KR100596718B1 - Paint composition comprising urushiol and manufacturing process thereof - Google Patents

Abstract

The present invention is an environmentally friendly natural lacquer consisting of 99.7 to 90% by weight of a highly polymerized recombinant lacquer composition having a viscosity of 3,000 to 20,000 cP, and 0.3 to 10% by weight of a curing agent selected from the group consisting of monomers of synthetic resins, metal curing agents and combinations thereof. A coating composition and its manufacturing method.

Specifically, the coating composition of the present invention is characterized by the fact that the lacquer sap is separated by each component, and then achieved high polymerization degree through enzymatic polymerization and thermal polymerization, so that the curing composition is rapidly cured even in a general environment instead of the conventional difficult curing conditions only by adding a minimum amount of curing agent. It is done.

Lacquer, paint, high polymerization, viscosity, curing agent, natural curing

Description

Lacquer coating composition and its manufacturing method {PAINT COMPOSITION COMPRISING URUSHIOL AND MANUFACTURING PROCESS THEREOF}

The paint is applied to the surface of the building, the interior and exterior walls of the structure, automobiles, etc. to the household goods to protect the material and give a sense of aesthetics.

Many paints have been developed and used for the purpose of performing the above functions, and synthetic resins separated from petroleum have been used as main raw materials for forming coating films in modern times.

However, petrochemical paints made mainly of synthetic resins contain substances that are harmful to the human body and the environment during the coating itself and the application process.

Specifically, heavy metals such as lead, cadmium, mercury and chromium, carcinogenic components such as formaldehyde, volatile organic solvents such as chlorinated hydrocarbons, benzene, toluene, xylene and glycol, which do not decompose in the ecosystem and remain the longest, are representative hazardous substances. However, these components do not decompose and remove from the ecosystem over time, but accumulate in the body through direct contact with the human body or respiration, causing various diseases.

The harmful effects of harmful components on the human body are considered to be the cause of carcinogenesis, neuropathy, hypertension, infertility and abnormal pregnancy. Formaldehyde is a carcinogenic component that causes headaches, anemia, nervous system problems and respiratory disorders. It is known. As mentioned above, chlorinated hydrocarbons are the longest remaining components of environmental pollutants without decomposition. Volatile organic solvents such as benzene are not only highly addictive but also have chronic fatigue, headaches, memory loss, anemia, anorexia and allergies. It also causes.

Due to the harmfulness of petrochemical paints as described above, in recent years, natural paints having excellent environmental friendliness have attracted attention. However, natural paints based on dry oils such as soybean oil and castor oil, despite the advantages of being environmentally friendly, have a problem of excellent flexibility but low strength due to the absence of phenol groups in the dry oil itself.

The natural lacquer has been used as a paint since about 5,000 years, while maintaining its environmental friendliness. The natural lacquer has been used as a paint for a long time, urushiol, the main component of the lacquer coating. This is because it has a phenol group. Because of this, lacquer has excellent coating film strength, and its gloss and feel are also excellent as well as functionality such as durability and waterproofness. Lacquer lacquer has unlimited potential as a paint from the report that a lacquer pottery excavated in China has maintained its original form almost 2,000 years ago despite the fact that it has been around 2,000 years.

However, natural lacquer is in an unstable suspended state of the oil and water components, it requires a purification process to uniform the suspended state and supply the oxygen necessary for the enzyme reaction for forming the coating film.

Conventionally, for the purification, water was evaporated by stirring at 30 to 40 ° C. for about 2 to 24 hours, and additives were added to prepare lacquer liquids suitable for the purpose. However, the method is difficult to remove impurities contained in natural lacquer liquid and dry conditions. It is determined according to the experience of the skilled person, and thus the reproducibility is reduced. As a result, quality control of the final product is difficult. Furthermore, the painting also has the disadvantage of being too difficult and poor workability for the general public to perform.

Korean Patent Application No. 2002-7004986 has achieved the uniformity, workability and economical efficiency of the above quality by separating and recombining natural lacquer by component and enzymatic polymerization.

