KR101176111B1 - The process for preparing high polymerized urushiol from natural lacquer and industrial lacquer-gold paintscoating materials - Google Patents

Abstract

PURPOSE: A manufacturing method of a high-polymerized urushiol polymer is provided to provide a high-polymerized urushiol polymer not scattering particles to air by using reformed urushiol, and having excellent compatibility with various vehicles. CONSTITUTION: A manufacturing method of a high-polymerized urushiol polymer comprises: a step of generating urushiol polymer by condensation polymerization of urushiol and formaldehyde under the presence of a basic catalyst; a step of removing a part of whole part of residual formaldehyde from the urushiol polymer; and a step of manufacturing high-polymerized urushiol through polymerization by heating the urushiol polymer under the presence of an inert gas. The urushiol is originated from natural lacquer.

Description

High-polymerization urushiol multimer using natural lacquer and sulfur lacquer coating and coating composition using same {The process for preparing high polymerized Urushiol from natural lacquer and industrial Lacquer-Gold paintscoating materials}

The present invention relates to a method for preparing a high polymerization urushiol multimer by separating urushiol, a main component of lacquer from a natural lacquer, and a method for preparing paints and coatings using a high polymerization urushiol multimer.

Lacquer is a natural paint that has antibacterial, mildew, weather resistance, heat resistance, abrasion resistance, pollution resistance, water resistance, chemical resistance, adhesion, and insect repellency. It has been regarded as a precious natural paint on air currents, dishes, furniture and woodwinds. However, the color is dark, and it is difficult to get close to the lacquer until it is completely hardened and hardened completely, and it is difficult to popularize due to the difficult drying conditions, difficult handling and supply, and a cheap lacquer coating similar to lacquer. I have used it.

The components of natural lacquer consist of urushiol, rubber, nitrogen-containing substance, laccase, moisture, clove component, etc., and curing of lacquer is achieved by combining urushiol monomer with adjacent monomers by laccase and oxygen. Is combined with the adjacent monomer or dimer to form a urushiol multimer and form a black coating film.

The traditional method of drying lacquer is to apply lacquer to the body, and then put it in a drying room equipped with a relative humidity of 70 to 80% and a temperature of 20 to 25 ° C. The urushiol multimer is further polymerized by laccase and oxygen to make macromolecules. It will form a hardened coating film, and after the lacquer is applied to the substrate (素 地), the drying time until the next work usually takes 2 to 8 days, which is a major factor to reduce the work efficiency. In addition, the lacquer containing foreign matter decays during storage, and the lacquer (Laccase) contained in the lacquer is decomposed and the coating does not dry.In case of contact with air during storage, the lacquer hardens or separates urushiol and the remaining components, which requires complicated pretreatment. Done.

In order to compensate for these problems, a method used in Japan has been used, such as a method of improving the dryness by using a method of adding a freshly dried raw chil and a method of adding phenol oxidase and hydrogen peroxide together. However, the method of improving the drying property by adding the raw paint having good dryness has different characteristics of the raw paint by each region, so the quality and tensile strength of the lacquer produced by this method decreases and the viscosity increases, resulting in phenol oxidase. The method of adding an enzyme such as is extracted and separated from the mushroom or plant, there is a costly disadvantage because the cost of the extraction and separation process is expensive.

In addition, the curing mechanism that is cured by enzymatic polymerization is widely known to be due to the polymerization of hydroxyl groups, and there are many general studies by curing such lacquer, but the curing speed is slow, and it should be cured in the dark with maintaining the proper temperature and humidity. There is a problem, so there are some problems to develop it as an industrial paint.

Recently, due to the development of the industrial society, environmental destruction and pollution problems, global warming phenomenon has been highlighted, the development of natural paints and eco-friendly paints are actively progressing.

In the meantime, the development technology of paint using natural lacquer is (a) separating urushiol from natural lacquer, mixing urushiol and various resins, (b) purifying lacquer, and then adding a specific ratio of laccase to enzyme. A method of preparing a recombinant paint by polymerization or thermal polymerization and then adding a laccase, (c) a method of preparing a urethane resin by reacting with urushiol and isocyanate, and then powdering it, and (d) condensing with formaldehyde to multimer It can be divided into a method of manufacturing.

However, by separating urushiol from natural lacquer and mixing urushiol with various resins (a), natural lacquer or monomer's urushiol is scattered in the air at room temperature and cannot be handled by people who burn lacquer. Occasional lacquer is generated by the lacquer, which causes severe phenomena that cannot be accessed even by those who burn the lacquer. Therefore, in order to use as a commercial painter should also be able to use lacquer, there is a problem that does not pollute the surroundings in the process of curing the coating film. In addition, the monomolecular urushiol not only has poor compatibility with various vehicles, but also has a problem of poor drying property of the coating film.

Purifying urushiol from natural lacquer, and then adding a specific ratio of laccase to enzymatic polymerization or heat polymerization, and then adding laccase to prepare laccase (laccase) or oxidase which natural lacquer has Since it proceeds by polyphenol oxidase, it has the limit of molecular weight in manufacturing urushiol multimer. In addition, specific conditions and time are required because it proceeds with the enzymatic reaction, and the disadvantages of hardening conditions become difficult, and when urushiol and laccase are mixed, when the air flows in during storage, the curing reaction proceeds and the hardening occurs. It entails a disadvantage. Therefore, it is too difficult to use it as an industrial paint.

Another method is to prepare a urethane resin by reacting purified urushiol and isocyanate and then powdering it. The reaction of urushiol and isocyanate is combined with the hydroxyl group (-OH) and isocyanate of urushiol, which is inherent in lacquer coating. The antimicrobial properties are gone. In order to maintain the antimicrobial catechol (catecol) hydroxyl group (-OH) must be present as it is. To overcome this, less isocyanate is used, but the characteristics of the coating film are deteriorated. In addition, a complex process for pulverizing the solid mixture is required, and when the powder is mixed with various plastics to form a film, a plastic layer is coated on the surface of the powder so that the properties of the lacquer powder are not exhibited or are greatly reduced.

As a method (d) of preparing a urushiol multimer by condensation reaction with formaldehyde, a method of preparing a phenol resin using a phenol derivative is a well known general reaction.

Industrially, phenol resins can be synthesized by condensation of excess formalin and phenol derivatives under a basic catalyst, and a method of preparing a noblock resin is well known as a method for synthesizing formalin using an amount less than phenol derivatives under an acid catalyst.

As a prior art of the method (d) of preparing a urushiol multimer by condensation reaction with formaldehyde, Korean Patent Laid-Open No. 2006-0098147 discloses an acrylic and acrylic acid under an acid catalyst to a urushiol multimer obtained by reacting urushiol with formaldehyde in the presence of a basic catalyst. A method of preparing sulfur lacquer by reacting is disclosed. Korean Unexamined Patent Publication No. 2007-0094109 discloses a urushiol multimer by a method similar to that of Korean Patent Publication No. 2006-0098147, and adds an epoxy resin and normal butanol. After dissolving at 140 ° C. for 2 h, phosphoric acid and xylene were added, and then heated for 1.5 h to prepare a coating solution.

