

Accordingly, an object of the present invention is to provide a lacquer coating composition comprising a natural lacquer itself or a lacquer and a hardening agent separated and recombined according to its components.                         

In addition, an object of the present invention is to provide a coating composition for the lacquer coating further comprising animal and vegetable dry oil or natural dye in the coating composition for the lacquer coating.

In addition, an object of the present invention is to provide a method for producing the coating composition for lacquer coating.

Paint coating composition of the present invention for solving the above problems (a) natural lacquer; (b) a layer containing urushiol by adding a polar organic solvent or a nonpolar organic solvent to the natural lacquer and centrifuging it; (B) a layer containing water-insoluble glycoproteins and water-soluble gums; And (c) a mixture of layers (a) and (c), or a mixture of layers (a), a portion of layer (b) and a layer (c) after separation into a layer containing a water soluble enzyme and a water soluble gum; And (c) from 50 to 99.9% by weight of any of the combinations of component (a) and component (b), preferably from 50 to 99% by weight, and (B) monomers of synthetic resins, metal curing agents and combinations thereof. It is characterized by consisting of 0.1 to 50% by weight, preferably 1 to 50% by weight of a curing agent selected from the group consisting of.

In addition, the monomers of the synthetic resin constituting the composition may include (a) a monomer for preparing a urethane resin, a polyisocyanate, an acrylic resin, an epoxy resin, a polyamide, an alkyd resin, a polyolefin and a combination thereof, preferably an epoxy resin, a polyolefin and Monomers for the preparation of combinations thereof and (b) aldehydes, silanes, nonyl phenols, furfuryl alcohols, butanone peroxides, dimethyl phthalate and combinations thereof It may be characterized as a monomer selected from the group consisting of water, preferably aldehydes, silanes and combinations thereof.

In addition, the metal curing agent constituting the composition may be characterized in that the metal curing agent selected from the group consisting of powders, oxides or salts of zinc, lead, iron, manganese or cobalt or combinations thereof.

In addition, the lacquer coating composition of the present invention, the component (A) further comprises (d) animal and vegetable dry oil, (e) natural dye or (f) a combination of the component (d) and component (e). It may be characterized by.

In addition, the animal and vegetable dry oil of (d) in the component (A) constituting the composition is linseed oil, drink oil, tung, olive oil, castor oil, soybean oil, castor oil, rapeseed oil, cottonseed oil, sunflower It may be characterized in that it is selected from the group consisting of oil, safflower oil, fish oil, fish oil, diesel oil (whale oil), sardine oil and combinations thereof.

In addition, the natural dyes of (e) of the component (A) constituting the composition are quince, cloves, gall bladder, Maddera, joiner, block, turmeric, buckthorn, persimmon tree, broad-leaved leaf, old tree, spruce tree, jujube tree, Oak, chestnut, mulberry, cedar, hiking tree, oak, acorn, pomegranate, ox, pine, fire wood, sorrel, gardenia, apricot, thistle, ocher, helminthia, animal bleeding, violet shell, cochineal , Commerce mud, volcanic ash, salt, (dogs), soft shells, (mountains) ducks, and combinations thereof.

In addition, the polar organic solvent or the non-polar organic solvent of (b) of the component (A) constituting the composition is selected from the group consisting of acetonitrile, benzene, toluene, chloroform, hexane, octane, heptane and combinations thereof. You can do

In addition, the water-soluble enzyme of (b) in the component (A) constituting the composition may be characterized in that the phenol oxidase.

In addition, the phenol oxidase may be characterized in that selected from the group consisting of laccase, peroxidase, catalase and combinations thereof.

The method of manufacturing a chilpi using the coating composition for the coating of the present invention (A) diluting the coating composition for coating the coating with a solvent or thinner (B) and the diluted coating composition for coating the coating of step (A) It is characterized in that it consists of a step of applying or spraying on leather or dipping the leather coating composition for diluting lacquer.

In addition, the manufacturing method of the chilpi is the step (A) prior to the step (A) of diluting the animal and vegetable dry oil with a solvent or thinner and (D) the diluted animal and vegetable dry oil of the step (C) to the leather or sprayed or leather It may be characterized in that it further comprises the step of immersing in dilute animal and vegetable dry oil.

Hereinafter, the concept of the present invention.