However, the recombinant lacquer paint also requires a humidity of 60 to 70% or more and a temperature of 20 ° C or more for curing, as in the conventional lacquer paint, and the adsorption of dust due to the change of gloss, wrinkles of the coating, and slow curing depending on the curing conditions. It is still difficult for the public to carry out their work.

On the other hand, a method of adding an excess of epoxy or polyolefin up to 20 to 50% by weight in lacquer solution for easy curing was devised, but these additives themselves are resins for forming a coating film, and above all, the environment of lacquer, which is derived from petroleum and is a natural paint Reduces affinity.

Therefore, there is still a need for development of an improved method for utilizing lacquer as a natural paint.

Accordingly, the present inventors have made various changes to the recombinant lacquer composition separated and recombined natural lacquer by component, and when a specific curing agent is added to the highly polymerized recombinant lacquer composition having a certain viscosity or more, it is not affected by humidity or temperature rapidly. It has been found that a high quality coating film can be obtained, and the present invention has been completed based on this.

Accordingly, an object of the present invention is to provide a coating composition comprising a highly polymerized recombinant lacquer composition and a curing agent.

In addition, an object of the present invention is to provide a method for producing a coating composition which adds a curing agent after separating and recombining the natural lacquer for each component, followed by high polymerization through enzyme polymerization and thermal polymerization.

In addition, an object of the present invention is to provide a coating composition prepared by the above production method.

The coating composition of the present invention for solving the above problems is (A) 99.7 to 90% by weight of a highly polymerized recombinant lacquer composition of viscosity 3,000 to 20,000 cP, preferably 4,000 to 18,000 cP, more preferably 5,000 to 15,000 cP, Preferably from 99.5 to 93% by weight, and (B) 0.3 to 10% by weight of a curing agent selected from the group consisting of monomers, metal curing agents and combinations thereof, preferably 0.5 to 7% by weight. .

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 being 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.

The method for producing a coating composition of the present invention comprises (A) adding a polar organic solvent or a nonpolar organic solvent to a natural lacquer and centrifuging it to (a) a layer containing urushiol; (b) a layer containing water-insoluble glycoproteins and water-soluble gums; And (c) separating into a layer containing a water-soluble enzyme and a water-soluble gum, (B ₁ ) using the lower solution layer containing the water-soluble enzyme of step (A) or a pure enzyme isolated therefrom as an enzyme source. Enzymatic polymerization of the urushiol of the layer containing urushiol of step (A) to a viscosity of 3,000 to 20,000 cP, preferably 4,000 to 18,000 cP, more preferably 5,000 to 15,000 cP, and (C ₁ ) the step (B _1). 99.7 to 90% by weight, preferably 99.5 to 93% by weight of the highly polymerized recombinant lacquer composition produced through the above), and 0.3 to 10% by weight of a curing agent selected from the group consisting of monomers of a synthetic resin, metal curing agents and combinations thereof. Preferably, 0.5 to 7 wt% is added and stirred.

In addition, the production method of the present invention, the steps to use pure enzyme embellish to the step (B ₁₎ is (B ₂₎ separated from the lower oil layer or which contains a water-soluble enzyme in the step (A) as an enzyme source (A It is characterized in that it is a step of raising the viscosity to 3,000 to 20,000 cP by the enzymatic polymerization of the urushiol of the layer containing the urushiol of)).

The method for producing a coating composition of the present invention comprises (A) adding a polar organic solvent or a nonpolar organic solvent to a natural lacquer and centrifuging it to (a) a layer containing urushiol; (b) a layer containing water-insoluble glycoproteins and water-soluble gums; And (c) separating the layer containing the water soluble enzyme and the water soluble gum, (B ₃ ) the urushiol of the layer containing the urushiol of step (A) has a viscosity of 3,000 to 20,000 cP, preferably 4,000 to 18,000 cP, more Preferably, the monomers of the synthetic resin in 99.7 to 90% by weight, preferably 99.5 to 93% by weight of the high polymerized recombinant lacquer composition produced through the step of thermal polymerization to 5,000 to 15,000 cP and (C ₃ ) the step (B ₃ ) , And a step of adding and stirring 0.3 to 10% by weight, preferably 0.5 to 7% by weight of a curing agent selected from the group consisting of metal curing agents and combinations thereof.

