JP2008050415A - Method for producing terpene and/or allylphenol-based polymer, terpene and/or allylphenol-based polymer and application thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a terpene and/or allylphenol-based polymer, advantageous in industrial production. <P>SOLUTION: The method for producing the terpene and/or allylphenol-based polymer involves polymerizing the terpene-based compound having a carbon-carbon double bond, and/or the allylphenol, or a mixture of the terpene-based compound having the carbon-carbon double bond, and/or the allylphenol, with other additionally polymerizable unsaturated compound in a basic hydrogen peroxide aqueous solution under heating. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a method for producing a terpene and / or allylphenol polymer which is advantageous for industrial production.
The present invention also relates to an antibacterial agent, a fungicide, and a pest repellent containing a terpene or / and allylphenol polymer.

  Conventionally, terpene compounds are known to have antibacterial properties, antifungal properties, and biological repellent properties (for example, see Non-Patent Documents 1 and 2). In addition, allylphenol, which is a synthetic compound similar in structure to a terpene compound, is also known to have antibacterial properties, antifungal properties, and biological repellent properties. However, since these terpene compounds and allylphenols are weak but volatile, there is a problem that their efficacy cannot be sustained over a long period of time.

  On the other hand, a terpene compound uses a double bond (carbon-carbon double bond) possessed by a terpene compound to radically copolymerize the terpene compound and vinyl acetate to increase the molecular weight. It is known that the volatility of the system compound can be suppressed (see, for example, Non-Patent Document 2). However, it is not clarified at all what kind of the copolymer can be practically applied as an antibacterial agent, an antifungal agent, or a pest repellent. In addition, allylphenol can maintain its antibacterial, antifungal and biological repellent efficacy by increasing the molecular weight, and can it be applied practically as an antibacterial, antifungal and pest repellent. What is not clear about.

Furthermore, for terpene compound polymers, copolymers of terpene compounds with other polymerizable compounds having other double bonds (carbon-carbon double bonds), allylphenol polymers, etc. No advantageous method has been found. For example, Patent Document 1 proposes that a polymer of terpene alcohol, which is one of terpene compounds, is used as a hydrolysis-resistant polymer for polyurethane raw materials, and heat-reacts terpene alcohol with an organic peroxide. Thus, a polymer of terpene alcohol is obtained. However, this heating reaction is a non-aqueous bulk polymerization using t-butyl peroxide, and is a severe reaction condition in which the reaction temperature is 110 to 180 ° C. in a nitrogen atmosphere, and is a method advantageous for industrial production. That's not true.
JP-A-2-20503 Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal”, Sankyo Publishing, 4-9, February 25 China Regional Industry-Academia-Government Collaboration Symposium in Yamaguchi Abstracts, p. 63

In view of the above circumstances, the problem to be solved by the present invention is to provide a method for producing a terpene and / or allylphenol polymer that is advantageous for industrial production.
Another object of the present invention is to provide a terpene and / or allylphenol polymer that can be practically applied as an antibacterial agent, an antifungal agent, and a pest repellent.

  As a result of intensive studies to solve the above problems, the present inventors have dissolved a terpene compound having a carbon-carbon double bond and an allylphenol having a structure similar to that of the terpene compound in a basic hydrogen peroxide solution. When dispersed and heated to about 50-100 ° C., the polymerization reaction proceeds rapidly, and a polymer having a practical level of antibacterial action, antifungal action, and pest repellent action can be obtained, and further carbon-carbon When a mixture of a terpene compound having a double bond or / and allylphenol and another addition polymerizable unsaturated compound is dissolved or dispersed in a basic hydrogen peroxide solution and heated to about 50 to 100 ° C., It has been found that the polymerization reaction proceeds rapidly and a polymer (copolymer) having a practical level of antibacterial action, antifungal action and pest repellent action can be obtained. A copolymer of a terpene compound having a carbon-carbon double bond and / or allylphenol and a (meth) acrylic compound (particularly, hydroxyalkyl (meth) acrylate, hydroxyalkyl crotonate, etc.) It has also been found that by copolymerizing a (meth) acrylic compound, processability is improved, and processing into a film or the like or mixing into a molding material is facilitated.

