JP5769769B2 - Non-allergenic urushiol polymer - Google Patents

Description

  The present invention relates to a urushiol polymer, and more specifically, urushiol derived from raw lacquer extracted from urushi is reacted with an ethylenically unsaturated monomer having a hydrophilic functional group to thereby produce a substantially non-allergenic urushi. The present invention relates to a method for producing an aqueous emulsion or powder of an all polymer, an aqueous emulsion or powder of the produced urushiol polymer, and uses thereof.

  Urushi (Rhus verniciflua or Rhus vernicifera) is a deciduous tree belonging to the family Uranaceae (Anacardiaceae). Widely distributed in rural areas, it is used for crafts and daily necessities as natural paint in East Asia such as Korea, China and Japan.

  Raw lacquer or lacquer liquid collected from urushi promotes blood circulation in Kampo and is known to be effective as an insecticide and fungicide against various diseases such as anthelmintic, abdominal pain, tuberculosis, menstruation, constipation, diabetes, and malaria. It is still used as a folk remedy for medicinal dishes such as lacquer chicken soup and lacquer duck soup. Recently, scientific research on the effects of traditional lacquer has revealed the antioxidant function of lacquer.

  Lacquer liquid contains urushiol, moisture, rubber, laccase, and nitrogen-containing substances. The urushiol is a main component occupying about 70% of the lacquer liquid, and is a catechol complex in which a hydrocarbon group represented by a C15-alkyl or alkenyl group is substituted at the 3-position. So far, 13 types of hydrocarbon groups having 0, 1 or 2 double bonds are known (Non-patent Document 1). In addition, it is known that a natural polymer in a form in which urushiol is naturally polymerized is mixed with the lacquer liquid (Non-Patent Documents 2, 3 and 4).

  Urushiol, the main component of lacquer, was reported to cause an allergic reaction in the early days, but after that, its strong antioxidant, antibacterial, waterproof, chemical resistance, insecticide and antiseptic effects will be elucidated. Traditionally, the durability of lacquer has been chemically demonstrated. Urushiol has little effect on normal cells, but has also been found to be a potential anticancer agent because it selectively attacks only cancer cells. Based on such basic efficacy, research on effective and various extraction methods or practical applications of urushiol has been conducted.

  However, unlike the synthetic resin paint, the conventional lacquer coating has a characteristic of drying under a specific environmental condition of high humidity (relative humidity 70%, 20 to 25 ° C.), and there is a problem that the operation is complicated and expensive. Furthermore, lacquering has the disadvantage that it is difficult to apply to daily products and industrial materials due to natural additives and moisture, and the side effects of inducing allergic phenomena when contacted with the skin are not solved.

  As an attempt to remove the impurities contained in such lacquer and apply purified urushiol, there are Patent Documents 2, 3, 4, and the like.

  Various attempts have been made to use purified urushiol in this way, but until now, lacquer liquor has concentrated on the separation of purified urushiol or development of new applications, and limitedly applied only by mixing purified lacquer. ing.

Korean Patent Application No. 10-1999-0016473 Specification Korean Patent Application No. 10-1997-0013163 Specification Korean Patent Application No. 10-1999-0016473 Specification Korean Patent Application No. 10-1999-0001740

Yumin Du and Ryuichi Oshima, J. of Chromatography, 284, 463-473 (1984) 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) Y. Du, R. Oshima and H. Iwatsuki, J. of Chromatography, 295, 179-186 (1984)

  An object of the present invention is to provide a method for producing a urushiol polymer that solves the problem of allergy induction and maximizes antibacterial, insecticidal and antiseptic effects.

  Another object of the present invention is to provide urushiol polymers and uses thereof.

  In order to achieve the above object, according to one aspect of the present invention, there is provided a method for producing a non-allergic urushiol polymer, comprising mixing urushiol, an ethylenically unsaturated monomer having a hydrophilic functional group, and water. Stirring to obtain an aqueous monomer dispersion; Stirring the aqueous monomer dispersion while adding a first radical polymerization initiator having a peroxy group and reacting to obtain a prepolymer; Neutralizing the prepolymer A step of adding an agent to obtain a neutralized prepolymer; a step of mixing the neutralized prepolymer with water to obtain a prepolymer aqueous emulsion; and a second radical polymerization initiator having a peroxy group in the prepolymer aqueous emulsion. And reacting to obtain a urushiol polymer aqueous emulsion.