In addition, in the preparation method of the present invention, the step (B ₃ ) (B ₄ ) thermally polymerizes the urushiol of the layer containing the urushiol of the step (A), and then contains the water-insoluble glycoprotein and the water-soluble gum in the step (A). To add the layer (b) or the natural lacquer and perform an enzymatic polymerization reaction to increase the viscosity to 3,000 to 20,000 cP, preferably 4,000 to 18,000 cP, more preferably 5,000 to 15,000 cP Can be.

In addition, the production method of the present invention is separated from the lower solution layer or the lower solution layer containing the water-soluble enzyme of the step (A) in the enzymatic polymerization of the step (B ₁ ), step (B ₂ ) or step (B ₄ ). It may be characterized in that it further comprises the step of adding a pure enzyme as the enzyme source.

In addition, the production method of the present invention may be characterized in that the thermal polymerization of the step (B ₂ ), step (B ₃ ) or step (B ₄ ) is carried out in a low oxygen to an oxygen-free state.

In addition, the preparation method of the present invention may be characterized in that the polar organic solvent or the non-polar organic solvent of step (A) is selected from the group consisting of acetonitrile, benzene, toluene, chloroform, hexane, octane, heptane and combinations thereof. have.

In addition, the production method of the present invention may be characterized by using a phenol oxidase as the enzyme source of the step (B ₁ ), step (B ₂ ) or step (B ₄ ).

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

In addition, the preparation method of the present invention is selected from the group consisting of dioxane, 2-propanol, tetrahydrofuran and combinations thereof in the enzymatic polymerization of step (B ₁ ), step (B ₂ ) or step (B ₄ ). The method may further include adding an organic solvent.

In addition, the production method of the present invention may be characterized in that the enzymatic polymerization reaction of step (B ₁ ), step (B ₂ ) or step (B ₄ ) is carried out in an air injection reactor.

The coating composition of the present invention is characterized in that it was prepared according to the above production method.

Hereinafter, the concept of the present invention.

The present invention is separated from and recombined urushiol, protein and polysaccharides, which are substances contained in urushiol and lacquer sap according to the components, and then 3,000 to 20,000 cP, preferably 4,000 to 2,000 obtained by enzymatic reaction or enzymatic reaction after heat treatment. It is characterized by using a highly polymerized recombinant lacquer composition of 18,000 cP, more preferably 5,000 to 15,000 cP. It is characterized by using 7% or less of a commercially available paint hardener in the high-polymerized lacquer composition.

 In the past, there was no enzyme polymerization method of lacquer other than Kurome, but a technique was developed using an enzymatic reaction in an organic solvent in a bubble column reactor (Korean Patent Application No. 2002-7004986), and the reaction proceeds gradually so that the lacquer does not harden. It was possible to obtain a high high viscosity polymer. At this time, by varying the amount and the reaction time of the polysaccharides, glycoproteins and proteins other than urushiol contained in the urushiol, enzymes, solvents and natural lacquer used in the reaction, products of various viscosities can be obtained. In addition, the viscosity of the urushiol is increased by using the well-known heat polymerization, and then, urethane is added by 5 to 90% or more of urushiol and a substance other than urushiol contained in the natural lacquer, followed by an enzymatic reaction to obtain a product having a very high viscosity. Could get In addition, the heat-treated urushiol has a low reactivity because the double bond of the alkyl group mainly participates in the reaction, but further reaction occurs due to the addition of unreacted urushiol and an enzyme, thereby increasing the reactivity as a product.

Such high reactivity high polymerization products can be cured by using alone or mixed commercially available curing agents or additives such as aldehydes, epoxies, silanes, polyolefins and metal curing agents of 0.5 to 7% or less.

As emphasized above, reducing the amount of additives other than natural substances is one of the most important factors in the manufacture of natural paints. Therefore, it is important to maintain high polymerization degree and reactivity.

In addition, depending on the intended use, a curing method may be applied by using only a minimum of additives and then applying a heat treatment technique to generate a coating film. This is because the degree of curing can be achieved only by having a thermosetting property which is cured without lowering the viscosity or the viscosity upon heating. Specifically, urushiol is cured by itself (eg, 150 ° C.) by applying heat, but if it is not a flat body that maintains an equilibrium, the viscosity decreases during heat treatment and flows down, making it difficult to apply industrially to reality. However, when the primary curing as in the present invention can be used for a variety of surfaces by using a heat treatment technique.