Both of the above methods are urushiol multimers that do not reach the molecular weight set forth herein, and because they use formaldehyde, there is a disadvantage that a small amount of formaldehyde may remain in the lacquer polymerization, so it is difficult to classify it as an environmentally friendly lacquer multimer. Have

On the other hand, materials that easily react with formaldehyde include peroxides, ammonium compounds and organic amines, and by removing the residual formaldehyde contained in amino resins or phenolic resins used as adhesives or construction panels of wood, A method for preparing a liquid to remove formaldehyde, which is a cause of sick house syndrome, is described.

Inventive for removing residual formaldehyde contained in phenol resins and urea resins used as adhesives or building panels of wood. Korean Patent No. 10-0715468 discloses methylol phenol as a method of removing formaldehyde contained in phenol resins. A method of removing unreacted formaldehyde is disclosed, which comprises adding 5-10% by weight of methylol melamine precursor to a precursor and condensation polymerization to prepare a resol-type modified phenol-melamine resin. No. 10 discloses a method for removing residual formaldehyde by adding 10-40% ammonium acetate or ammonium bicarbonate aqueous solution maintained at 40 to 60 DEG C to formaldehyde resin to react with residual formaldehyde to generate hexamine. Korean Laid-Open Patent Publication No. 2005-0072996 includes urea resin and phenol resin adhesive used as an adhesive for wood. A and discloses a deodorant composition and a production method comprising the amine and the acid, a polyhydric aliphatic alcohol in order to remove the formaldehyde, Korea Patent Publication No. 1996-034354 discloses a barium hydroxide, a component with an aqueous formaldehyde solution (Ba (OH) ₂ ) A method of preparing an odorless urea resin adhesive is disclosed by reaction under a catalyst, followed by administration of concentrated hydrochloric acid, followed by administration of a mixed solution of caustic soda and sodium carbonate and a mixture of barium hydroxide and sodium carbonate.

As a method of removing formaldehyde, a causative agent of sick house syndrome, Korean Patent Publication No. 2007-0083090 discloses 5 to 50% of β- (1,4) -poly-D-glucosamine derivative (C ₆ H ₁₁ NO ₄ ) n. And a method for preparing a liquid composition for decomposition and removal of indoor pollutants including 1-20% of vegetable essential oil components and water, and Korean Patent No. 10-0480808 discloses a powdery, granular, three-dimensional pellet-like sodium puper. A method of removing low aldehyde for preventing sick house syndrome and chemical hypersensitivity is disclosed by storing a carbonate in a sealed or airtight container and then removing it in use. Korean Patent Laid-Open Publication No. 2002-0073534 discloses at least one selected from the group consisting of hydrazides, azoles and azines, weak acid metal salts, and ammonium compounds for deodorizing compositions for removing aldehyde species. However, ammonium compounds, organic amines, and peroxides that react with formaldehyde are those obtained by anyone who majored in the field. Using these compounds, the removal of residual formaldehyde in phenol resins or urea resins or the sick house syndrome As an example of a removal agent, there is no example of a method for producing a urushiol polymer by removing purified urushiol and formaldehyde in a reactor and removing residual formalin.

Republic of Korea Patent Publication No. 2007-0094109 Republic of Korea Patent No. 10-0715468 Republic of Korea Patent Publication No. 2002-0043678 Republic of Korea Patent Publication No. 2005-0072996 Republic of Korea Patent Publication No. 1996-034354 Republic of Korea Patent Publication No. 2007-0083090 Republic of Korea Patent No. 10-0480808 Republic of Korea Patent Publication No. 2002-0073534

Therefore, the present invention is to separate and purify the urushiol, the main component of lacquer from natural lacquer to solve this problem, and is not scattered in the air using purified urushiol and good compatibility with various vehicles (vehicle) as well as vehicle Even if it gets on the skin after mixing, the phenomenon of lacquer rise is weak, so it is possible to secure the stability of lacquer as much as possible. It aims to provide a way to.

It is also an object of the present invention to provide a method for producing a sulfur lacquer coating and a coating agent in which high polymerization urushiol multimers are prepared as paints and coatings or combined with various vehicles.

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

In order to achieve the above object, the present invention provides a method for producing a high polymerization urushiol multimer using urushiol derived from natural lacquer. It also provides various sulfur lacquer coating and coating composition using this.

In the present invention, the natural lacquer refers to raw lacquer obtained from lacquer trees, and urushiol, the main component of lacquer, has a difference in component content and molecular structure for each acid.

The molecular structure of urushiol, the main component of lacquer, is a catechol structure with an unsaturated aliphatic chain. Generally, lacquer of Korea, Japan, and China has 15 aliphatic chains of carbon, and the number of double bonds is 1 It has 3 to 3, Vietnamese lacquer has 17 carbon atoms, and double bonds have 0 to 2 aliphatic chains.

In addition to urushiol, the ingredients included in natural lacquer contain allergens, and some people who are lacquer because they are scattered in some air are dangerous even near the workplace. In particular, allergic symptoms due to lacquer are allergic after 2 days of contact, so the condition progresses for 2 weeks, so if anyone in the family burns lacquer, it is contagious when contacted. I have avoided the following. However, highly polymerized urushiol multimers are relatively safe and safe to contact after the lacquer is fully cured.

Hereinafter, a method for synthesizing a high polymerization urushiol multimer using urushiol will be described.

Synthesis of high polymerized urushiol multimers using purified urushiol

(Iii) condensation polymerization of urushiol with formaldehyde under a basic catalyst to produce urushiol multimers;

(Ii) removing some or all of the residual formaldehyde from the urushiol multimers from step (iii); And

(Iii) heating the urushiol multimer from step (ii) in the presence of an inert gas to polymerize to prepare a high polymerized urushiol multimer.

More specifically, the step (ⅰ) of the method for producing a high polymerization urushiol oligomer according to the present invention is heated to reflux reaction by heating in an oil bath with stirring while adding formaldehyde, a basic catalyst, an organic solvent to the urushiol and cooled to room temperature When the reaction product is separated is the step of separating the upper urushiol multimer obtained.

Urushiol used in the present invention may be derived from natural lacquer, it can be used by separating and purifying the urushiol derived from natural lacquer.

As a method of separating urushiol from natural lacquer, acetone or ethanol can be added to the lacquer, and then divided into soluble and insoluble components. Then, soluble urushiol and water are separated, and the solvent and water are evaporated under reduced pressure to obtain purified urushiol. have. At this time, the insoluble component is called acetone powder and when water is added to the powder, it is further divided into an insoluble component (nitrogen-containing substance) and a soluble component (rubber, laccase).

Purification method of urushiol used in the present invention is mixed with an organic solvent of 1 to 3 times the weight ratio of urushiol derived from natural lacquer and left to stand after mixing to separate the supernatant, or to separate the precipitate by centrifugation, filtration, etc. The silver organic solvent can be purified by evaporation under reduced pressure.