  The method may further include the step of drying the urushiol polymer aqueous emulsion.

The hydrophilic functional group, -COOM (M is hydrogen, an alkali metal or ammonium), - _SO 3 M (M is hydrogen, an alkali metal or ammonium), _- PO 3 HM (M is hydrogen, an alkali metal or ammonium), -PO 3 _{M '(M'} is an alkaline earth metal) may be selected from and mixtures thereof.

  The first radical polymerization initiator and the second radical polymerization initiator may be the same or different from each other.

  The second radical polymerization initiator may be selected from t-butyl hydroperoxide, ethyl hydroperoxide, hydroperoxide, ketone peroxide, diacyl peroxide, peroxyketal, peroxyester, peroxydicarbonate, and mixtures thereof.

  The neutralizing agent may be selected from organic bases, inorganic bases and mixtures thereof.

  The mixing ratio of the unsaturated monomer may be 1 to 100 parts by weight with respect to 100 parts by weight of the urushiol.

  The addition amount of the second radical polymerization initiator may be 1.5 times or more compared to the addition amount of the first radical polymerization initiator.

  The non-allergic urushiol polymer may have an average particle size of less than 0.5 μm.

  In another aspect of the present invention, a non-allergic urushiol polymer produced by the above method is provided.

  Furthermore, in another aspect of the present invention, the use of the non-allergenic urushiol polymer is provided.

  As described above, the urushiol polymer aqueous emulsion and urushiol polymer powder produced according to the present invention do not induce allergies while maintaining the antibacterial, insecticidal, antiseptic and other effects inherent in urushiol. Therefore, it can be more easily applied to various products such as soaps, cosmetics, natural dyes, water-based paints, and various plastic additives.

  In addition, the urushiol polymer aqueous emulsion and powder thereof of the present invention can be used for life that is beneficial to the human body through development in the field of application by making it possible to more easily and selectively use the effects of lacquer as a natural material. The possibilities in the field of goods are presented.

  Hereinafter, the present invention will be specifically described.

  In the method for producing a non-allergic urushiol polymer of the present invention, the starting monomer is urushiol and an ethylenically unsaturated monomer having a hydrophilic functional group.

  Preferably, the urushiol is obtained by extracting pure urushiol from the raw lacquer component derived from urushi using ethanol, removing water, gum, and laccase enzyme, and centrifuging and distillation under reduced pressure. Of refined raw materials.

  The ethylenically unsaturated monomer having a hydrophilic functional group has a double bond and a hydrophilic functional group in the molecule, preferably one double bond is in the α-position, and the hydrophilic functional group is at the terminal.

Preferably, the hydrophilic functional group, -COOM (M is hydrogen, an alkali metal or ammonium), - _SO 3 M (M is hydrogen, an alkali metal or ammonium), _- PO 3 HM (M is hydrogen, an alkali metal or _{ammonium), - PO 3 M '(} M' may be selected from alkaline earth metals) and mixtures thereof.

  Specific examples of the ethylenically unsaturated monomer having the hydrophilic functional group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, aconitic acid, maleic acid, monomethylmalic acid, monomethylfumaric acid, monomethylitaconic acid, Examples thereof include vinyl sulphonic acid, vinyl phosphonic acid, and derivatives thereof, preferably acrylic acid, methacrylic acid, vinyl sulfonic acid, vinyl phosphoric acid, or salts thereof.

  The starting monomer is mixed with water and stirred to produce an aqueous monomer dispersion, and then a first radical polymerization initiator having a peroxy group is added and reacted while stirring to produce a prepolymer.

  When the starting monomer is directly mixed with the first radical polymerization initiator and polymerized, it is difficult to produce a prepolymer having a uniform molecular weight, and as a result, it is difficult to produce a urushiol polymer having a uniform particle size. However, according to the present invention, when the first radical polymerization initiator is added and polymerized while maintaining the aqueous dispersion state of the starting monomer, the urushiol monomer and the ethylenically unsaturated monomer having the hydrophilic functional group are uniformly obtained. While contacting, radical polymerization occurs between the unsaturated group in the urushiol monomer and the unsaturated group of the ethylenically unsaturated monomer having a hydrophilic functional group, thereby producing a urushiol polymer having a uniform and fine particle size. Can be manufactured. The molecular weight, molecular weight distribution, particle size and the like of the prepolymer obtained in the prepolymer production stage can be controlled by the reaction time, reaction temperature, first radical initiator amount and the like.