In the present invention, the polymerization of the recombinant lacquer polymerization is important when the polymerization is performed by lowering the partial pressure of oxygen. If the lacquer is thermally polymerized in an open container where the partial pressure of oxygen is relatively high, a rapid reaction and A viscosity synergistic effect can be obtained, but gelation rapidly occurs at a certain point before the desired viscosity is reached, resulting in a compound similar to jelly, and this gelled urushiol is impossible to use in coating production. The low oxygen to anoxic heat polymerization reaction environment as described above can be achieved by using a reduced pressure or by injecting a gas that does not participate in the reaction, such as nitrogen, and thus prevents gelation of urushiol when controlling and minimizing the amount of oxygen introduced. It is also possible to produce high viscosity polymers of 20,000 cP or more.

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

Preparation Example : Preparation of High Polymerization Urushiol Polymer Using Lacase

[Enzyme polymerization]

2 L of Chinese natural lacquer and 2 L of acetone were mixed well, followed by centrifugation at 1,500 rpm to carefully rinse the supernatant. The same volume of acetone was added to the supernatant again, and the above procedure was repeated three times, followed by separation under reduced pressure at 65 ° C. to purify urushiol.

The laccase enzyme solution was mixed with 1 ml of 30 ml of natural lacquer and 30 ml of acetonitrile and left to stand for 1 hour, followed by centrifugation at 4,000 rpm for 10 minutes using a centrifuge. After separating the blue aqueous layer formed on the lowermost layer, 60 ml of water was added to and diluted with 6 ml of the separated solution, which was then used as an enzyme solution. The enzyme solution was added to 300 ml of 2-propanol and 600 ml of urushiol purified with acetone, followed by enzymatic polymerization using a 2 L bubble column reactor. The reaction was carried out for 48 hours while maintaining the injection of 2 L per minute at 45 ℃ to obtain a product of 4,100 cP, and then reacted again for 30 hours by adding 200 ml of natural lacquer solution to give a product of 5,800 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.

[Enzyme polymerization after primary thermal polymerization]

In the above method, 300 ml of acetone-separated urushiol was stirred at a temperature of 200 ° C. for 5 hours to obtain a high polymer of 8,000 cP. During the reaction, the reactor was decompressed to minimize the oxygen inflow.

60 ml of natural lacquer and 200 ml of 2-propanol were added to 300 ml of the reacted lacquer polymer and mixed well, followed by reaction in a 2 L bubble column reactor for 14 hours. The resultant was left at a temperature of 50 ° C. for at least 24 hours to remove residual 2-propanol and water, and the viscosity measurement result was 8,600 cP.

Example 1

50 g of the polymerized lacquer polymer having a viscosity of 5,800 cP as described above was diluted and dissolved in 50 ml of diethyl benzene, followed by heating at 100 ° C. for 2 hours by adding 3 g of formaldehyde and 2 g of ammonia water. . At this time, the water produced by the condensation reaction was separated and evaporated again in an evaporation vessel for 20 minutes to obtain a liquid with fluidity. To this, 2 ml of 4% Ca-Octoate and 0.1 g of titanium oxide (TiO ₂ ) were added, diluted in 50 ml of toluene, and applied to wooden boards, glass plates and aluminum plates using a commercial paint sprayer. Then left for 2 hours. Thereafter, the mixture was slowly heat cured at 120 ° C. for 3 hours to form a black coating film. The coating film showed a pencil strength of 5 H regardless of the material of the surface to be painted and had a high luminous intensity.

Example 2

3 g of Nb (aminoethyl) aminopropyl trimethoxy silane (dry weight) was added to 50 g of the second enzymatically polymerized lacquer polymer after the first thermal polymerization having a viscosity of 8,600 cP as described above, followed by stirring for 1 hour. Reacted. The reaction was carried out in a hood as a slight rise in temperature produced ammonia-specific gas. After the reaction, 40 ml of xylene and 5 ml of isopropanol were dissolved, sealed, and left to stand for 3 days. It was applied to wooden boards, glass plates and aluminum plates using a commercial paint sprayer. After 1 hour of application, heat curing was performed at 120 ° C. for 3 hours to obtain a transparent brown coating film having a pencil strength of 5 H.