That is, the present invention is as follows.
(1) A terpene compound or / and allylphenol having a carbon-carbon double bond, or a terpene compound or / and allylphenol having the carbon-carbon double bond and another addition-polymerizable unsaturated compound A method for producing a terpene and / or allylphenol-based polymer, wherein the mixture is polymerized in a basic hydrogen peroxide solution under heating.
(2) A terpene compound or / and allylphenol having a carbon-carbon double bond, or a terpene compound or / and allylphenol having the carbon-carbon double bond and another addition polymerizable unsaturated compound A method for producing a terpene and / or allylphenol-based polymer, wherein the mixture is put into basic hydrogen peroxide water, stirred, emulsified, and polymerized under heating.
(3) The method according to (1) or (2) above, wherein the heating temperature is 50 to 100 ° C.
(4) The method according to (1) or (2) above, wherein the atmosphere surrounding the basic hydrogen peroxide solution is an air atmosphere.
(5) A terpene compound having a carbon-carbon double bond is citral, citronellal, citronellol, eugenol, geraniol, isoeugenol, α-ionone, limonene, terpinolene, γ-terpinene, 3-carene, perylaldehyde, β- The method according to any one of (1) to (4) above, which is at least one selected from ionone, β-pinene, alloocimene, myrcene, α-terpineol and linalool.
(6) The method according to any one of (1) to (5) above, wherein the other addition polymerizable unsaturated compound is a vinyl ester compound or / and a (meth) acrylic compound.
(7) An allylphenol polymer having an average degree of polymerization of 3 to 10.
(8) A copolymer of a terpene compound or / and allylphenol having a carbon-carbon double bond and a (meth) acrylic compound, having an average degree of polymerization of 2 to 100, A terpene or / and allylphenol polymer in which the copolymerization ratio of a terpene compound or / and allylphenol having a heavy bond and a (meth) acrylic compound is 1: 1 to 20 (molar ratio).
(9) The polymer according to (8), wherein the (meth) acrylic compound is hydroxyalkyl (meth) acrylate.
(10) A copolymer of allylphenol and a vinyl ester compound, having an average degree of polymerization of 2 to 100, and a copolymerization ratio of allylphenol and the vinyl ester compound of 1: 1 to 20 (molar ratio). Allylphenol polymer.
(11) The polymer as described in (10) above, wherein the vinyl ester compound is vinyl acetate.
(12) An antibacterial agent containing the polymer according to any one of (7) to (11) above.
(13) An antifungal agent containing the polymer according to any one of (7) to (11) above.
(14) A pest repellent containing the polymer according to any one of (7) to (11) above.

  In the present invention, “terpene or / and allylphenol polymer” means “polymer of terpene compound”, “polymer of allylphenol”, “copolymer of terpene compound and allylphenol”. Or “terpene compound or / and copolymer of allylphenol and other addition polymerizable unsaturated compound”.

  According to the method for producing a terpene and / or allylphenol polymer of the present invention, a polymerization reaction proceeds at a relatively low reaction temperature in a water-based reaction system in an air atmosphere, and can be practically used in a relatively short time. A polymer having a level of antibacterial action, antifungal action and pest repellent action can be produced. Therefore, the reaction control is easy, the safety is excellent, and the production cost can be reduced, which is advantageous for the production of terpenes and / or allylphenol polymers on an industrial scale.

  The terpene and / or allylphenol polymer produced by the method of the present invention has a practical level of antibacterial action, antifungal action, and insect pest repellent action, and also eliminates the problem of volatilization due to polymerization. These effects persist for a long time. Furthermore, since the functionalization involved in the antibacterial action, the antifungal action, and the insect pest repellent action is locally increased due to the polymerization, these actions are increased by the accumulation effect.

  Among the terpenes and / or allylphenol polymers, in particular, for the terpene compounds or / and copolymers of allylphenol and (meth) acrylic compounds, (meth) acrylic compounds are copolymerized. As a result, processability is improved, processing into a film or the like, and mixing into a molding material is facilitated. Further, the (meth) acrylic compound is a hydroxyalkyl (meth) acrylate or hydroxyalkyl crotonate. In the case of a compound containing a hydroxyalkyl group, hydrophilicity is imparted to the copolymer. Therefore, the copolymer can be widely applied to various uses in which the polymer itself is required to have hydrophilicity and various uses in which an aqueous solvent is used.

