KR20100013516A

KR20100013516A - Process for producing urushiol extracts being removed lacquer poison

Info

Publication number: KR20100013516A
Application number: KR1020080075071A
Authority: KR
Inventors: 김형철
Original assignee: 한국내쇼날주식회사
Priority date: 2008-07-31
Filing date: 2008-07-31
Publication date: 2010-02-10

Abstract

PURPOSE: A process for producing urushiol extracts is provided to reduce lacquer poison of urushiol and to maintain effects of lacquer as a natural paint by reacting the urushiol with various effects with anhydrous organic acids. CONSTITUTION: A process for producing urushiol extracts from which lacquer poison is removed comprises the steps of: mixing raw lacquer with organic solvent excluding hydroxyl groups and centrifuging the mixture to separate an urushiol layer in which the organic solvent is dissolved; heating the urushiol layer and removing organic solvent and moisture to obtain urushiol extracts; mixing the urushiol extracts with anhydrous organic acids to prepare a reactant of urushiol extracts and anhydrous organic acids; and evaporating the mixed solution.

Description

Production method of urushiol extract with lacquer poison removed {PROCESS FOR PRODUCING URUSHIOL EXTRACTS BEING REMOVED LACQUER POISON}

The present invention relates to a method for preparing urushiol extract from which lacquer is removed, and more particularly, to a method of preparing urushiol extract from which lacus poison is removed by mixing urushiol extract extracted from raw lacquer with anhydrous organic acid and removing lactose obtained by the method. Urushiol extract is mixed with various paints such as UV paint, urethane paint, epoxy paint, one-component paint, ink, etc., and the coating material is coated with various methods such as roll coating, curtain coating, film coating, spray coating, silkscreen printing, offset printing, and dyeing. The present invention relates to a method for producing a product which is safe against lacquer poison and has antimicrobial activity, far infrared radiation and insect repellent effect.

Sumac ( Rhus verniciflua or Rhus vernicifera ) is a deciduous tree belonging to the Anacardiaceae family and is native to the highlands of the Central Asia and the Himalayas. It is cultivated mainly for the sake solution in Southeast Asia.

Raw lacquer or lacquer extract from lacquer trees has been known to be effective in eliminating bleeding, promoting blood circulation, and making insects, abdominal pain, excess stomach acid, cough, pulmonary tuberculosis, tuberculosis, constipation, diabetes mellitus, malaria, etc. The anti-cancer effect has also been reported. Especially in Korea, lacquer is used for lacquer chicken, lacquer duck, etc. for body care or medicine. In addition, lacquer liquid has a durable property and has been used in a large amount as a natural paint for manufacturing daily necessities such as cabinets, bowls, cutlery, and tableware by applying it to wood or paper, and has flame resistance, heat resistance, antiseptic property, insect repellent and insulation properties It is a well-known fact that it has the advantage of being excellent, and in particular, the preservation is excellent.

Lacquer liquid consists of urushiol, water, rubber, Lacase, and nitrogenous material, of which urushiol is the main component of about 70% of lacquer liquid, and is a 3-substituted cateche having a C ₁₅ -alkyl or alkenyl group. It is a complex of calls, the main component of which is 3- (8'Z, 11'E, 13'Z-pentadectrienyl) catechol (3- (8'Z, 11'E, 13 ') having 3 double bonds. Z-pentadecatrienyl) catechol). To date, 13 components of 3-substituted alkylcatechols having 0, 1, 2 or 3 double bonds in the C ₁₅ side chain have been identified (Yumin Du and Ryuichi Oshima, J. of Chromatography, 284, 463-473 (1984) Urushiol is a mixture of these monomers and polymers in which the monomers are naturally polymerized by LaCase (Yamauchi, Y., T. Murakami and J. Kumanotani, J. of Chromatography, 214, 343-348 (1981); Yamauchi, Y., R. Oshima and J. Kumanotani, J. of Chromatography, 243, 71-84 (1982); and Y. Du, R. Oshima and H. Iwatsuki, J. of Chromatography, 295, 179-186 (1984)).

As described above, various attempts have been made to utilize lacquer which has excellent pharmacological action and can be used for medicinal purposes, and is also useful as a natural paint for preparing household goods and the like. However, lacquer has been a reason for limiting attempts to utilize lacquer because it contains ingredients that cause allergies such as skin diseases when it comes into contact with or ingested due to its unique properties.