The organic solvent may be a solvent that can separate urushiol from natural lacquer, and can be conveniently selected by an operator such as hexane, acetone, and ethanol.

In the present invention, any one of the above methods may be used, but the centrifugal separation method requires a lot of equipment costs, and the filtration method has a disadvantage in that the precipitate has to be filtered through several stages of filtration process due to fine precipitates, and is suitable for mass treatment. The method of leaving the mixture to stand and taking the supernatant to evaporate the solvent may take time, but it may be preferable to process a small amount because it is natural and very easy to work.

Condensation polymerization of the urushiol with formaldehyde under a basic catalyst to form the urushiol multimer in the step (iii) is characterized in that formaldehyde is used as an aqueous formaldehyde solution of 35 to 38%. The formalin may be used in an amount of 10 to 99 equivalent% based on urushiol, and more specifically, in an amount of 30 to 90 equivalent% based on urushiol. If the amount of formaldehyde added is too small, the synthesis yield of urushiol multimers may be reduced. If formaldehyde is added in excess of the above range, an excess amount of unreacted formaldehyde may be present even after completion of the synthesis reaction of urushiol multimers. The post-treatment process to remove may be lengthy and inefficient.

In the present invention, the basic catalyst used in the polycondensation reaction to produce the urushiol multimer may be used one or more selected from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide, barium hydroxide and lithium hydroxide, the total weight of urushiol It is most preferred to use 1 to 10 parts by weight relative to. If the amount of addition of the basic catalyst is too small, the synthesis yield of the urushiol multimer may be lowered, and if the basic catalyst is added in excess in excess of the above range, it may be accompanied by a disadvantage that the purity of the synthesized urushiol multimer is lowered.

The organic solvent is preferably lower alcohols such as methanol, ethanol and propanol, and the amount of the organic solvent may be 50 to 150 parts by weight based on urushiol.

The reaction temperature of the polycondensation reaction is a temperature condition in which water and alcohol are actively reflux can be adjusted as needed by those skilled in the art, but in one embodiment of the present invention, a temperature of 80 to 120 ℃ is most preferred. At a temperature in the above range, the reaction time is preferably 3 to 8 hours, more specifically 5 to 7 hours. The reaction product layer and the solvent layer are well separated by cooling to room temperature after the condensation polymerization reaction at the temperature and reaction time under the above conditions. If the reaction time is too short, it will not be separated. If the reaction time is too long, it will be rubberized and cannot be used.

After the condensation polymerization reaction is completed, the reactor is left until it reaches room temperature, and when the layers are separated, the solvent layer in the lower layer is discharged, the residual solvent is evaporated in a reduced pressure rotary evaporator at 60 to 80 ° C, and a trace amount of formaldehyde contained in the urushiol oligomer In order to remove the addition of one or more selected from the group consisting of inorganic and organic ammonium salts, aliphatic and aromatic organic amines, hydrazides, azoles and azines.

Specific examples of the inorganic ammonium salts of the present invention include ammonium carbonate, ammonium chloride, ammonium phosphate, ammonium sulfate, triammonium citrate, ammonium sulfite, ammonium acetate, ammonium bicarbonate, and the like. Ammonium salts of fatty acids, saturated dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suveric acid and sebacic acid, and saturated tricarboxylic acids such as citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 1 Ammonium salts of aromatic carboxylic acids such as naphthoic acid, toluic acid, toroic acid, gepic acid, and heterocyclic carboxylic acids such as nicotinic acid and isoninicotinic acid.

Specifically, the organic amines of the present invention are aliphatic amines such as triethylamine, diethylenetriamine, hexaethylenetetraamine, ethylenediamine, laurylamine, toluenediamine, diphenylmethanediamine, hexamethylenediamine, 4,4 And aromatic amines such as diaminodiphenylmethane and m-phenylenediamine, and compounds having amino groups such as urea, hydrazide and glucosamine. Specific examples of hydrazides include monohydrazides (R-CO- NHNH ₂ ) is formic acid hydrazide, acetic acid hydrazide, propionic acid hydrazide, lauryl acid hydrazide, salicylic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthenic acid hydrazide, and the like. , Malonic acid hydrazide, adipic acid hydrazide, succinic acid hydrazide, azelaic acid hydrazide, sebacic acid hydrazide, maleic acid hydrazide, fumaric acid hydride And the like dihydrazide, diglycolic acid hydrazide, tartaric acid hydrazide, malic acid hydrazide, isophthalic acid hydrazide, terephthalic acid hydrazide, di immersion acid hydrazide such as dibasic acid dihydrazide and polyacrylic acid hydrazide of.

Specific examples of azoles include 1, 3-dimethyl-5-pyrazolone, 3-methyl-1-phenyl-5-pyrazolone, 3-phenyl-6-pyrazolone, 3-methyl-1- (3-sulfo Pyrazolones such as phenyl) -5-pyrazolone and 3-methyl-5-pyrazolone; Pyrazole, 3-methylpyrazole, 1, 4-dimethylpyrazole, 3, 5-dimethylpyrazole, 3, 5-dimethyl-1-phenylpyrazole, 3-aminopyrazole, 5-amino-3-methyl Pyrazole, 3-methylpyrazole-5-carboxylic acid, 3-methylpyrazole-5-carboxylic acid methyl ester, 3-methylpyrazole-5-carboxylic acid ethyl ester, 3, 5-methylpyrazoledicarboxylic acid Diazoles, such as these; 1, 2, 3-triazole, 1,2,4-triazole, 3-n-butyl-1, 2, 4-triazole, 3, 5-dimethyl-1,2,4-triazole, 3, 5-di-n-butyl-1, 2, 4-triazole, 3-mercapto-1, 2, 4-triazole, 3-amino-1,2,4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 5-amino-3-melcapto-1, 2, 4-triazole, 3-amino-5-phenyl-1 , 2, 4-triazole, 3, 5-diphenyl-1, 2, 4-triazole, 1, 2, 4-triazole-3-one, urazole (3, 5-dioxy-1, 2 , 4-triazole), 1, 2, 4-triazole-3-carboxylic acid, 1-hydrobenzotriazole, 5-hydroxy-7-methyl-1, 3, 8-triazindolisin, 1H- Triazoles, such as benzotriazole, 4-methyl- 1H- benzotriazole, and 5-methyl- 1H- benzotriazole, are mentioned.

Specific examples of the azine include 6-methyl-8-hydroxytriazolopyridazine, 4, 5-diclo-3-pyridazine, and the like.

The material for removing formaldehyde described above advantageously uses a minimum amount for reacting with the residual amount of formaldehyde, and adds 1 to 5 parts by weight with respect to 100 parts by weight of urushiol multimer, and adds to 100 parts of urushiol multimer It may be added by dissolving in 50 to 100 parts by weight of a solvent.

At this time, any solvent may be used as long as it can dissolve a substance for removing formaldehyde, and lower alcohols such as distilled water, methanol, ethanol and propanol are preferable, and an organic solvent and distilled water may be mixed and used.