  The mixing ratio of the starting monomer is preferably 1 to 100 parts by weight of the ethylenically unsaturated monomer having the hydrophilic functional group with respect to 100 parts by weight of urushiol monomer. If the ethylenically unsaturated monomer having a hydrophilic functional group is used in an amount of less than 1 part by weight, the production of the prepolymer emulsion described below may be difficult, and the ethylenically unsaturated monomer having the hydrophilic functional group may be difficult. When the amount exceeds 100 parts by weight, the viscosity may increase and it may be difficult to control the reaction.

  The reaction for producing the prepolymer can be carried out in the presence or absence of a catalyst. Examples of the catalyst include a redox active catalyst. As the oxidation-reduction active catalyst used in the present invention, one or more compounds may be selected and used from metal salts, metal complexes, hydrophilic amines, and mixtures thereof. Metal salts such as monovalent or higher valent sodium and calcium are used as metal salts, metal complexes such as higher valent nickel, cobalt, manganese, iron, and copper are used as metal complexes, and tertiary amines are mainly used as hydrophilic amines. Amines are preferred.

  The prepolymer is produced as a prepolymer in a hydrophilic salt state by a neutralization reaction with a neutralizing agent such as an inorganic base, an organic base or a mixture thereof.

  Examples of the neutralizing agent for neutralizing the prepolymer include triethylamine, triethanolamine and dimethylethanolamine as tertiary amines as examples of organic bases, and sodium hydroxide and sodium carbonate as examples of inorganic bases.

  The mixture is stirred while slowly adding deionized water to the hydrophilic salt-state prepolymer produced by the neutralization reaction as described above. During this process, a phase transition from the water-in-oil phase to the oil-in-water phase occurs, resulting in a prepolymer emulsion containing a particulate hydrophilic prepolymer salt. Is manufactured.

  The prepolymer emulsion is reacted in the presence of a second radical polymerization initiator having a peroxy group. In this process, a polymerization reaction further occurs between the prepolymers, and the allergenic part disappears, and the target non-allergic urushiol polymer is produced.

  In this method, when a peroxy-type initiator is used as the first and second radical polymerization initiators, a particulate non-allergic urushiol polymer is produced, but when an azo-type initiator is used, the particle size becomes large. In addition, it is difficult to produce the desired urushiol polymer while maintaining allergenicity.

  In the present invention, the first and second radical polymerization initiators may be the same or different from each other. Examples of the initiator include t-butyl hydroperoxide, ethyl hydroperoxide, hydroperoxide, ketone peroxide, diacyl peroxide, peroxy ketal, peroxy ester, peroxy dicarbonate, or a mixture thereof.

  The addition amount of the second radical polymerization initiator is preferably larger than the addition amount of the first radical polymerization initiator. Preferably, the addition amount of the second radical polymerization initiator is 1.5 times or more, more preferably 2 to 10 times the addition amount of the first radical polymerization initiator. When the amount of the second radical polymerization initiator added is increased by the method of the present invention, the non-allergenicity of the produced urushiol polymer can be sufficiently achieved. This is because the second radical polymerization initiator is used in a large amount. This is probably because the allergenic part of the urushiol molecule is almost completely consumed.

  The average particle size of the urushiol polymer produced according to the present invention is several tens to several hundreds of nanometers and is non-allergenic. In addition, the urushiol polymer of the present invention can be commercialized as an aqueous emulsion, and further dried to be commercialized as a powder. The urushiol polymer of the present invention does not induce the inherent allergy expressed by the lacquer component, and has excellent anti-oxidant properties, so that the composition needs to be antibacterial, antifungal and antiatopic. It can be added as an anti-atopic ingredient. For example, it can be effectively applied to compositions that produce soaps, cosmetics, natural dyes, paints, various coating agents, extruded or injection plastic products and the like.

  In particular, the urushiol polymer of the present invention is different from urushiol in that it has excellent compatibility with ordinary coating materials or paints, and exhibits unique functions such as antibacterial, insecticidal and antifungal properties of existing lacquer coatings. It can be effectively used for the production of new coating materials or paints.