Attempts to remove the lacquer poison contained in such lacquer include Korean Patent Application No. 10-2000-0035434 (method of treating lacquer shell and removing toxicity of lacquer), and Korean Patent Application No. 10-2000-0055559 ( Extraction method of lacquer extract from which the toxicity has been removed) and Korean Patent Application No. 10-2006-0041742 (Lacquer of the lacquer and a lacquer tea bag prepared using the same).

Accordingly, in the present invention, while reducing the lacquer poison due to the lacquer by reacting the urushiol having an excellent effect of the above with anhydrous organic acid, while maintaining the efficacy of the lacquer as a natural paint.

It is an object of the present invention to provide a method for preparing urushiol extract from which lacquer is removed.

Another object of the present invention is to provide a coating composition containing the urushiol extract from which lacquer is removed.

The object of the present invention is to apply a paint containing the urushiol extract from the lacquer poison according to the present invention to the subjects, such as wood, plastic, metal and paper, while reducing the lacquer rise far-infrared radiation effect, electromagnetic wave blocking effect, antibacterial To provide an eco-friendly and health-saving lacquer coated product exhibiting the effect and insect repellent effect.

Hereinafter, the present invention will be described in detail.

The present invention

Separating the urushiol layer dissolved in the organic solvent by mixing and centrifuging an organic solvent containing no raw lacquer and a hydroxy group;

Heating the urushiol layer to remove an organic solvent and water to obtain an urushiol extract;

Mixing the obtained urushiol extract with anhydrous organic acid to prepare a reaction product of the urushiol extract with anhydrous organic acid; And

It is a method for producing the urushiol extract from which the lacquer poison is removed, comprising the step of evaporating the mixed solution.

In the method for preparing the urushiol extract from which the lactose is removed according to the present invention, the separating of the urushiol layer may include mixing an organic solvent, preferably acetone, containing no raw lacquer and a hydroxy group in a weight ratio of 1: 0.5 to 1.5. , The mixture of fresh lacquer and the organic solvent is injected at a rate of 8 l / min or less, rotated at 10,000 rpm or more and centrifuged. The urushiol layer dissolved in the organic solvent not containing a hydroxy group obtained by centrifugation is heated at a temperature of 40 to 100 ° C. to remove the organic solvent and water to extract urushiol.

In the present invention, the anhydrous organic acid is mixed and reacted with the urushiol extract obtained by the above-described method. When the urushiol extract and the anhydrous organic acid are mixed and reacted, the anhydrous organic acid is substituted with hydrogen of the hydroxyl group of the urushiol. At this time, the urushiol extract and the anhydrous organic acid reacts at room temperature to produce the urushiol extract from which the lacquer is removed, but may be heated to increase the reaction rate.

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

The raw lacquer used in the present invention may be either Korean, Chinese or Japanese, and the lacquer is centrifuged by mixing the lacquer with an organic solvent containing no hydroxyl group.

In the present invention, the reason for mixing the raw lacquer and the organic solvent containing no hydroxy group is that the raw lacquer itself is too high in viscosity, so it is not centrifuged, so that the viscosity is lowered and the urushiol is dissolved in the organic solvent, such as rubber and nitrogen compounds such as urushiol. To facilitate separation. At this time, as the organic solvent to be mixed with fresh lacquer, both polar and non-polar organic solvents such as ethanol or xylene can be used, but there is no risk of generating an additional reactant because it does not have a hydroxyl group that reacts with anhydrous organic acid in the mixing process with anhydrous organic acid. It is preferable to use an organic solvent containing no hydroxy group. In the present invention, acetone is less environmentally harmful than other organic solvents and has a lower boiling point, which is environmentally and economically advantageous, and does not have a hydroxy group that reacts with anhydrous organic acid in a mixing process with anhydrous organic acid, thereby causing an additional reactant. It is suitable as a small solvent.

When mixing organic solvents containing no raw lacquer and hydroxy group, preferably acetone, if the mixing ratio is less than 1: 0.5, the acetone does not sufficiently dissolve urushiol and the centrifugation is not completed completely. When the ratio exceeds 1: 1.5, the centrifugation is fine, but there is a problem in that the time and cost required for evaporation are increased when evaporating acetone and water by distillation under reduced pressure. After mixing the raw lacquer and acetone in a weight ratio of 1: 0.5 to 1.5, dissolving it, and centrifuging at 10,000 rpm or more, the solid foreign substances in which the rubbery and nitrogen compounds are deposited sink in the lower layer, and the urushiol dissolved in the acetone in the upper layer is dissolved. Can be separated.