After adding the substance for removing formaldehyde, the reaction was stirred at 60 to 80 ° C. for 30 minutes to 1 hour, and then allowed to stand at room temperature to release when separated from urushiol multimer, and 20 to 20 parts by weight of urushiol multimer based on 100 parts by weight. After washing several times with 100 parts by weight of the same new solvent, the solvent may be removed by evaporation under reduced pressure.

After the post-treatment process, the urushiol multimer may be polymerized by heating in the presence of an inert gas to prepare a high polymerization urushiol multimer.

In the polymerization reaction for preparing the high polymerized urushiol oligomer, the higher the reaction temperature, the shorter the reaction time, and the lower the temperature, the longer the time, and those skilled in the art can control the reaction temperature and reaction time as needed to control the amount of the polymerized polymer. Sieves can be prepared.

In more detail, the polymerization is carried out at 100 to 210 ° C, more preferably at 130 to 190 ° C. If the reaction temperature is too high, it is difficult to control the reaction rate due to the rapid progress of the polymerization, it may be accompanied by a disadvantage that the choice of the reactor is not free.

The time to terminate the polymerization reaction is a time point at which a substance other than urushiol oligomer is evaporated and the fluidity of urushiol decreases significantly, which is possible by visual judgment of the operator, and more specifically, the polymerization reaction is performed for 10 to 120 minutes. More preferably for 30 to 60 minutes.

The high-polymerized urushiol oligomer prepared according to the production method of the present invention has a weight average molecular weight of 70,000 to 160,000, and has excellent solubility in organic solvents in the state just before rubberization and may bring about an effect of minimizing allergy induction. have.

Hereinafter, a lacquer coating composition and a coating composition including a high polymerization urushiol multimer prepared according to the present invention will be described.

The lacquer coating composition and the coating composition in the present invention are both a lacquer coating composition and a coating composition comprising a high polymerization urushiol multimer prepared according to the manufacturing method of the present invention, but are included in the scope of the present invention, specifically, lacquer coating May be thermosetting sulfur lacquer coating, photocurable sulfur lacquer coating, urethane sulfur lacquer coating, epoxy sulfur lacquer coating, water soluble acrylic sulfur lacquer coating, water soluble urethane sulfur lacquer coating or oily sulfur lacquer coating, and lacquer coating agent is silicone sulfur lacquer sealant Can be.

Hereinafter, a method of manufacturing a thermosetting sulfur lacquer coating and a method of manufacturing a coating film will be described.

In the thermosetting sulfur lacquer coating composition, the amount of the highly polymerized urushiol oligomer prepared according to the present invention is used in an amount of 20 to 60% by weight based on the total amount of the paint, and is dissolved in an organic solvent and applied to a member for forming a coating film. By curing at 200 ° C, a yellow lacquer coating film is formed.

In addition, a thermosetting catalyst may be used to lower the curing temperature and increase the curing speed.

The type of thermosetting catalyst is one of a thermal polymerization initiator consisting of peroxides, a redox initiator consisting of a peroxide and a reducing agent, and an organometallic compound, and can be used in a range that does not impair durability to lower the curing temperature or improve the curing property.

Specific examples of thermal polymerization initiators include benzoyl peroxide, methyl ethyl ketone peroxide, hexyl ethyl ketone peroxide, p-chlorobenzoyl peroxide, t-butyl peroxide, t-butyl hydroperoxide, succinic acid peroxide and didecanyl peroxide. Oxide, cumene hydroperoxide, dicumyl peroxide, lauroyl peroxide, 2,4-pentadione peroxide, diisopropyl peroxide, di-2-ethylhexyl peroxycarbonate, t-butylperoxybenzoate, t -Butyl peroxyvalate, t-butylperacetate, cyclohexanone peroxide, t-amylperoxybenzoate, peracetic acid, 2,2-bis (t-butylperoxy) butane, 1,1- Bis (t-butylperoxy) cyclohexane, 2,5-bis (t-butylperoxy) -2,5-dimethylhexane, 2,5-bis (butylperoxy) -2,5-dimethyl-3 Peroxides such as hexine, bis (1- (t-butylperoxy) -1-methylethyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane Can be.

The thermal polymerization initiator may be used alone or two or more types, but is not limited thereto. In order to advance the reaction faster, it is effective to use a plurality of radical thermal polymerization initiators having different half-life temperatures, and the reaction can be further advanced.

The redox initiator is composed of the above-mentioned peroxides and tertiary amines, naphthenates, mercaptans, organometallic compounds and other reducing agents, and these radical initiation reactions are carried out with a small amount of activation energy (10 Kcal / mol). It is possible to initiate radical polymerization at.

Specific examples of redox initiators may be benzoyl peroxide, dimethyl aniline, methyl ethyl ketone peroxide organic metal complex or oxygen organic metal complex.

The organometallic complex has organic ligands such as unsaturated aliphatic, unsaturated cyclic compounds, aromatic compounds, phosphorus, nitrogen, oxygen, and sulfur having a non-covalent electron pair in the transition metal having the outermost electron of the element having an d orbit, Or, it is defined as a transition metal complex that forms a single bond with some halogen compounds and is a relatively stable compound in air, and then forms a radical when heated, and the transition metal is present in 4 to 6 cycles of the periodic table. It includes a metal. However, in terms of price, a transition metal complex containing four cycles of metal is advantageous.

Specific examples include metallocenes, metal naphthenates, metal cyclooctaates, metal octoates, including four- and five-cycle transition metals such as calcium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, and tin. Metal triphenylphosphine chromide, and the like, but is not limited thereto.

The thermosetting catalyst is used in an amount of 0.01 to 5% by weight, and preferably 0.1 to 3% by weight based on urushiol multimer.

The organic solvent is a solvent capable of dissolving urushiol multimers, and specific examples thereof include benzene, toluene, ethylbenzene, diethylbenzene, xylene, ethyl acetate, methyl ethyl ketone, acetone, tetrahydrofuran, 1,4-di At least one selected from oxane, terepine oil and mineral oil is used, and the amount of solvent is used so that the solid content is 20 to 60% by weight, but the operator can appropriately adjust the urushiol multimer according to the application method to the desired viscosity. Can be used after adjustment.

The temperature for curing after applying the above-mentioned heat-curable lacquer coating to the subject is carried out in the range of 20 to 200 ℃, when the curing accelerator is added, the curing temperature according to the properties of the added curing accelerator and the material of the subject And time may be appropriately adjusted by the practitioner.

Another method for producing a thermosetting sulfur lacquer coating may be sulfur lacquer added to commercially available heat-drying paint. Heat-drying paint is an industrial paint generally formed by combining a resin such as epoxy, melamine, alkyd, acrylic, etc., and forming a coating film by heating. The thermosetting sulfur lacquer coating composition according to the present invention can be stirred by adding sulfur lacquer to the heat-drying paint, and the amount of sulfur lacquer added is 5 to 95% by weight based on the total amount of the heat-drying paint. It can be added to produce a thermosetting sulfur lacquer coating.