Example 3

To 50 g of the second enzymatically polymerized lacquer polymer after the first thermal polymerization having a viscosity of 8,600 cP described above, 3 g of Lupranat M11R (manufactured by BASF) and 50 ml of butyl acetate were added and stirred well. To this, 20 mg of 1,4-butanediol, 20 mg of ethylene glycol, 20 mg of dibutyltin diacetate, and 100 mg of Toray's modified silicone surfactant were added. It was. The coating was applied to the surface of wood, glass and aluminum using a 50 μm applicator, and left for 1 hour and then thermally cured at 120 ° C. for 3 hours to form a coating film having a pencil strength of 5 H.

Example 4

The same procedure as in the case of enzyme polymerization was carried out in the preparation example, but the enzyme polymerization was carried out for 40 hours, and the addition of natural lacquer was not performed in the middle of the enzyme polymerization. The viscosity of the obtained lacquer polymer showed 3,400 cP.

Using the 3,400 cP lacquer polymer, the same method as in Example 1, but the amount of formaldehyde used was 4.5 g, was applied to the surface to be left for 2 hours, and then thermally cured at 120 ℃ for 6 hours, A black coating film with a pencil strength of 5 H was obtained.

Example 5

In the preparation examples, the first thermal polymerization was carried out in the same manner as in the second enzymatic polymerization, but the thermal polymerization time was 8 hours (16,500 cP), and the amount of natural lacquer used in the enzyme reaction was 90 ml, 2-propanol. The amount was 225 ml. The viscosity of the lacquer polymer obtained as a result of the second enzymatic polymerization after the first thermal polymerization showed 18,500 cP.

The 18,500 cP lacquer polymer was used in the same manner as in Example 2, except that the amount of Nb (aminoethyl) aminopropyl trimethoxy silane used was 0.15 g, after 2 hours of application to the surface, and then 120 Thermal curing at 占 폚 for 5 hours yielded a black coating film with a pencil strength of 5 H.

Example 6

After the first thermal polymerization in the preparation example was carried out in the same manner as in the second enzymatic polymerization, the thermal polymerization time was 2 hours (3,300 cP), the amount of natural lacquer used in the enzyme reaction was 40 ㎖, 2-propanol The amount was 185 ml and the enzyme polymerization time was 12 hours. The viscosity of the lacquer polymer obtained as a result of the second enzymatic polymerization after the first thermal polymerization showed 4,300 cP.

Using the lacquer polymer of 4,300 cP, it was carried out in the same manner as in Example 3, the amount of Lupranat M11R used was 3.2 g, was applied to the surface to be left for 2 hours, and then thermally cured at 120 ℃ for 6 hours As a result, a black coating film having a pencil strength of 5 H was obtained.

Example 7

Enzyme polymerization was carried out in the same manner as in the above preparation, but the enzyme solution used for the enzyme polymerization was used as the stock solution, which was centrifuged without dilution. After performing the first enzyme polymerization for 72 hours, 300 ml of natural lacquer solution was added. Then, the second enzymatic polymerization was carried out for 60 hours. At this time, the air injection rate was 2.5 L / min, and the viscosity of the lacquer polymer obtained as a result of the enzyme polymerization was 16,000 cP.

The 16,000 cP lacquer polymer was carried out in the same manner as in Example 1, but the amount of formaldehyde used was 0.5 g, which was applied to the surface of the coating and left for 2 hours, and then thermally cured at 120 ° C. for 3 hours. A black coating film having a pencil strength of 5 H was obtained.

Example 8

After diluting and dissolving 50 g of a 5,800 cP lacquer polymer obtained in the same manner as in the case of enzyme polymerization in the preparation example in 50 ml of diethylbenzene, 2 g of hexamethylene diisocyanate and 1 g of 1,4-butanediol were added. Heated at 80 ° C. for 3 hours. After standing at room temperature for 24 hours, 2 ml of 4% calcium octoate and 0.1 g of titanium oxide were added, diluted in 50 ml of toluene, and applied to wooden boards, glass plates and aluminum plates using a commercial paint sprayer. It was left for 1 hour. After slowly thermal curing at 120 ° C. for 5 hours, a black coating film having a pencil strength of 5 H was obtained.