The urushiol and acetone separated by centrifugation were heated under reduced pressure or vacuum at 40 to 100 ° C. to evaporate acetone and water to extract only urushiol.

The anhydrous organic acid is mixed and stirred with the thus obtained urushiol extract to induce a reaction of replacing hydrogen with anhydrous organic acid in a hydroxy substituent of urushiol. At this time, the mixing ratio of the urushiol extract and the anhydrous organic acid should be considered equivalent, and considering the amount of hydrogen substitution in the urushiol hydroxy group, the weight ratio of urushiol: anhydrous organic acid is mixed in a ratio of 1: 0.3 to 3. When the mixing ratio is exceeded, energy and time are required to evaporate an adduct such as anhydrous organic acid or organic acid, and when anhydrous organic acid is used below the mixing ratio, unreacted urushiol remains.

Instead of the urushiol extract, the urushiol extract obtained by extracting the raw lacquer and the raw lacquer by dissolving it in an organic solvent and centrifuging the urushiol layer, and / or the centrifuged urushiol layer may be used. Natural raw lacquer can also be used, but it is preferable to use centrifuged urushiol or urushiol extract because the function of lacquer may be impaired by impurities such as rubbery and nitrogen compounds.

In addition, organic anhydrides that can be used in the present invention include acetic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, benzoic anhydride, and the like, preferably acetic anhydride having a low molecular weight and high reactivity, and having a double bond and decomposing the product. It is also preferable to use maleic anhydride and succinic anhydride without. It is also possible to use at least one mixture selected from the group consisting of anhydrous organic acids described above.

As described above, the urushiol extract prepared by reacting with anhydrous organic acid according to the present invention is significantly removed from the lacquer toxic and is much easier to handle than raw lacquer, thereby allowing universal use. In addition, the urushiol extract from the lacquer poison according to the present invention has the effect of far-infrared radiation effect, electromagnetic wave blocking effect, antibacterial action and insect repellent effect of raw lacquer is maintained as it is so that lacquer can be applied more easily to various products of excellent lacquer Efficient products can be mass produced.

Hereinafter, the configuration of the present invention will be described in detail by way of examples. However, the scope of the present invention is not limited by the following examples.

Example 1 Mixed Reaction of Urushiol with Acetic Anhydride

25 kg of acetone was mixed with 25 kg of fresh lacquer, followed by stirring well with a rod. The mixture was poured into a continuous centrifuge at 4 l / min, and then rotated at 15,000 rpm to obtain 46 kg of urushiol solution. The obtained urushiol solution was heated at 60 ° C. under reduced pressure to evaporate acetone and water to prepare 13 kg of urushiol.

1 kg of the prepared urushiol was taken and 660 g of acetic anhydride was mixed and reacted in a constant temperature bath at 120 ° C. for 24 hours. At this time, the thermostat used a sealed container to prevent acetic anhydride from evaporating and diffusing into the air. After the reaction was completed 1.6kg of a mixture was obtained, and the acetic anhydride and acetic acid which was evaporated by heating under reduced pressure at 80 ℃ 12 hours was recovered by cooling. After completion of the reduced pressure heating, 1.22 kg of modified urushiol were obtained.

0.2 g of the obtained modified urushiol was collected and component analysis was carried out by absorbance using saturated urushiol as a standard product. As a result, the urushiol content was 0.5%.

As a result of performing the lacquer rise test with urushiol before reaction with the product, the lacquer rise was significantly reduced.

Example 2 Mixed Reaction of Urushiol and Maleic Anhydride

1 kg of urushiol and 300 g of maleic anhydride were mixed and reacted in a thermostat at 140 ° C. for 24 hours. At this time, the thermostat used a sealed container to prevent maleic anhydride from evaporating and diffusing into the air. After the reaction was completed, 1.3 kg of a mixture was obtained, and the maleic anhydride, which was evaporated by cooling under reduced pressure at 150 ° C., was cooled and recovered. After completion of the reduced pressure heating, 1.22 kg of modified urushiol were obtained.

0.2 g of the obtained modified urushiol was collected and component analysis was carried out by absorbance using saturated urushiol as a standard product. As a result, the urushiol content was 2.5%.