Hereinafter, a method of manufacturing a photocurable sulfur lacquer coating and a method of manufacturing a coating film will be described.

The photocurable sulfur lacquer coating may be prepared by adding a high polymerization urushiol oligomer, an acrylic oligomer, a photoinitiator and an organic solvent to prepare a photocurable sulfur lacquer coating or an acrylic monomer instead of the organic solvent. Or acrylic monomers and an organic solvent can be mixed and used.

In the photocurable sulfur lacquer coating composition, the amount of the highly polymerized urushiol oligomer prepared according to the present invention may include 1 to 80 parts by weight based on the total amount of the acrylic oligomer, and may be adjusted according to the use, but may be white to yellow gloss. When the coating film is formed on the metal, in order to express the golden color, the urushiol multimer includes 20 to 60 parts by weight with respect to the total amount of the acryl oligomer, and has a feature capable of adjusting the golden color.

The acrylic oligomer is an acrylic oligomer having two or more functional groups, such as alkyl acrylate, alkyl methacrylate, polyester acrylate, polyether acrylate, urethane acrylate, epoxy acrylate, alkyt acrylate, melamine acrylate, poly Butadiene acrylate, spiran acrylate, silicone acrylate, fluorine acrylate, fluorinated (meth) acrylate, various modified acrylates and the like.

One of these may be used, and two or more kinds of acrylates may be mixed and used. Since the properties of the coating film vary depending on the number of functional groups, the kind of acrylate may be appropriately selected or modified to suit the application.

Examples of acrylic monomers are methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, lauryl acrylate , Acrylates such as stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl Methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl Methacrylates such as methacrylate, methoxyethyl methacrylate and ethoxymethyl methacrylate Relates are used, including methacrylates substituted with silicon instead of carbon or with fluorine instead of hydrogen. Moreover, 2 or more types of (meth) acryl monomers can also be used, and unsaturated aliphatic and aromatic olefins can also be added.

The photoinitiator, acetophenone compound, benzophenone compound, halogen compound, carbonyl compound, dicarbonyl compound, benzoin ether compound, aminocarbonyl compound, organic peroxide, diphenylhalonium salt, aromatic ketone, tertiary amine , Ketal compounds, thiol compounds, halogenated compounds, cyclic ring compounds, polycyclic compounds, bisamidazole compounds, N-arylglycidyl compounds, acridine compounds, peroxyketa, azo compounds, iron-arene Complexes or titanocene compounds may be used.

Specific examples of photoinitiators include acetophenone, propiophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl Propane-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one, dimethoxyacetophenone, diethoxyacetophenone, 2,2- Dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1,2-diphenylethan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, dichloroacetophenone, p-tert-butyltrichloroacetphenone, trichloroacetophenone, N, N-dimethylaminoacetophenone , p-dimethylaminopropiophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholin Nophenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholinopropanoyl ) -9 Acetophenone compounds selected from -butylcarbazole, α-hydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cyclohexylacetophenone, diacetylacetophenone ; Benzophenone, 4-methylbentophenone, 4-phenylbenzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4- (4 -Methylylthio) benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4 ' -Methyldiphenylsulfide, 3,3-dimethyl-4-methylbenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxatridecyl) benzophenone, 3,3 Benzophenone compounds selected from ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone; 4-benzoyl-N, N, N-methylbenzenemethanealuminum chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propaneamichloride, 4-benzoyl -N, N-dimethyl-N-[(2- (1-oxo-2-propenoxy) ethyl) -benzenemethanealuminum chloride, 4-benzoyl-N, N-dimethyl-N-[(2- ( Halogen compound selected from 1-oxo-2-propenyloxy) ethyl) -benzenemethanealuminum bromide; Thioxanthone, 2-chlorothioxanthone, thioxanthone, 2-isopropylthioisopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl tea Oxanthone, 2,4-diisopropyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxycyxanthone, 2-hydroxy-3- (3,4-dimethyl-9 -Oxo-9H-thioxanthone-2-yl-oxy) -N, N, N-trimethyl-1-propaneaminium chloride, 2-benzoylmethylene-3-methylnaphtho (1,2-d) thiazoline Carbonyl compounds selected from; Benzyl, 1,7,7-trimethyl-bicyclo [2,2,1] heptan-2,3-dione (also known as camphorquinone), 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butyl Dicarbonyl compounds selected from anthraquinone, 1-chloroanthraquinone, 2-aminoanthraquinone, 2,3-diphenylanthraquinone, 9,10-phenanthrenequinone, methyl a-oxobenzene acetate; Benzoin (2-hydroxy-1,2-diphenylethanone), benzoin methyl ether (2-methoxy-1,2-diphenylethanone), benzoin ethyl ether (2-ethoxy-1, 2-diphenylethanone, benzoin isopropyl ether (2-isopropoxy-1,2-diphenylethanone), benzoin-n-butyl ether (2-butoxy-1,2-diphenylethanone ), Benzoin isobutyl ether (benzoin ether compound selected from 2-isobutoxy-1,2-diphenylethanone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dichloro) Arylphosphine oxide compounds selected from benzoyl)-(4-n-propylphenyl) phosphine oxide; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate-n-butoxy Ethyl ester, isoamyl-4-dimethylaminobenzoate, benzoate-2-dimethylaminoethyl ester, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,5'-bis Aminocarbonyl compound selected from 4-dimethylaminobenzal) cyclopentanone; benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butylhydroperoxide, di-t-butyldiperoxyisophthalate Organic peroxides selected from 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, cumene peroxide; diphenylhaloselected from diphenyliodobromide, diphenyliodochloride Rhonium salt; aromatic ketone; tertiary amine; ketal compound selected from acetphenone dimethyl ketal, benzyl dimethyl ketal; 2,4,5-triarylimidazole dimer, riboflavin tetrabutylate, 2-mercaptobenzoimi Thiol compounds selected from dazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,2,2-trichloro-1- (4'-tert-butylphenyl) ethan-1-one, 2 , 2-dichloro-1- (4-phenoxyphenyl) ethan-1-one, α, α, α-tribromomethylphenyl Sulfone, 2,2,2-tribromoethanol, 2,4,6-tris (trichloromethyl) triazine, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) triazine , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) triazine , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuryl) ethylidedine] Halogenated compounds selected from triazine, 2,4-bis (trichloromethyl) -6- [2-burylethylidine] triazine; Heterocyclic and polycyclic compounds selected from 3-phenyl-5-isoxazoron, 2,4,6-tris (trichloromethyl) -1,3,5-triazinebenzanthrone; Bisimidazole-based compounds; N-aryl glycidyl compounds; Acridine-based compounds; Peroxyketa; 2,2'- azo (2,4-dimethylvaleronitrile), 2,2 'azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'- Azo compounds selected from azobis (2-methylbutyronitrile); Iron-areren complexes; Or one or two or more compounds selected from titanocene compounds.