The present invention will be described in detail below.
The production method of the terpene and / or allylphenol polymer of the present invention is a terpene compound having a carbon-carbon double bond or / and allylphenol, or a terpene compound having the carbon-carbon double bond, or / And a mixture of allylphenol and other addition-polymerizable unsaturated compounds (that is, addition-polymerizable unsaturated compounds other than terpene compounds and allylphenol) is polymerized under heating in basic hydrogen peroxide water. The main feature is that

  In the method of the present invention, it is important to use basic hydrogen peroxide water, and the polymerization reaction proceeds using a radical generated from hydrogen peroxide as an initiator. The polymerization form (radical polymerization form) may be any of aqueous solution polymerization, suspension polymerization, emulsion polymerization, etc., but the point that water is used as a medium and the generated polymer (terpene or / and allylphenol polymer) are dispersed in water. It is obtained as latex that is emulsified in the medium, and can be used as it is for paints (antibacterial paints, antifouling paints, etc.) and adhesives (antibacterial adhesives, antifouling adhesives, etc.), or modification of paints, adhesives, etc. Emulsion polymerization is preferred because it can be used as it is as an agent. That is, a terpene compound having a carbon-carbon double bond and / or allylphenol, or a terpene compound having a carbon-carbon double bond or / and a mixture of allylphenol and another addition polymerizable unsaturated compound Is preferably put into basic hydrogen peroxide water, stirred, emulsified, and polymerized under heating.

  In the method of the present invention, the basic hydrogen peroxide solution is a monomer (that is, a terpene compound having a carbon-carbon double bond or / and allylphenol, or a terpene compound having a carbon-carbon double bond, or / And a mixture of allylphenol and another addition-polymerizable unsaturated compound) is preferably used in an amount of 2 volumes or more. That is, it is considered that the water-based reaction system in which a sufficient amount of water is present makes it easy for the positions of double bonds in the terpene structure in terpenes and the like to approach and the polymerization reaction proceeds rapidly. Therefore, the amount of the basic hydrogen peroxide solution is more preferably 5 volume times or more with respect to the monomer. In addition, although the upper limit of the quantity of basic hydrogen peroxide water is not specifically limited, 10 volume times or less is preferable from a viewpoint of reaction control, such as reaction rate.

  The concentration of hydrogen peroxide in the basic hydrogen peroxide solution is preferably 5 to 15% by weight, more preferably 8 to 10% by weight, based on the entire hydrogen peroxide solution. If the concentration of hydrogen peroxide is less than 5% by weight, the reaction rate becomes slow and the efficiency tends to decrease. If it exceeds 15% by weight, the reaction tends to be too intense, which is not preferable.

  Basic hydrogen peroxide solution is prepared by blending alkali with hydrogen peroxide solution. Usually, hydrogen peroxide solution and aqueous alkali solution are mixed, or water is further mixed with these. Prepared. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide; ammonia, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, pentylamine, octylamine, nonylamine Amines such as decylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, cyclohexylamine, etc. Although mentioned, alkali metal hydroxide is preferable from points, such as cost, and sodium hydroxide is more preferable.

  The pH of the basic hydrogen peroxide solution is generally 12 to 14, preferably 12 to 13. A pH of less than 12 is not preferable because the reaction rate tends to extremely decrease. In addition, even if pH is 14, the reaction is not greatly affected, but the amount of alkali used is increased, which is disadvantageous in terms of cost.

  In the method of the present invention, the atmosphere surrounding the polymerization system (that is, the basic hydrogen peroxide solution) does not need to be an inert gas atmosphere such as nitrogen, and the polymerization reaction proceeds sufficiently in an air atmosphere. Therefore, the temperature of the polymerization reaction can be substantially controlled only by temperature control.

  The polymerization temperature (heating temperature) is generally 50 to 100 ° C, preferably 70 to 80 ° C. In the method of the present invention, the polymerization reaction proceeds rapidly at such a relatively low heating temperature.

  As described above, the method of the present invention preferably adopts a polymerization form of emulsion polymerization. However, the monomer during emulsion polymerization (that is, a terpene compound having a carbon-carbon double bond and / or allylphenol, or A method of emulsifying a terpene compound having a carbon-carbon double bond or / and a mixture of allylphenol with another addition polymerizable unsaturated compound) in basic hydrogen peroxide water has been conventionally used in emulsion polymerization. A common stirring device (for example, a combination of a homogenizer, a stirrer, and a reaction vessel) may be used. The terpene compound and allylphenol have preferable properties that can be sufficiently emulsified if they are put into water and stirred with a stirrer, and a surfactant for emulsification is not always necessary. That is, in the method of the present invention, a target polymer (a polymer having a practical level of antibacterial action, fungicidal action, and pest repellent action) is obtained in an aqueous solvent without substantially using a surfactant. Can be manufactured. In the case of using the surfactant, an appropriate amount of a known anionic surfactant, cationic surfactant, nonionic surfactant or the like used in general emulsion polymerization may be used.