Example 3 Urushiol and Mixed reaction of phthalic anhydride

1 kg of the prepared urushiol and 460 g of phthalic anhydride were mixed and reacted in a thermostat at 140 ° C. for 24 hours. At this time, the thermostat used a sealed container to prevent phthalic anhydride from evaporating and diffusing into the air. 1.4 kg of the mixture was obtained after the completion of the reaction, and the resultant was heated under reduced pressure at 180 ° C. for 2 hours to recover the phthalic anhydride by evaporation. After completion of the reduced pressure heating, 1.36 kg of modified urushiol was obtained.

0.2 g of the obtained modified urushiol was collected and component analysis was carried out by absorbance using saturated urushiol as a standard product, and the urushiol content was 2.2%.

Example 4 Urushiol and Mixed reaction of succinic anhydride

1 kg of urushiol and 320 g of succinic anhydride were mixed and reacted in a thermostat at 120 ° C. for 24 hours. At this time, the thermostat used an airtight container to prevent evaporation of succinic anhydride and diffusion into the air. After the reaction was completed, 1.25 kg of a mixture was obtained, and the mixture was heated under reduced pressure at 180 ° C. for 2 hours to recover by cooling succinic anhydride. After completion of the reduced pressure heating, 1.20 kg of modified urushiol was obtained.

0.2 g of the obtained modified urushiol was collected, and component analysis was carried out by absorbance using saturated urushiol as a standard product. As a result, the urushiol content was 3.3%.

Preparation Example 1 UV paint coating of aluminum sheet using lacquer removal paint

30 g of the lacquer-free lacquer liquid prepared by the method of Example 1 was mixed with 1 kg of UV paint and spray-coated on an aluminum sheet, and cured with ultraviolet rays to prepare a lacquer-free lacquer-coated aluminum sheet. Antimicrobial tests were performed on the prepared specimens, and the results are shown in Table 1 below.

Preparation Example 2 Melamine (HPM, HIGH PRESSURE MELAMIN) resin coating of paper with lacquer removal paint

100 g of the lacquer sap from which the method of Example 1 was removed was mixed with 100 g of castor oil-based surfactant, and then stirred and mixed with 2 kg of melamine resin. After impregnating the solution into the shape paper and dried for 4 minutes at 160 ℃ and pressed with a core material 180 ℃ 20 minutes. Antimicrobial tests were performed on the prepared specimens, and the results are shown in Table 2 below.

Preparation Example 3 Wood Grain Urethane Paint Coating Using Lacquer Removal Paint

30 g of the lacquer-free lacquer liquid prepared by the method of Example 1 was mixed with 600 g of a urethane paint containing an isocyanate, sprayed onto a wood grain material, and dried at 80 ° C. for 60 minutes. Antimicrobial tests were performed on the prepared specimens, and the results are shown in Table 3 below.

Preparation Example 4 Coating a one-component paint on a steel plate using a lacquer removal paint

2.5 kg of the lacquer liquid from which the lacquer poison prepared by the method of Example 1 was removed was mixed with 75 kg of an acrylic one-part coating material, coated with a roll coating on a steel sheet, and dried at 200 ° C. for 30 seconds. Antimicrobial tests were performed on the prepared specimens, and the results are shown in Table 4 below.

Test Example 1 Lacquer Test

1 ml each of modified urushiol (HLL-301) according to Example 1 and purified urushiol (HLL-201), which was not reacted with anhydrous organic acid, was taken and applied to the inner skin of the subject's arm. After standing for 1 hour, it was washed with ethanol and observed the change of skin according to the drop of the sample.

Skin changes were visually observed over time and photographed and recorded. 1 to 3 are photographs showing the skin reactions of the subjects after 6 hours, 24 hours, and 72 hours after instilling the modified urushiol and the purified urushiol not reacted with the anhydrous organic acid according to Example 1, respectively.

As shown in Figures 1 to 3, the modified urushiol solution according to the present invention can be confirmed that the symptoms of the lacquer rarely appears.

Test Example 2 Antibacterial Effect Test

Each specimen prepared in Preparation Examples 1 to 4 was commissioned by the Korea Testing Institute for the antibacterial test.

In the antibacterial test, Escherichia coli ) ATCC 8739 and Staphylococcus aureus ) ATCC 6538 was used as a test strain, and a sterilized bag for Stomacher 400 was used as a coated film and a control specimen.