Representative examples of the photocuring initiator is commercially available Irgacure 184, Irgacure 819, BPO, TPO, Irganox 1010, Irganox 1035, Irganox 1076, among which Irgacure 184, Irgacure 819, Irganox 1076, TPO and the like are preferable. Do.

In the present invention, an organic solvent may be used instead of an acrylic monomer, and an acrylic monomer and an organic solvent may be mixed and used. The amount of the organic solvent is preferably added in an amount of 1 to 90 parts by weight, preferably 10 to 70 parts by weight based on the total weight of the photocurable sulfur lacquer paint. When the amount of the organic solvent used is more than 90 parts by weight, the viscosity is so low that the thickness of the coating film becomes less than a certain thickness, the surface hardness is lowered, the transparency of the film is affected by the coating film working conditions. Representative examples of the organic solvent, ethanol, isopropyl alcohol, diacetone alcohol, n-butanol, toluene, xylene, ethyl cell solution, butyl cell solution, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, n-butyl acetate Etc. Among these, isopropyl alcohol, n-butanol, toluene, ethyl cellosolve, methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate and the like are preferable. The organic solvent may use a single solvent or two or more mixed solvents to adjust the performance of the coating film according to the working conditions.

Hereinafter, the manufacturing method of urethane sulfur lacquer coating is described.

Urethane sulfur lacquer coating in the present invention is a two-component urethane sulfur lacquer paint is composed of a polyol part (A part) and an isocyanate part (B part) to be mixed before use, the reaction starts to proceed before the pot life It is paint.

In the method for producing a two-component urethane sulfur lacquer coating, urushiol multimer is added to the polyol portion (part A), and the amount of urushiol multimer added is 5 to 30 parts by weight based on the solid content of the polyol part (A part), When mixed with Part B during use, each is cured by reaction with a curing agent, so the total hydroxyl value of the urushiol multimer and the polyol must be calculated to determine the amount of corresponding isocyanate used.

The usage-amount of B part corresponding to the hydroxyl value of A part uses polyisocyanate corresponding to 50-120 equivalent%. However, in order to give antimicrobial property which is a characteristic of lacquer, 70 to 90 equivalent% is suitable.

In addition, the organic solvent used may be an organic solvent used in a conventional two-component urethane paint, and the amount of the solvent is used so that the solid content is 20 to 50% by weight, but appropriate for the purpose of controlling the coating method and pot life. Can be used after adjustment.

Hereinafter, the method of manufacturing an epoxy sulfur lacquer coating is described.

Epoxy sulfur lacquer coating in the present invention is a two-component epoxy sulfur lacquer coating is composed of a polyol portion (A portion) and an isocyanate portion (B portion) to mix before use, the reaction begins to proceed before the pot life It is a paint that should be. The amount of polyamine used in Part B corresponding to Part A is suitably 70 to 120 equivalent%, epoxy urethane lacquer is added urushiol multimer to part B, and 5 to 30 parts by weight based on epoxy paint solids, Excess urushiol multimer is present so as to have the characteristics of lacquer in a range that does not significantly harm. In addition, the organic solvent may be used an organic solvent used in conventional epoxy paints, it can be used by those skilled in the art as appropriate for the purpose of coating method and pot life control.

Hereinafter, the manufacturing method of water-soluble acrylic sulfur lacquer coating and water-soluble urethane sulfur lacquer coating is described.

The water-soluble acrylic sulfur lacquer paint and the water-soluble urethane sulfur lacquer paint can be selected and used commercially available water-soluble paints, and after dispersing urushiol polymer in a commercially available emulsifier, it is added to the water-soluble acrylic paint and the water-soluble urethane paint, respectively, to add the characteristics of the lacquer. It is a method of manufacturing a functional eco-friendly paint.

The urushiol multimer is added 1 to 30% by weight based on the total amount of the paint, the emulsifier is a common industrial and food emulsifier with an HLB value of 8 to 16, depending on the type of emulsifier, so that the urushiol multimer can be sufficiently dispersed 50-300 weight part is used with respect to the total amount of the urushiol multimer added. In general, the amount of emulsifier used can be prepared by a person of a suitable ratio according to the molecular weight of sulfur lacquer or the kind of acrylic paint.

The water-soluble acrylic sulfur lacquer paint and the water-soluble urethane sulfur lacquer paint in the present invention can be prepared by adding a pigment of various colors to add a color of the lacquer. The addition amount of the pigment can be usually added by the manufacturer according to the hiding power of the pigment, it may be added 10 to 40% by weight of the total amount of the paint. In addition, in order to adjust the content of the solid content it can be diluted by adding 1 to 30% by weight of purified water to the total amount of paint.

Hereinafter, a method for producing an oily sulfur lacquer coating will be described.

One or two or more composite synthetic resins, such as oil-based paints such as alkyd, polyolefin, nitrocellulose, shellac, and oil stains, are dissolved in organic solvents, and urushiol multimers are added to various industrial oil-based vehicles used as paints. Since the method for producing the oily sulfur lacquer coating is well mixed with the high polymerization urushiol oligomer by the organic solvent, it is possible to manufacture by adding and mixing the urushiol oligomer to the commercially available paint, respectively. The amount of urushiol multimer added may be 3 to 30% by weight based on the total amount of the paint. More preferably, 5 to 20% by weight is added. If the added amount of the sulfur lacquer is lower than 3% by weight, the characteristics of the sulfur lacquer, such as mold resistance, antibacterial properties are lowered, and if higher than 30% by weight, the dryness may be poor.

Hereinafter, the method of manufacturing silicone sulfur lacquer sealant is described.

Silicone sealant used as a building finishing material is well mixed with a high polymerization urethane oligomer, so it can be produced as a silicone sulfur lacquer sealant having antibacterial and antiseptic function by adding it without solvent. The addition amount of the high polymerization urushiol oligomer to the silicone sealant is preferably 3 to 20% by weight of the total amount of the sealant. If the addition amount of the high polymerization urushiol oligomer is added in a small amount less than the above range may be less mold resistance, if the excess is added outside the above range may be less dry.

As described above, the method for producing various lacquer coatings by combining the high polymerization urushiol oligomer according to the present invention with various industrial paints is not limited to the industrial paints described above, and various paints and coating agents that are commonly used. All methods for adding urushiol multimers to each belong to the scope of the present invention.

The high polymerization urushiol oligomer according to the present invention is excellent in antibacterial, weather resistance, heat resistance, abrasion resistance, fouling resistance, water resistance, chemical resistance, adhesion, insect repellent and induce allergy while maintaining the characteristics of natural lacquer, such as electromagnetic wave absorption effect It is difficult to dry and has the effect of improving the shortcomings of the natural lacquer that the coating is limited to black. When used directly or added to various vehicles, the coating is easily cured, and the compatibility and compatibility are good. Bring the features.

In addition, the high polymerization urushiol oligomer according to the present invention can be used as a paint or added to various industrial paints to produce industrial lacquer coating, coating agent having at least one or more of the properties of the lacquer can be expected industrial effects of various purposes.