  In the method of the present invention, the polymerization time is usually 24 to 48 hours when a terpene compound polymer, an allylphenol polymer, or a copolymer of a terpene compound and allylphenol is produced. In the case of producing a copolymer of a compound or / and allylphenol and another addition polymerizable unsaturated compound, it takes about 2 to 24 hours. That is, in the method of the present invention, a terpene compound or / and a copolymer of allylphenol and another addition polymerizable unsaturated compound can be produced in a very short time.

  After completion of the polymerization reaction, the reaction system is usually heated to 100 ° C. or higher in order to remove water and unreacted monomers from the reaction product. In this case, the heating time is preferably about 1 to 4 hours.

  The method for recovering (isolating) the polymer is not particularly limited. For example, the method of distilling off the solvent and residual monomers under reduced pressure, the reaction mixture is put into a large amount of poor solvent for the polymer, and the precipitate is filtered. The method etc. which collect | recover by are mentioned.

  In the method of the present invention, a terpene or / and allylphenol polymer can be produced in a yield of preferably 30% or more, more preferably 50% or more. In the case of a copolymer with a polymerizable unsaturated compound, it can be produced at a high yield of 60% or more, preferably 70% or more, and more preferably 90% or more.

  The terpene compound having a carbon-carbon double bond used in the method of the present invention is not particularly limited, but preferably citral, citronellal, citronellol, eugenol, geraniol, isoeugenol, α-ionone, limonene, terpinolene, γ -Terpinene, 3-carene, peryl aldehyde, β-ionone, β-pinene, alloocimene, myrcene, α-terpineol, linalool and the like. These can use 1 type, or 2 or more types.

  The addition polymerizable unsaturated compound other than the terpene compound and allylphenol that can be used in the method of the present invention is not particularly limited as long as it can be radically copolymerized with the terpene compound or allylphenol. From the viewpoint of reactivity with terpene compounds and allylphenol, vinyl ester compounds, (meth) acrylic compounds and the like can be mentioned. The “(meth) acrylic compound” in the present invention means a compound having a (meth) acryloyl group in the skeleton. In addition to (meth) acrylic acid and esters thereof, crotonic acid and esters thereof are used. It also includes methylacrylic acid compounds such as The vinyl ester compound and the (meth) acrylic compound may be used alone or in combination.

  Examples of the vinyl ester compound include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl benzoate, vinyl valerate, vinyl caprate, vinyl laurate, and vinyl stearate. And vinyl ester compounds. Among these, a vinyl ester compound having 4 to 9 carbon atoms is preferable, and vinyl acetate and vinyl benzoate are particularly preferable from the viewpoint of easy availability of raw materials, and molding when a copolymer with terpenes or allylphenol is used. From the viewpoint of ease of application to materials and films, vinyl acetate is preferred. These vinyl ester compounds can be used alone or in combination of two or more.

  Examples of the (meth) acrylic compound include (meth) acrylic acid, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, crotonic acid, alkyl crotonic acid, hydroxyalkyl crotonic acid and the like. The alkyl part of (alkyl) (meth) acrylate, hydroxyalkyl (meth) acrylate, alkyl crotonic acid, and hydroxyalkyl crotonic acid is preferably linear or branched having 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. It is a chain alkyl. Specific examples of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid isooctyl, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl, etc. Is mentioned. Specific examples of alkyl crotonic acid and hydroxyalkyl crotonic acid include, for example, methyl crotonic acid, butyl crotonic acid, crotonic acid-ethylhexyl, 2-hydroxyethyl crotonic acid, 2-hydroxypropyl crotonic acid, and the like.

  The (meth) acrylic compound is preferably hydroxyalkyl (meth) acrylate, particularly from the viewpoint of imparting hydrophilicity to the copolymer, imparting reactivity, etc., and 2-hydroxyethyl (meth) acrylate is preferred. Particularly preferred.