Antimicrobial Test Results for UV Coating of Aluminum Sheets Test Items sample Result Test Methods E. coli A 2.4 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 1.1 × 10 ⁷ CFU / Sample JIS Z2801: 2000 C <10 CFU / sample JIS Z2801: 2000 Antimicrobial activity 6.0 and above JIS Z2801: 2000 S.aureus A 2.9 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 8.2 × 10 ⁵ CFU / Sample JIS Z2801: 2000 C <10 CFU / sample JIS Z2801: 2000 Antimicrobial activity 4.9 or later JIS Z2801: 2000

Antimicrobial Test Results for Melamine Resin Coating Test Items sample Result Test Methods E. coli A 3.1 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 5.5 × 10 ⁵ CFU / Sample JIS Z2801: 2000 C <10 CFU / sample JIS Z2801: 2000 Antimicrobial activity 4.7 and above JIS Z2801: 2000 S.aureus A 3.0 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 4.8 × 10 ⁵ CFU / Sample JIS Z2801: 2000 C <10 CFU / sample JIS Z2801: 2000 Antimicrobial activity 4.7 and above JIS Z2801: 2000

Antimicrobial Test Result for Urethane Paint Coating of Wood Grain Test Items sample Result Test Methods E. coli A 1.5 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 1.7 × 10 ⁷ CFU / Sample JIS Z2801: 2000 C 1.4 × 10 ³ CFU / Sample JIS Z2801: 2000 Antimicrobial activity 4.08 JIS Z2801: 2000 S.aureus A 1.5 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 6.8 × 10 ⁵ CFU / Sample JIS Z2801: 2000 C <10 CFU / sample JIS Z2801: 2000 Antimicrobial activity 4.83 JIS Z2801: 2000

Antimicrobial Test Results for Single Component Coating of Steel Plate Test Items sample Result Test Methods E. coli A 2.4 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 3.4 × 10 ⁷ CFU / Sample JIS Z2801: 2000 C 4.5 × 10 ² CFU / Sample JIS Z2801: 2000 Antimicrobial activity 4.9 JIS Z2801: 2000 S.aureus A 3.0 × 10 ⁵ CFU / Sample JIS Z2801: 2000 B 6.4 × 10 ⁵ CFU / Sample JIS Z2801: 2000 C 1.3 × 10 ² CFU / Sample JIS Z2801: 2000 Antimicrobial activity 3.7 JIS Z2801: 2000

In each test, A is the initial number of bacteria (average) of the control specimen, B is the number of bacteria (average) of the control specimen after 24 hours of incubation, C is a test of each test specimen prepared in Preparation Examples 1 to 4 after 24 hours of incubation The number of bacteria (average) is shown, and the antimicrobial activity value (R) is log (B / A) minus log (C / A), which is (log (B / C)).

As shown in Tables 1 to 4, the coatings coated with a paint containing the urushiol extract prepared by the present invention can be confirmed that the excellent antimicrobial activity is maintained despite being modified by reacting with anhydrous organic acid. have.

The above embodiments are merely for the purpose of describing the contents of the invention in detail, and are not intended to limit the scope of the technical idea of the invention, the invention described above is a person having ordinary knowledge in the art to which the present invention belongs In the range without departing from the spirit of the present invention, various substitutions, modifications, and changes are possible to the scope of the present invention, of course, not limited to the above embodiments, including the equivalent scope as well as the claims to be described later It must be judged.

1 is a photograph showing the results of skin reaction 6 hours after the modified urushiol (pictured right) and the unmodified control urushiol (pictured left) in accordance with the present invention on the skin.

Figure 2 is a photograph showing the skin reaction results after 24 hours after the modified urushiol (pictured right) and the unmodified control urushiol (pictured left) in accordance with the present invention on the skin.

Figure 3 is a photograph showing the result of skin reaction after 72 hours of the modified urushiol (pictured right) and the unmodified control urushiol (pictured left) according to the present invention on the skin.

Claims

Method for producing a urushiol extract from which the lactose is removed, characterized in that comprising the step of evaporating the mixed solution.

The method of claim 1, wherein the raw lacquer and the organic solvent containing no hydroxy group are mixed at a weight ratio of 1: 0.5 to 1.5.

The method of claim 1, wherein the organic anhydride is at least one anhydrous organic acid selected from the group consisting of acetic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, and benzoic anhydride, the preparation of the urushiol-free urushiol extract Way.

The method of claim 1, wherein the urushiol extract and the anhydrous organic acid are mixed at a weight ratio of 1: 0.3 to 3. 5.

Urushiol extract is removed from the lactose prepared by the method of claim 4.