The present invention is coated or penetrated into a leather or coating agent containing 50% by weight or more of natural additives such as protein, glycoprotein and polysaccharides, animal and vegetable dry oil, and natural dyes, which are substances contained in urushiol and urushiol and natural lacquer. It is about what constitutes chilpi.

It relates to the construction of lacquer coating by coating or penetrating the leather mixed lacquer coating which can be easily cured at low humidity or temperature using commercially available paint additives or hardeners or additives used in manufacturing or drying synthetic resins as described above.

As described above, lacquer liquid has very excellent physical properties as a paint. Furthermore, according to Korean Patent Application No. 2002-7004986, it is possible to obtain a high viscosity polymer by gradually reacting lacquer not to harden, and to arbitrarily control the content of a component that does not directly participate in the film formation, thereby achieving uniform film quality. Can be.

According to the present invention, by adding a monomer or a metal curing agent of a synthetic resin to such a lacquer component, it is possible to easily give the physical properties of the lacquer to the leather even if it is not the difficult humidity and temperature conditions required for curing the conventional lacquer.

The monomer of the synthetic resin is a monomer for preparing a urethane resin, a polyisocyanate, an acrylic resin, an epoxy resin, a polyamide, an alkyd resin, a polyolefin and a combination thereof, in consideration of reactivity with urushiol, preferably an epoxy resin, a polyolefin and Monomers for the preparation of combinations thereof. As well as aldehydes, silanes, nonyl phenols, furfuryl alcohols, butanone peroxides, dimethyl phthalate and combinations thereof, preferably aldehydes, silanes and these The combination of is also an effective additive for the curing of lacquer solutions.

In addition, the metal curing agent is also a powder, oxide or salt of zinc, lead, iron, manganese or cobalt or a combination thereof, preferably zinc, lead and iron powder, oxide or salt or combination thereof in consideration of reactivity with urushiol It may be water.

The lacquer mixed paint of the present invention may be applied to leather by itself using a spray, a brush, a fiber, or a roller, or diluted with various commercial solvents or thinners, and then applied or penetrated to the leather. It is also possible to infiltrate the leather by raising it.

Leather coated with or mixed with lacquer coating is dried on its own, or after partial drying, heat of 60 ° C to 300 ° C is hardened by drying or increasing the degree of drying by commonly available heat treatment methods such as infrared rays, hot air, and oven. It is possible to, and through the drying or curing process it is possible to obtain the strength of the coating film required.

There is a tendency to strongly absorb the paint due to the leather material itself and the fine pores inside the material when applying and coating the coating composition for lacquer coating consisting of the above components, the lacquer as the main ingredient. The absorbency of such leather may cause problems such as forming an uneven coating film, unnecessarily increasing the amount of paint applied, or hardening the leather due to absorption of a lacquer liquid above an appropriate level.

However, prior to applying lacquer to leather, dilution of animal and vegetable dry oils such as castor oil, soybean oil and castor oil to commercial solvents or thinners, or first application to leather without dilution will minimize absorption of lacquer fluid. Can be. Specifically, in the case of applying the lacquer after partially or completely curing by applying heat treatment after drying oil, the quality of the coating film can be remarkably improved by minimizing absorption of the lacquer solution and evenly forming the coating film.

Animal and vegetable dry oil for the purpose of the above purpose is linseed oil, drinking oil, tung, olive oil, castor oil (castor oil), soybean oil, castor oil, rapeseed oil, cottonseed oil, sunflower oil, safflower oil, fish oil, liver oil, diesel oil ( Whale oil) and sardine oil may be used, and may be preferably selected from the group consisting of castor oil, soybean oil and castor oil.

On the other hand, leather dyes have conventionally used chemical dyes to impart a color other than the brown color itself, but due to an increase in consumer preference for natural products with an emphasis on environmental friendliness, natural dyes such as spines, marionettes, or joiners have been spotlighted. have. Natural dyes applicable to leather include spines, cloves, gall bladder, marionettes, joiner, lumps, turmeric, buckthorn, persimmon, larch, oak, locust, jujube, oak, chestnut, mulberry, cedar, hiking Tree, oak, acorn, pomegranate, noble tree, pine, fire wood, worship, gardenia, apricot, thistle, ocher, thunder, animal bleeding, violet shell, cochineal, commerce mud, volcanic ash, yeast, (dog ), Cactus and (mountain) duck are mentioned. Preferably, it may be selected from the group consisting of spines, marionettes, joiners and combinations thereof.