  The terpene and / or allylphenol polymer obtained by the method of the present invention is generally a polymer having an average degree of polymerization of 3 to 100. That is, in the polymer of the terpene compound and the polymer of allylphenol, the degree of polymerization is 3 to 20 (preferably 3 to 15, particularly preferably 3 to 10, more preferably 2 to 5). Alternatively, and / or in a copolymer of allylphenol and another addition polymerizable unsaturated compound, the degree of polymerization is 3 to 100 (preferably 3 to 50). A polymer having such an average degree of polymerization has an excellent antibacterial action, antifungal action, and pest repellent action.

  In the present invention, as described above, instead of the terpene compound, or together with the terpene compound, allylphenol having a structure similar to that of eugenol is used. It is a novel finding that a polymer having an antibacterial action, antifungal action, and pest repellent action at a practical level can be obtained by being copolymerizable with other addition polymerizable unsaturated compounds. It was.

  That is, the allylphenol polymer, copolymer of allylphenol and vinyl ester compound, and copolymer of allylphenol and (meth) acrylic compound obtained by the above-described method of the present invention are at a practical level. It has not been known so far to be a polymer having antibacterial action, antifungal action, and pest repellent action. Therefore, when a copolymer of allylphenol and a vinyl ester compound was produced by a general emulsion polymerization method using ammonium peroxodisulfate as a polymerization initiator and polyvinyl alcohol (PVA) as a dispersion stabilizer (emulsifier). The copolymer of allylphenol and vinyl ester compound (especially vinyl acetate) thus obtained also has a specific polymerization degree and copolymerization ratio, so that it can have a practical level of antibacterial action, antifungal action, pest It was found to have a repellent effect.

  Furthermore, when a copolymer of allylphenol and a (meth) acrylic compound was produced by a bulk polymerization method using general 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator, The copolymer of allylphenol thus obtained and a (meth) acrylic compound (especially a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl acrylate) also has a specific degree of polymerization and copolymerization ratio. Thus, it was found that it has a practical level of antibacterial action, antifungal action, and pest repellent action.

  Furthermore, in the bulk polymerization method using 2,2′-azobisisobutyronitrile (AIBN), which is a general polymerization initiator, a terpene compound (terpene compound having a carbon-carbon double bond) and ( When a copolymer with a meth) acrylic compound was produced, the copolymer thus obtained (particularly a copolymer of a terpene compound and a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl acrylate). It was also found that having a specific degree of polymerization and copolymerization ratio has practical levels of antibacterial action, antifungal action, and pest repellent action.

  Therefore, the present invention relates to a terpene compound or / and allylphenol having a carbon-carbon double bond, a (meth) acrylic compound (particularly, a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl acrylate), and the like. The average polymerization degree is 2 to 100, and the copolymerization ratio of the terpene compound or / and allylphenol and the (meth) acrylic compound is 1: 1 to 20 (molar ratio). A terpene and / or allylphenol polymer useful as an antibacterial agent, antifungal agent or pest repellent is provided.

  That is, if the average degree of polymerization and the copolymerization ratio are both within the above ranges, the copolymer has excellent antibacterial action, antifungal action, and pest repellent action. Furthermore, from the viewpoints of low volatility (odorlessness) and durability of the effect, the average degree of polymerization of the copolymer is preferably 3 to 50, more preferably 3 to 15, and 3 to 5. It is particularly preferred that there is. The copolymerization ratio is more preferably in the range of 1: 1 to 8 in terms of molar ratio from the viewpoint of the functional group accumulation effect.

  Further, the present invention is a copolymer of allylphenol and a vinyl ester compound (particularly vinyl acetate), having an average degree of polymerization of 2 to 100, and a copolymerization ratio of allylphenol and the vinyl ester compound of 1: Provided is an allylphenol-based polymer which is useful as an antibacterial agent, antifungal agent or pest repellent having a molar ratio of 1 to 20 (molar ratio).

  That is, if the average degree of polymerization and the copolymerization ratio are both within the above ranges, the copolymer has excellent antibacterial action, antifungal action, and pest repellent action. Furthermore, from the viewpoints of low volatility (odorlessness) and sustainability of the effect, the average degree of polymerization of the copolymer is preferably 3 to 50, more preferably 10 to 50, and 10 to 30. It is particularly preferred that there is. The copolymerization ratio is more preferably in the range of 1: 1 to 8 in terms of molar ratio from the viewpoint of the functional group accumulation effect.

  In the present invention, the copolymerization ratio is determined by quantifying and calculating the carbon content (%) of the copolymer using an elemental analyzer (Perkin Elmer model 2400, CHNS / O). Say.