  Hereinafter, the configuration of the present invention will be described in detail with reference to examples. However, the scope of rights of the present invention is not limited to the following examples.

[Example 1]
A reactor equipped with a stirrer, thermometer, dropping tank and reflux condenser was charged with 300 parts by weight of deionized water, 100 parts by weight of urushiol and 40 parts by weight of acrylic acid, and stirred at room temperature (20 ° C.). An aqueous monomer dispersion was prepared. While stirring the aqueous monomer dispersion, 5 parts by weight of t-butyl hydroperoxide was added dropwise for 30 minutes, the temperature was maintained at 70 ° C. for 30 minutes, and then cooled to room temperature to prepare a prepolymer aqueous solution. As a neutralizing agent, 10 parts by weight of triethylamine was dropped into the aqueous prepolymer solution for 30 minutes to produce a neutralized prepolymer.

  The neutralized prepolymer was stirred while dropping 300 parts by weight of deionized water for 30 minutes to prepare a prepolymer aqueous emulsion. The emulsion was stirred at 50 ° C., 10 parts by weight of t-butyl hydroperoxide was added dropwise for 1 hour, and then kept at 80 ° C. for 2 hours to produce a urushiol polymer aqueous emulsion. The produced aqueous emulsion was filtered, and the obtained filter cake was dried to produce urushiol polymer powder. The produced urushiol polymer powder had a uniform particle distribution, and the average particle size of the fine particles was 0.2 μm or less.

[Example 2]
300 parts by weight of deionized water, 100 parts by weight of urushiol, 35 parts by weight of methacrylic acid and 0.1 parts by weight of cobalt octoate in a reaction vessel equipped with a stirrer, thermometer, dropping tank and reflux condenser And stirred at room temperature (20 ° C.) to prepare an aqueous monomer dispersion. While stirring the aqueous monomer dispersion, 30 parts by weight of hydrogen peroxide (30% aqueous solution) was added dropwise for 1 hour, kept at a temperature of 80 ° C. for 30 minutes, and then cooled to room temperature to produce a prepolymer aqueous solution. did. As a neutralizing agent, 10 parts by weight of triethylamine was dropped into the aqueous prepolymer solution for 30 minutes to produce a neutralized prepolymer.

  The neutralized prepolymer was stirred while dropping 300 parts by weight of deionized water for 30 minutes to prepare a prepolymer aqueous emulsion. The emulsion was stirred at 50 ° C., 65 parts by weight of hydrogen peroxide (30% aqueous solution) was added dropwise for 2 hours, and held at 80 ° C. for 2 hours to produce a urushiol polymer aqueous emulsion. The produced aqueous emulsion was filtered, and the obtained filter cake was dried to produce urushiol polymer powder. The produced urushiol polymer powder had a uniform particle distribution, and the average particle size of the fine particles was 0.2 μm or less.

[Example 3]
Except that 40 parts by weight of vinyl sulfonic acid was used in place of methacrylic acid, the same experiment as in Example 2 was repeated to produce fine urushiol polymer powder. The produced urushiol polymer powder had a uniform particle distribution, and the average particle size of the fine particles was 0.2 μm or less.

[Example 4]
Except that 45 parts by weight of vinyl phosphoric acid was used in place of methacrylic acid, the same experiment as in Example 2 was repeated to produce fine urushiol polymer powder. The produced urushiol polymer powder had a uniform particle distribution, and the average particle size of the fine particles was 0.2 μm or less.

[Comparative Example 1]
100 parts by weight of urushiol, 35 parts by weight of methacrylic acid and 0.1 part by weight of cobalt octylic acid were added to a reaction vessel equipped with a stirrer, thermometer, dropping tank and reflux condenser, and after mixing, hydrogen peroxide ( 30 parts by weight of 30% aqueous solution) was dropped for 1 hour, the temperature was kept at 80 ° C. for 30 minutes, and then cooled to room temperature to produce a prepolymer. As a neutralizing agent, 10 parts by weight of triethylamine was added dropwise to the prepolymer for 30 minutes to produce a neutralized prepolymer.