Chilpi has been developed and used mainly in Korea, Japan, and China for thousands of years, and currently maintains only its context. It is impossible to mass-produce because it can only be manufactured by craftsmanship by technicians or craftsmen. In the present invention, it is possible to maximize the natural and environmental friendliness of the leather by using the lacquer mixture paint, which is easy to use as described above, and also has the same resistance as antibacterial, antibacterial, waterproof, water repellent and chemical durability that the lacquer possesses itself. It is possible to impose physical properties on the leather as a functional.

The present invention as described above will be described in detail based on the following examples. However, the scope of the present invention is not limited to the following examples, and it is natural to those skilled in the art to which the present invention pertains to all the embodiments easily derived based on the technical idea of the present invention. Do.

Example 1

Acetone was mixed with 1 kg of Chinese natural lacquer at a ratio of 1: 1, centrifuged at 1,500 rpm to remove precipitates, and acetone and water were evaporated under reduced pressure at 65 ° C. to purify urushiol. To 200 g of urushiol, 50 g of N-b (aminoethyl) aminopropyl trimethoxy silane and 50 g of ethyl trimethoxy silane were reacted at room temperature. At this time, it stirred, injecting slowly so that temperature might not exceed 50 degreeC. It was diluted in 100 ml of xylene and then applied to the leather of 30 cm X 30 cm using a commercial paint sprayer. The leather was left for 1 day and then placed in an oven at 90 ° C. for additional drying for 3 hours. As a result of the treatment, the leather had a high brightness, and 5 was obtained as a result of measuring the fastness of friction by the KSM 6890 method.

Example 2

50 g of natural lacquer was mixed with acetonitrile 1: 1 and left to stand for 1 hour, followed by centrifugation at 4,000 rpm for 10 minutes. A blue liquid layer was formed in the middle and separated and used as an enzyme liquid. After 200 mL of 2-propanol and 400 mL of urushiol were mixed, the enzyme solution and 30 mL of water were further added, followed by reaction using a 2 L bubble column reactor. The reaction was carried out for 24 hours while maintaining 2 L of air injection per minute at 45 ℃ to obtain a polymer of 3500 cP. The viscosity was measured according to the method described in 'Rotational Rheometry (1)' Polymer Science and Technology, Vol. 5, No. 3, 1994, pages 275-283. 100 g of an enzyme-polymerized lacquer polymer having a viscosity of 3500 cP was dissolved in 100 ml of diethylbenzene, and 40 g of formaldehyde and 7 ml of ammonia were added thereto, followed by heating at 100 ° C. for 2 hours. At this time, the water produced by the condensation reaction was separated and evaporated again in the evaporation vessel for 20 minutes to obtain a liquid with fluidity. 4 ml of 4% calcium octoate (Ca-Octoate) was added thereto, diluted in 140 ml of toluene, and 3 ml of the side liquor was added and stirred, and then applied to the leather of 30 cm X 30 cm using a commercial paint sprayer. . Immediately after application, the resulting film was dried in an oven at 100 ° C. for 5 hours. As a result of measuring friction fastness by KSM 6890 method, 4.5 was obtained and indigo leather with perfect waterproofness was obtained.

Example 3

To 100 g of the 3500 cP urushiol polymer specified in Example 2, 80 g of Lupranat M11R from BASF was diluted and mixed in 150 ml of butyl acetate. 100 mg of 1,4-butanediol, 100 mg of ethylene glycol, 100 mg of modified silicone surfactant (Toray Corporation) and 100 mg of castor oil were added and mixed. This was applied to a 30 cm X 30 cm leather that had been previously applied and cured with caster oil using a commercial paint sprayer to obtain a leather with a lacquer mixture coating.The result was measured by the KSM 6890 method to obtain 4.5. there was.

Leather is a natural animal skin, but in the production process of the actual product, heavy metal tanning, chemical dyeing and chemical coating process has caused problems of environmental pollution.

In the present invention, attention has been paid to the traditional chilpi technique to reduce the environmental pollution, mass production of chilpi is possible by appropriately adding a curing agent to alleviate the strict coating conditions, which was a problem of the conventional chile skin manufacturing process.

Furthermore, by performing primary coating with animal and vegetable drying oils, a more uniform quality lacquer coating was obtained, and natural dyes were used instead of chemical dyes to further improve environmental friendliness and naturalness.