  In the present invention, the average degree of polymerization refers to an average degree of polymerization obtained by quantifying and calculating the content of nitrogen at the end of the polymer using an elemental analyzer (Perkin Elmer 2400 type, CHNS / O). In addition, about the polymer which does not have nitrogen at the terminal, it is an average degree of polymerization measured by polyethylene glycol as a standard sample by GPC (manufactured by Shimadzu Corporation, Chromatopack C-R3A).

  In the terpene or / and allylphenol-based polymer of the present invention, the terpenes are particularly preferably eugenol, geraniol, citral, citronellal, citronellol, perillaldehyde, nerol, linalool, etc., geraniol, Linalool is particularly preferred. Moreover, geraniol, (gamma) -terpinene, etc. are especially preferable from a viewpoint of an antifungal action. Further, from the viewpoint of pest repellent action, isoeugenol and eugenol are particularly preferable, and isoeugenol is particularly preferable. Allylphenol is excellent in antibacterial action, antifungal action, and pest repellent action.

The terpene and / or allylphenol polymer of the present invention is useful as an antibacterial agent, a fungicide, and a pest repellent.
The target bacteria when used as an antibacterial agent are pathogenic bacteria such as Escherichia coli, Bacillus subtilis, Enterococcus, Pneumoniae, Proteus mitavibilis, Streptococcus pyogenes, and Pseudomonas aeruginosa.
The target moths when used as an antifungal agent are blue mold, black mold and the like, and particularly exhibit excellent antifungal action against blue mold and black mold.
The target pests when used as a pest repellent are slugs, snails, termites, ants, keratoids, ticks, protists (eg, amoeba, Paramecium, Aomidoro, etc.), especially slugs, ants, protozoa Excellent pest repellent action on living organisms.

  When used as an antibacterial agent, an antifungal agent, or a pest repellent, the usage form is not particularly limited. Examples of the usage form are: (A) the terpene and / or allylphenol polymer of the present invention. (B) The terpene or / and allylphenol polymer of the present invention is formed or formed into a film, (C) The terpene or / and allylphenol polymer of the present invention is a solution. (D) The terpene or / and allylphenol-based polymer of the present invention is made into a solution and applied to a substrate (film, tape, fiber, molded article, etc.), or the substrate is terpene of the present invention and / or It is immersed in an allylphenol polymer solution, dried, and the substrate surface is coated with the terpene polymer of the present invention. (E) The terpene polymer of the present invention is mixed with a paint. (F) Base sex The latex of the terpene and / or allylphenol polymer of the present invention produced by emulsion polymerization in hydrogen peroxide solution is applied to a substrate (film, tape, fiber, molded product, etc.), or the substrate is immersed in the latex. And drying to coat the surface of the base material with the terpene polymer of the present invention, (G) mixing the latex with an adhesive, or using it as it is as an adhesive.

  Specific examples of these modes of use include antibacterial catheters coated with a solution or latex of the terpene and / or allylphenol-based polymer of the present invention and / or dried on a catheter; A sanitary tissue dipped in an allylphenol polymer solution or latex and dried, and a slug repellent tape and ant coated with the terpene or / and allylphenol polymer solution or latex of the present invention coated on a tape and dried. Anti-repellent tape, anti-fouling paint for ship bottom mixed with terpene or / and allylphenol polymer of the present invention in paint, and net to dip coating terpene or / and allylphenol polymer solution or latex of the present invention to prevent coating Dirty net, terpene and / or allylfe of the present invention Disinfectant or lotion containing a water-based polymer aqueous solution or latex, fruit wrapping paper obtained by immersing and drying the wrapping paper in the terpene or / and allylphenol-based polymer aqueous solution or latex of the present invention, and the terpene of the present invention Or / and a drain pipe, an antiseptic label, artificial soil etc. which shape | molded the allyl phenol type polymer are mentioned.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited to the Example described below.