Example 9

After diluting and dissolving 50 g of a 5,800 cP lacquer polymer obtained in the same manner as in the case of enzyme polymerization in the preparation example in 50 ml of diethylbenzene, 3 g of zinc powder was added and stirred and heated at 115 ° C. for 3 hours. . After standing at room temperature for 24 hours, 2 ml of 4% calcium octoate and 0.1 g of titanium oxide were added, diluted in 50 ml of toluene, and applied to wooden boards, glass plates and aluminum plates using a commercial paint sprayer. It was left for 2 hours. After slowly thermal curing at 120 ° C. for 5 hours, a black coating film having a pencil strength of 5 H was obtained.

Comparative Example 1

Enzyme polymerization was carried out in the same manner as in the above preparation, but the enzymatic polymerization was carried out for 24 hours, and the addition of natural lacquer was not performed in the middle of the enzymatic polymerization. The viscosity of the obtained lacquer polymer showed 1,500 cP.

The 1,500 cP lacquer polymer was carried out in the same manner as in Example 1, but the amount of formaldehyde used was 6 g, the amount of ammonia water was 4 g, and after application to the surface to be coated, in a drying chamber having a humidity of 65% and a temperature of 37 ° C. 48 After curing for an hour, heat curing at 120 ° C. for 6 hours yielded a black coating film having a pencil strength of 5 H.

Comparative Example 2

Enzyme polymerization was carried out in the same manner as in the above preparation, but the enzyme solution used during enzyme polymerization was used as the stock solution, which was centrifuged without dilution. After performing the first enzyme polymerization for 84 hours, 300 ml of natural lacquer solution and lacquer 0.5 g of an aze (Fluka) was added, followed by a second enzymatic polymerization for 72 hours. At this time, the air injection rate was 2.5 L / min, the viscosity of the lacquer polymer obtained as a result of the enzyme polymerization was 22,000 cP.

After diluting and dissolving 50 g of the enzyme polymerized urushiol polymer having a viscosity of 22,000 cP in 250 ml of diethylbenzene, 6 g of formaldehyde and 4 g of ammonia water were added, followed by heating at 100 ° C. for 3 hours. At this time, the water produced by the condensation reaction was separated and evaporated again in an evaporation vessel for 15 minutes to obtain a liquid having fluidity. 4 ml of 4% calcium octoate and 0.2 g of titanium oxide were added thereto, diluted with 200 ml of toluene, and then applied to a wooden board, a glass plate, and an aluminum plate using a commercial paint sprayer, and left for 1 hour. Thereafter, the product was slowly thermoset at 120 ° C. for 3 hours, whereby a black coating film having a pencil strength of 5 H was obtained. However, it was difficult to obtain a uniform coating film thickness.

Comparative Example 3

50 g of a 5,800 cP lacquer polymer obtained in the same manner as in the case of the above-described preparation was carried out in the same manner as in Example 1 except that the amount of formaldehyde used was 50 mg and the amount of ammonia water was 33 mg. After coating on the surface to be cured for 36 hours in a drying chamber at a humidity of 65% and a temperature of 37 ℃, and heat-cured at 120 ℃ for 6 hours to obtain a black coating film having a pencil strength of 5 H.

Comparative Example 4

After diluting and dissolving 50 g of a 5,800 cP lacquer polymer obtained in the same manner as in the case of enzyme polymerization in 50 ml of diethylbenzene, 3.3 ml of styrene monomer and benzoyl peroxide 33 Mg was added and it stirred and heated at 90 degreeC for 2 hours. After standing at room temperature for 24 hours, 2 ml of 4% calcium octoate and 0.1 g of titanium oxide were added, diluted in 50 ml of toluene, and then applied to wooden boards, glass plates, and aluminum plates using a commercial paint sprayer, followed by humidity. It was cured for 36 hours in a drying chamber at 65% and a temperature of 37 ℃. Thereafter, thermal curing was carried out slowly at 120 ° C. for 6 hours to give a black coating film having a pencil strength of 5 H.