In addition, various yellow lacquer coatings added with a high polymerization urushiol oligomer according to the present invention exhibits a transparent yellow color, and when applied to a white to yellow metal, it expresses a golden color. Unlike the black lacquer, it can maintain the inherent saturation of the pigment, which makes it possible to manufacture highly saturated color lacquer paints. When applied to various genres of art, industrial products, and traditional buildings, high value-added products It is expected.

Figure 1 shows the change in weight average molecular weight according to the reaction time in Example 1.
Figure 2 shows the change in the number average molecular weight according to the reaction time in Example 1.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The hardness of the coating film in the Example was confirmed by the pencil hardness check method, the pencil hardness tester (PENCIL TESTER) using Japan YOSHIMITSU was confirmed using a pencil of hardness range 6B ~ 9H (17 steps). The viscometer used BROOKFIELD LVDVE230.

In case of the material of wood, one of brushing and spraying method was selected and the metal was applied by spraying method on 5x7cm stainless steel plate. After hardening, the thickness of coating film was Mitutoyo thickness meter Model ID- C112BS was used, and in the case of wood, the coating film was manufactured to have a dry coating thickness of 25 to 45 μm and a metal to 5 to 25 μm. The UV lamp used to cure the coating film was cured by irradiating a 30 cm / 70 cm mercury lamp on 30 cm of the subject.

Preparation Example Purification of Urushiol from Natural Lacquer

500g of Chinese natural lacquer and 1000g of acetone were mixed well, and left to stand for 3 days. The supernatant was filtered using 1μm filter cloth, and the precipitated filter cloth was washed with two portions of 200g of acetone, and the filtrate was concentrated under reduced pressure using a rotary evaporator. Urushiol was purified.

Example 1 Preparation of High Polymerized Urushiol Multimer by Purified Urushiol and Formalin Condensation Reaction

Into a 1000 ml round flask equipped with a stirrer and a reflux apparatus, 314 g (1 mol) of purified urushiol, 65 g (0.8 mol) of formalin (37% aqueous solution), 21 g of ammonia water (25% aqueous solution, 15 wt%) and 200 g of ethanol were added thereto, followed by stirring. The mixture was heated in a hot pot and refluxed for 5 hours, then left to cool to room temperature.

When the reaction temperature was reached and the reaction product was separated, the lower solvent layer was discharged, and the upper urushiol polymer obtained was washed twice with 200 ml of distilled water, followed by adding 30 g of 10% urea-ethanol solution for 30 to 60 hours. After heating at room temperature and cooled to room temperature again, 200 ml of distilled water was further added, stirred for 10 minutes and left to separate the layers after separation of the water layer. The obtained urushiol multimer was concentrated under reduced pressure with a rotary evaporator to completely evaporate the water to obtain urushiol multimer. The weight average molecular weight of the GPC analysis was about 16,000, and the specific peak of formaldehyde could not be confirmed by 1H NMR. .

In addition, the obtained urushiol oligomer was sampled with the progress of time while heating to 150 ℃, the sample was stabilized for 12 hours at 65 ℃ in a constant temperature water tank to measure the viscosity and then measured the viscosity, GPC analysis The molecular weight was confirmed by.

As shown in Table 1, the change in weight average molecular weight and number average molecular weight of the urushiol multimer produced by formalin condensation reaction at 150 ° C. for 60 minutes is shown in FIGS. 1 and 2. The rubber nitriding was carried out until 40 to 60 minutes, it was confirmed that the weight average molecular weight is about 80,000 to 160,000. The weight average molecular weight of 70,000 to 80,000 immediately before the rubber nitriding process is the most ideal molecular weight, and after 60 minutes, as the acetone-insoluble substance is formed, the rubber nitriding proceeds rapidly. Synthesis condition of GPC was determined to be appropriate, and after the rubber nitriding was confirmed, the weight average molecular weight was lowered as the urushiol oligomer which had been polymerized and rubber nitriding was removed without being dissolved in THF, a solvent used for GPC analysis. Error was confirmed.

Example 2 Thermosetting Coating Film Preparation of Urushiol Multimer

Synthesis of urushiol multimer by the method of Example 1, 6g of high polymerization urushiol oligomer heated to 150 ° C. for 40 minutes was dissolved in toluene, applied to a stainless plate and allowed to stand at room temperature for 20 minutes to evaporate the solvent and then room temperature and 80 Tack curing time was measured while drying at ℃, 100 ℃, 150 ℃, and the pencil hardness was confirmed twice while standing at room temperature for 15 days.

In addition, experiments were conducted under the same method of adding a thermosetting catalyst such as BPO (benzoyl peroxide), Fc (Ferrocene), CoNp (Cobaltnaphtenate), and the drying properties of the coating film were confirmed by confirming the thermal curing time and the pencil hardness.

In addition, the purified urushiol in the comparative group was tested under the same conditions and compared with the urushiol multimer.

As shown in [Table 2], when the curing catalyst was used and when it was not, the curing time at room temperature, 80 ° C., 100 ° C. and 150 ° C., respectively, and the hardness of the coating film depended on the curing temperature. As the curing temperature was increased, the curing time was shortened and the hardness of the coating was increased. In addition, it was confirmed that the curing time is shortened when using the curing catalyst, and showed a slight difference depending on the type of curing catalyst.

However, the hardness of the coating film was irrelevant to the use of the catalyst. The higher the molecular weight of the lacquer multimer and the higher the curing temperature, the higher the hardness. In addition, when the hardness of the coating film after 7 days and 15 days at room temperature after curing, the hardness was confirmed to increase. Although slowly cured at room temperature, it was confirmed that heat curing was advantageous in terms of hardness and curing time.

Example 3 Preparation of Photocurable Yellow Lacquer Coating Using Urushiol Multimer

Synthesis of urushiol oligomer by the method of Example 1, 4g of high polymerized urushiol oligomer heated to 150 ° C. for 40 minutes, 10g urethane acrylate oligomer (Ebecryl 1290) and 18g toluene were added for 10 minutes Stirred. When completely mixed, 0.56 g (4 wt% of uriva oligomer and acryl oligomer) of CA184 (Chivacure 184, 1-hydroxy cyclohexyl phenyl ketone), a photoinitiator, was added, stirred at 60 ° C. for 1 hour, and applied onto a stainless plate, followed by UV lamp (80 w). / cm) under 30 cm cured coating film. After curing, the hardness of the pencil was confirmed, and after 15 days, the hardness was confirmed.

In addition, purified urushiol was tested in the same manner for comparative experiments.

As shown in [Table 3], the three kinds of urushiol multimers were photocured with an acrylic oligomer, and after 15 days of room temperature, the hardness was increased to form a coating film having a high hardness of 8H or more. However, purified urushiol did not cure in the photocuring process and exhibited a phenomenon of separation from acryl oligomer.