Due to the characteristics of the present invention as described above, it is possible to introduce a lacquer film having antibacterial, antibacterial, antifouling, waterproof, water repellent, flame retardant, chemical durability, etc. into leather in an easy, reproducible, and easy quality control manner. It became.

Claims (15)

(A) 50 to 99.9% by weight of any of the following components (a) to (c): and (a) natural lacquer; (b) a layer containing urushiol by adding a polar organic solvent or a nonpolar organic solvent to the natural lacquer and centrifuging it; (B) a layer containing water-insoluble glycoproteins and water-soluble gums; And (c) separating the layer containing a water soluble enzyme and a water soluble gum. A mixture of said layers (a) and (c), or a mixture of layer (a), part of layer (b) and layer (c); And (c) a combination of component (a) and component (b), (B) 0.1 to 50% by weight of a curing agent selected from the group consisting of monomers of synthetic resins, metal curing agents and combinations thereof Made up of In the component (A), the polar organic solvent or the nonpolar organic solvent of (b) Acetonitrile, benzene, toluene, chloroform, hexane, octane, heptane and combinations thereof, The monomer of the synthetic resin is (a) monomers for the preparation of urethane resins, polyisocyanates, acrylic resins, epoxy resins, polyamides, alkyd resins, polyolefins and combinations thereof; And (b) aldehydes, silanes, nonyl phenol, furfuryl alcohol, butanone peroxide, dimethyl phthalate and combinations thereof Selected from the group consisting of The metal curing agent Selected from the group consisting of powders, oxides or salts of zinc, lead, iron, manganese or cobalt or combinations thereof, The component (A) is (d) animal and vegetable dry oils; (e) natural dyes; or (f) a combination of component (d) and component (e) A coating composition for lactating, characterized in that it further comprises. delete The method of claim 1, wherein the monomer of the synthetic resin A coating composition for lactating coating, characterized in that the monomer for the preparation of epoxy resins, polyolefins and combinations thereof and monomers selected from the group consisting of aldehydes, silanes and combinations thereof. delete delete The method of claim 1, wherein the animal and vegetable dry oil of the component (d) Linseed oil, drinking oil, tung, olive oil, castor oil, soybean oil, castor oil, rapeseed oil, cottonseed oil, sunflower oil, safflower oil, fish oil, fish oil, light oil (whale oil), sardine oil and combinations thereof A coating composition for lacquer, characterized in that selected from the group consisting of water. 7. The method of claim 6, wherein the animal and vegetable dry oil of the component (d) Castor oil (castor oil), soybean oil, castor oil and a coating composition for the lacquer, characterized in that selected from the group consisting of. The method of claim 1 wherein the natural dye of component (e) is Side, cloves, gall bladder, marionette, joiner, flower, turmeric, buckthorn, persimmon, broad-leaved tree, fir tree, pine, jujube, oak, chestnut, mulberry, cedar, hike, oak, acorn, pomegranate , Nymph, pine, fire wood, worship, gardenia, apricot, thistle, ocher, thrush, animal bleeding, purple shell, cochineal, commerce mud, ash, salt, dogs, soft shell, (mountain A coating composition for lactating, characterized in that selected from the group consisting of duck and combinations thereof. The method of claim 8 wherein the natural dye of component (e) is The coating composition for lacquer coating, characterized in that selected from the group consisting of buckwheat, madder, joiner and combinations thereof. The method according to any one of claims 1, 3, or 6 to 9, A coating composition for lactating coating comprising 50 to 99% by weight of the component (A) and 1 to 50% by weight of (B). delete The lacquer coating composition according to any one of claims 1, 3, or 6 to 9, wherein the water-soluble enzyme of (b) in the component (A) is a phenol oxidase. The method of claim 12, wherein the phenol oxidase Lacquer coating, peroxidase, catalase, and combinations thereof A coating composition for lactating, characterized in that selected from the group consisting of. Method for preparing chilpi consisting of the following steps: (A) diluting the lacquer coating composition of any one of claims 1, 3 or 6 to 9 with a solvent or thinner; And (B) applying or spraying the diluted lacquer coating composition of step (A) to the leather or immersing the leather in the diluted lacquer coating composition and drying. The method of claim 14, wherein before step (A), (C) diluting the animal or vegetable dry oil of claim 1 with a solvent or thinner; And (D) applying or spraying the diluted animal or vegetable dry oil of step (C) to the leather or immersing the leather in the diluted animal or vegetable dry oil and drying the same. Method for producing chilpi characterized in that it further comprises.