The results of the Examples and Comparative Examples are summarized in Table 1 below.

As described above, the present invention provides a highly polymerized lacquer composition of 3,000 to 20,000 cP obtained by enzymatic reaction or enzymatic reaction of a protein or polysaccharide, which is a substance contained in urushiol and lacquer sap, and a content of 7% or less. It is shown that by adding 1% or less of a commercially available paint hardener and desiccant, it is possible to produce a paint which is easy to thermoset after primary drying. The purity of lacquer paint as a lacquer and natural paint, ie the low amount of additives in the paint composition, is not only the value of the lacquer itself, but also one of the most important factors for consumers, and also the closest coating to the basic properties of lacquer by minimizing the amount of additives. It can be produced, and various industrial effects can be expected.

Claims (36)

(A) 99.7 to 90 weight percent of a highly polymerized recombinant lacquer composition having a viscosity of 3,000 to 20,000 cP; And (B) 0.3 to 10% 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 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 Coating composition, characterized in that selected from the group consisting of powders, oxides or salts of zinc, lead, iron, manganese or cobalt or combinations thereof. The method of claim 1, Coating composition, characterized in that the viscosity of the component (A) is 4,000 to 18,000 cP. The method of claim 2, The viscosity of the said component (A) is 5,000-15,000 cP, The coating composition characterized by the above-mentioned. delete The method of claim 1, wherein the monomer of the synthetic resin A coating composition, 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 The method of claim 1, A coating composition comprising 99.5 to 93% by weight of the highly polymerized recombinant lacquer composition of component (A) and 0.5 to 7% by weight of a curing agent of component (B). (A) 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 into a layer containing a water soluble enzyme and a water soluble gum; (B ₁ ) The urushiol of the layer containing the urushiol of step (A) using the lower solution layer containing the water-soluble enzyme of step (A) or the pure enzyme isolated therefrom as an enzyme source has a viscosity of 3,000 to 20,000. enzymatic polymerization up to cP; And (C ₁ ) 0.3 to 10% by weight of a curing agent selected from the group consisting of monomers, metal curing agents, and combinations thereof of synthetic resins is added to 99.7 to 90% by weight of the highly polymerized recombinant lacquer composition produced through step (B ₁ ). · Stirring Step As a method for producing a coating composition of any one of claims 1 to 3, 5 or 7, The polar organic solvent or nonpolar organic solvent of step (A) 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 A process for producing a coating composition, characterized in that it is selected from the group consisting of powders, oxides or salts of zinc, lead, iron, manganese or cobalt or combinations thereof. 9. A process according to claim 8, wherein step (B ₁ ) is (B ₂ ) enzymatic polymerization of the urushiol of the layer containing the urushiol of step (A) using the lower solution layer containing the water-soluble enzyme of step (A) or the pure enzyme isolated therefrom as an enzyme source Thermally polymerize to raise the viscosity to 3,000 to 20,000 cP The manufacturing method of the coating composition characterized by the above-mentioned. The method of claim 9, The thermal polymerization of the step (B ₂ ) is a method for producing a coating composition, characterized in that carried out in a low oxygen to an anoxic state. The method of claim 8, Method for producing a coating composition, characterized in that the polymerization of step (B ₁ ) or step (B ₂ ) is carried out until the viscosity is 4,000 to 18,000 cP. The method of claim 11, Method of producing a coating composition, characterized in that the polymerization of step (B ₁ ) or step (B ₂ ) is carried out until the viscosity is 5,000 to 15,000 cP. The method of claim 8, wherein step (C ₁ ) (C ₂ ) 0.5 to 99.5 to 93% by weight of the highly polymerized recombinant lacquer composition produced through step (B ₁ ) or step (B ₂ ), a curing agent selected from the group consisting of monomers of synthetic resins, metal curing agents and combinations thereof. Adding and stirring to 7% by weight The manufacturing method of the coating composition characterized by the above-mentioned. delete The method of claim 8, Method for producing a coating composition, characterized in that using a phenol oxidase as the enzyme source of step (B ₁ ) or step (B ₂ ). The method of claim 15 wherein the phenol oxidase