Example 4 Preparation of Water-Based Urethane Sulfur Lacquer Coating and Aqueous Acrylic Sulfur Lacquer Coating Using Urushiol Multimer

The production method of the water-based acrylic paint and the water-based urethane paint is 10 g of high-polymerized urushiol polymers synthesized by the method of Example 1, and dispersed in 10 g of olive oil, and then 80 g of water-based urethane paint and water-based acrylic paint (solid content 40) %) Was added and dispersed, respectively, and they were each coated with wood as a coating film and confirmed dryness, and dried within 30 minutes, and a beautiful coating film was obtained.

Also, for the comparative experiment, 10g of purified urushiol instead of urushiol multimer was taken and dispersed in olive oil in the same manner as urushiol multimer, and then dispersed in 80g of water-based urethane paint and water-based acrylic paint, respectively. It was confirmed that the coating and drying properties using the adhesive was not dried and sticky, and was not dried at room temperature by purified urushiol.

Example 5 Preparation of 2-component urethane sulfur lacquer coating using high polymerization urushiol multimer

10 g of the high polymerization urushiol polymer synthesized by the method of Example 1 was taken and added to 50 g of alkyd polyol (OH value 2.1), respectively, followed by urethane thinner (butyl acetate: MIBK: cellosolve acetate: xylene = 10: 10: 10: To prepare Part A by adding 60 g of 30 v / v), 36 g of polyisocyanate (NCO value 5.25) was added to a mixed solution of 20 g of ethyl acetate, 25 g of butyl acetate, 13 g of MIBK, and 6 g of xylene to prepare a curing agent (B part). Part B was prepared. Before use, A and B parts were mixed and applied to a pine board with a brush to obtain a clear yellow beautiful coating film with wood texture. In addition, it was able to express the same texture as the traditional floorboard coated with soybean oil by applying on the floorboard.

In addition, the two-component urethane lacquer coating was sprayed onto aluminum foil to obtain a glossy golden coating.

Example 6 Preparation of Epoxy Sulfur Lacquer Coating Using High Polymerized Urushiol Multimer

10 parts by weight of the total amount of the paint was added to the B portion of the epoxy paint (Samhwa Paint Co., Ltd. Epicoat 210 PLUS, A: B = 5.5: 1), and stirred well. Next, A and B parts (curing agents) were mixed and brushed on the steel before use, and an epoxy lacquer coating film having a hardness of 6H or more after 1 day at room temperature was obtained.

Example 7 Preparation of Oil-Based Sulfur Lacquer Coating Using High Polymerization Urushiol Multimer

High polymerization prepared by the method of Example 1 in an oil-based lacquer enamel paint, which is produced by dissolving resin components such as alkyd resin, modified alkyd, nitrocellulose, unsaturated polyester, etc., which are commercial oil-based paints alone or in combination, in an organic solvent. Alkyd enamel paint (Samhwa Paint Spimel S), Nitrocellulose and Alkyd Resin Combination Paint (Samhwa Paint) for the production of oil-based lacquer yellow lacquer paint and oily enamel sulfur lacquer paint by adding 10% by weight of urushiol multimer resin, respectively. LOV HS lacquer) was added to each of the high polymerization urushiol oligomers, mixed and the solvent was added to prepare a solid content of 40% to prepare an oil-based lacquer coating. In addition, the wood was selected as a subject to be brushed and then confirmed the dryness, the results of the comparative experiment with the paint without the addition of high polymerization urushi oligomer as a control is shown in [Table 4].

Example 8 Preparation of Yellow Lacquer Sealant Using Urushiol Multimer

80 g of a commercially available silicone sealant (Aniseal N) and 20 g of a high-polymerization urushi oligomer synthesized by the method of Example 1 were added and stirred with a polymer mixing stirrer to prepare a silicone sulfur lacquer sealant. As a result of measuring surface dry time at, it took 3.5 hours, and the silicone sealant without high polymerized urushi oligomer was dried in 3 hours. The sulfur lacquer silicone sealant showed a difference in the drying time of 30 minutes from the silicone sealant before addition.

As described above, a method of preparing a high lacquer paint by synthesizing a high polymerization urushiol oligomer according to the present invention and using them as it is or in combination with various industrial paints is not limited to the examples of the above embodiments.

Claims (13)

(Iii) condensation polymerization of urushiol with formaldehyde under a basic catalyst to produce urushiol multimers;
(Ii) removing some or all of the residual formaldehyde from the urushiol multimers from step (iii); And
(Iii) heating the urushiol multimer from step (ii) in the presence of an inert gas to polymerize to prepare a high polymerized urushiol multimer.
The method of claim 1,
Urushiol of the step (ⅰ) is a method for producing a high polymerization urushiol multimer, characterized in that derived from natural lacquer.
The method of claim 1,
Urushiol multimer of the step (iii) is a method for producing a high-polymerization urushiol multimer, characterized in that the weight average molecular weight of 3,000 to 70,000.
The method of claim 1,
The basic catalyst of step (iii) is one or more selected from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide, barium hydroxide and lithium hydroxide;
The formaldehyde is a method for producing a high polymerization urushiol multimer, characterized in that using formalin.
The method of claim 4, wherein
The basic catalyst adds 1 to 10 parts by weight based on the total weight of urushiol;
The formalin is a method for producing a high-polymerization urushiol multimer, characterized in that 10 to 99 equivalent% added to the urushiol.
The method of claim 1,
The polycondensation reaction of the step (iii) is a method for producing a high polymerization urushiol multimer, characterized in that carried out for 3 to 8 hours at 80 to 120 ℃.
The method of claim 1,
Residual formaldehyde of step (ii) is one to two or more to urushiol multimers selected from the group consisting of inorganic ammonium salts, organoammonium salts, aliphatic and aromatic organic amines, hydrazides, azoles and azines. Method for producing a high polymerization urushiol oligomer, characterized in that the removal by adding a weight%.
The method of claim 1,
The high polymerization urushiol multimer of step (iii) has a weight average molecular weight of 70,000 to 160,000, characterized in that the manufacturing method of high polymerization urushiol multimer.
The method of claim 1,
The polymerization of step (iii) is carried out for 10 to 120 minutes at 100 to 210 ℃ method for producing a high polymerization urushiol multimer.
A lacquer coating composition comprising a high polymerization urushiol multimer having a weight average molecular weight (Mw) prepared according to any one of claims 1 to 9 selected from 70,000 to 160,000.
The method of claim 10,
The lacquer coating is one selected from the group consisting of thermosetting sulfur lacquer coating, photocurable sulfur lacquer coating, urethane sulfur lacquer coating, epoxy sulfur lacquer coating, water-soluble acrylic sulfur lacquer coating, water-soluble urethane sulfur lacquer coating or oily sulfur lacquer coating. Lacquer coating composition.
A lacquer coating composition comprising a high polymerization urushiol multimer having a weight average molecular weight (Mw) prepared according to any one of claims 1 to 9 selected from 70,000 to 160,000.
13. The method of claim 12,
The lacquer coating agent is a lacquer coating agent composition of silicone sulfur lacquer sealant.

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