  The neutralized prepolymer was stirred while dropping 300 parts by weight of deionized water for 30 minutes to prepare a prepolymer aqueous emulsion. The emulsion was brought to 50 ° C. with stirring, 65 parts by weight of hydrogen peroxide (30% aqueous solution) was dropped for 2 hours, and then kept at 80 ° C. for 2 hours to produce a urushiol polymer aqueous emulsion. The produced aqueous emulsion was filtered, and the obtained filter cake was dried to produce urushiol polymer powder. The produced urushiol polymer powder had a non-uniform particle distribution and an average particle size of 1 μm or more.

[Comparative Example 2]
Except that 40 parts by weight of acrylic acid was used in place of methacrylic acid, the experiment was repeated with Comparative Example 1 to produce fine urushiol polymer powder. The produced urushiol polymer powder had a non-uniform particle distribution and an average particle size of 1 μm or more.

  Skin irritation and antibacterial properties were tested on compositions obtained by mixing the urushiol polymer powders obtained in Examples 1 to 4 and Comparative Examples 1 and 2 and glycerin at a weight ratio of 1: 3. For skin irritation, a patch applied with the composition was applied to 30 participants who participated in the test, the test substance was removed 48 hours later, and the skin condition after 30 minutes and 24 hours after removal was observed. Expressed as the number of people with irritation. Antibacterial activity was measured by adding 5% urushiol polymer aqueous emulsion to aqueous urethane resin, producing a 10μm thick film, inoculating E. coli and staphylococcus, and then measuring the number of viable bacteria. It was expressed as survival rate (%). The results are shown in Table 1.

表１に示すように、本発明の方法で製造したウルシオール重合体の非アレルギー性及び抗菌性は全て優良であったが、出発モノマーを直接重合してプリポリマーを製造する比較実施例１及び２では、非アレルギー性が十分でないことが示された。

As shown in Table 1, the non-allergenic and antibacterial properties of the urushiol polymer produced by the method of the present invention were all excellent, but Comparative Example 1 in which the prepolymer was produced by directly polymerizing the starting monomer and 2 showed that non-allergenicity was not sufficient.

Claims (10)

A method for producing a non-allergenic urushiol polymer comprising:
Mixing urushiol, an ethylenically unsaturated monomer having a hydrophilic functional group capable of reacting with a neutralizing agent to form a hydrophilic salt and water, and stirring to obtain an aqueous monomer dispersion;
A step of adding a first radical polymerization initiator having a peroxy group while stirring the aqueous monomer dispersion to react to obtain a prepolymer;
Adding a neutralizing agent to the prepolymer to obtain a neutralized prepolymer;
Mixing the neutralized prepolymer with water to obtain a prepolymer aqueous emulsion; and
Adding a second radical polymerization initiator having a peroxy group to the prepolymer aqueous emulsion and reacting it to obtain a urushiol polymer aqueous emulsion;
Including a method.   The production method according to claim 1, further comprising the step of drying the urushiol polymer aqueous emulsion. The hydrophilic functional group, -COOM (M is hydrogen, an alkali metal or ammonium), - _SO 3 M (M is hydrogen, an alkali metal or ammonium), _- PO 3 HM (M is hydrogen, an alkali metal or ammonium), -PO 3 _{M '(M'} is an alkaline earth metal) selected from and mixtures thereof the process of claim 1.   The first radical polymerization initiator and the second radical polymerization initiator may be the same or different from each other, t-butyl hydroperoxide, ethyl hydroperoxide, hydroperoxide, ketone peroxide, diacyl peroxide, peroxyketal, peroxyester, The production method according to claim 1, which is selected from peroxydicarbonate and a mixture thereof.   The production method according to claim 1, wherein the neutralizing agent is selected from an organic base, an inorganic base, and a mixture thereof.   The manufacturing method of Claim 1 whose mixing ratio of the ethylenically unsaturated monomer which has the said hydrophilic functional group is 1-100 weight part with respect to 100 weight part of said urushiol.   The manufacturing method of Claim 1 whose addition amount of the said 2nd radical polymerization initiator is 1.5 times or more compared with the addition amount of the said 1st radical polymerization initiator.   The manufacturing method of Claim 1 whose average particle diameter of the said non-allergenic urushiol polymer is smaller than 0.5 micrometer.   The non-allergic urushiol polymer manufactured by the method of any one of Claims 1-8. Use of the non-allergic urushiol polymer according to claim 9 as an anti-atopic application .