A method of preparing a coating composition, characterized in that selected from the group consisting of laccase, peroxidase, catalase, and combinations thereof. The method according to claim 8, wherein in the enzymatic polymerization of step (B ₁ ) or step (B ₂ ) Adding the layer (b) or natural lacquer containing the water-insoluble glycoprotein and the water-soluble gum in the step (A) Method of producing a coating composition further comprising. The method according to claim 8, wherein in the enzymatic polymerization of step (B ₁ ) or step (B ₂ ) Adding an organic solvent selected from the group consisting of dioxane, 2-propanol, tetrahydrofuran and combinations thereof Method of producing a coating composition further comprising. The method of claim 8, Method for producing a coating composition, characterized in that for performing the enzymatic polymerization of the step (B ₁ ) or step (B ₂ ) in an air injection reactor. (A) 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 into a layer containing a water soluble enzyme and a water soluble gum; (B ₃ ) thermally polymerizing the urushiol of the layer containing urushiol of step (A) to a viscosity of 3,000 to 20,000 cP; And (C ₃ ) To the high polymerized recombinant lacquer composition 99.7 to 90% by weight obtained through the step (B ₃ ) is added 0.3 to 10% by weight of a curing agent selected from the group consisting of monomers, metal curing agents and combinations thereof. · Stirring Step As a method for producing a coating composition of any one of claims 1 to 3, 5 or 7, The polar organic solvent or nonpolar organic solvent of step (A) 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 A process for producing a coating composition, characterized in that it is selected from the group consisting of powders, oxides or salts of zinc, lead, iron, manganese or cobalt or combinations thereof. The method of claim 20, The thermal polymerization of step (B ₃ ) is a method for producing a coating composition, characterized in that carried out in a low oxygen to anoxic state. The process of claim 20, wherein step (B ₃ ) is (B ₄ ) thermally polymerizing the urushiol of the layer containing urushiol of step (A), and then adding the layer (b) or natural lacquer containing the water-insoluble glycoprotein and water-soluble gum in step (A) and enzymatic polymerization Conducting the reaction to raise the viscosity to 3,000 to 20,000 cP The manufacturing method of the coating composition characterized by the above-mentioned. The method of claim 22, wherein the enzyme polymerization of step (B ₄ ) The method for producing a coating composition, further comprising the step of adding the lower solution layer containing the water-soluble enzyme of step (A) or the pure enzyme isolated therefrom as an enzyme source. The method of claim 22, The thermal polymerization of step (B ₄ ) is a method for producing a coating composition, characterized in that carried out in a low oxygen to anoxic state. The method of claim 23, The thermal polymerization of step (B ₄ ) is a method for producing a coating composition, characterized in that carried out in a low oxygen to anoxic state. The method of claim 20, Method of producing a coating composition, characterized in that the polymerization of step (B ₃ ) or step (B ₄ ) is carried out until the viscosity is 4,000 to 18,000 cP. The method of claim 26, Method of producing a coating composition, characterized in that the polymerization of step (B ₃ ) or step (B ₄ ) is carried out until the viscosity is 5,000 to 15,000 cP. The process of claim 20, wherein step (C ₃ ) is (C ₄ ) A curing agent selected from the group consisting of monomers, metal curing agents and combinations thereof of 99.5 to 93% by weight of the highly polymerized recombinant lacquer composition produced through step (B ₃ ) or step (B ₄ ). Adding and stirring to 7% by weight The manufacturing method of the coating composition characterized by the above-mentioned. delete The method of claim 23, Method for producing a coating composition, characterized in that the phenol oxidase is used as the enzyme source of step (B ₄ ). 31. The method of claim 30, wherein the phenol oxidase A method for producing a coating composition, characterized in that selected from the group consisting of laccase, peroxidase, catalase and combinations thereof. The method of claim 22, wherein the enzyme polymerization of step (B ₄ ) Adding an organic solvent selected from the group consisting of dioxane, 2-propanol, tetrahydrofuran and combinations thereof Method of producing a coating composition further comprising. The method of claim 22, Method for producing a coating composition, characterized in that to carry out the enzymatic polymerization of step (B ₄ ) in an air injection reactor. delete delete delete