Examples 1-14
Prepare 12 types of monomers (allylphenol and 13 types of terpenes (isoeugenol, eugenol, geraniol, citral, citronellol, citronellal, linalool, nerol, α-ionone, phthal, peryl aldehydr, limonene, myrcene) The polymerization reaction was carried out by

Basic hydrogen peroxide solution (about 5 ml of 0.5 mol / l NaOH aqueous solution, 10 ml of 35% hydrogen peroxide (H ₂ O ₂ ) water and 35 ml of mixed solution of water 20 ml (pH: 13, hydrogen peroxide concentration: 10% by weight)) and 100 mmol of monomer (based on one double bond) were placed in a sample bottle (110 ml), stirred vigorously at room temperature to make it emulsion, and then the temperature was gradually raised. The reaction was performed at about 70 ° C. for 1 day. Then, water was removed with a 100 ° C. oil bath. Acetone was added and the reaction was removed and separated from NaOH. The filtrate was applied to an evaporator. This operation (decantation) was performed a few times to purify the synthesized product. Table 1 below shows the yield of the produced polymer. In addition, confirmation of polymer production was performed by FT-IR. FIG.1 and FIG.2 is the example, and shows the measurement result of FT-IR of allylphenol and an allylphenol polymer.

  Here, the yield of linalool is extremely low because the molecular structure in which the hydroxyl group unique to linalool exists in the middle of the molecule has an effect, and when it is dispersed in water, it does not orient in a certain direction and the double bond is sufficient. This is probably because bulk polymerization is also occurring due to the lack of proximity. However, the presence of water and the action of hydrogen peroxide were observed in controlling the polymerization reaction of linalool.

Examples 15-26
The same as the above Examples (Examples 1 to 14) except that a mixture of terpenes (11 species) or allylphenol (50 mmol) and 2-hydroxyethyl acrylate (100 mmol) described in Table 2 below was used as a monomer. The polymerization reaction was carried out by the procedure described above. Table 2 below shows the yield of the produced polymer. In addition, confirmation of polymer production was performed by FT-IR.

The average degree of polymerization of the polymers obtained in Examples 1 to 26 was determined by the following method. Moreover, the copolymerization ratio of the copolymers obtained in Examples 15 to 26 was determined by the following method. The measurement results of the terpene compound or homopolymer of allylphenol (Examples 1 to 12) are shown in Table 3, and the copolymer of terpene compound or allylphenol and 2-hydroxyethyl acrylate (Examples 15 to 26). Table 4 shows the measurement results.
[Average polymerization degree]
Using an elemental analyzer (Perkin Elmer model 2400, CHNS / O), the content of nitrogen at the end of the polymer was determined and calculated.
[Copolymerization ratio]
Using an elemental analyzer (Perkin Elmer model 2400, CHNS / O), the carbon content (%) of the copolymer was determined and calculated.

Example 27 (allylphenol-vinyl acetate copolymer)
6 g of polyvinyl alcohol (degree of polymerization 2000) was dissolved in 60 ml of water. After dissolving 1.5 g of sodium acetate in the dissolved polyvinyl alcohol, 60 ml of water was further added. Next, allylphenol and vinyl acetate were added to 30 g. 1/50 mol of ammonium peroxodisulfate (APS) was added as an initiator with respect to the total amount of allylphenol and vinyl acetate.
When the molar ratio of allylphenol to vinyl acetate is 1: 4 (Example 27A)
Allylphenol: Vinyl acetate: APS = 58.8 mmol: 235.3 mmol: 5.88 mmol
When the molar ratio of allylphenol to vinyl acetate is 1: 9 (Example 27B)
Allylphenol: Vinyl acetate: APS = 33.4 mmol: 300.6 mmol: 6.67 mmol
When the molar ratio of allylphenol to vinyl acetate is 1:15 (Example 27C)
Allylphenol: Vinyl acetate: APS = 20.0 mmol: 30.0 mmol: 6.40 mmol
The reaction was carried out for about 3 days. Then, to destroy the micelles, the water was removed, 10 times the product methanol was added, and the mixture was run for 1 to 2 minutes. The polyvinyl alcohol was removed, and the methanol product was blown off with an evaporator to recover the compound.
Moreover, as a reference example, terpenes (isoeugenol) were used instead of allylphenol, and the same polymerization reaction was performed (reference examples 1A to 1C).
These results are shown in Table 5. The average degree of polymerization and the copolymerization ratio were determined by the same method as described above.

Examples 28-46
(Copolymer of terpenes or allylphenol and 2-hydroxyethyl acrylate (HEA))
For terpenes (17 species) and allylphenol shown in Tables 6 to 9 below, 2-hydroxyethyl acrylate (HEA) and 1: 1, 1: 2, 1: 4, and 1: 6 molar ratios, respectively. AIBN was put in a shaker at about 60 ° C. at 0.05 times the total amount and allowed to react for 3-4 hours.
-When the molar ratio of terpenes or allylphenol and HEA is 1: 1 Terfenes or allylphenol: HEA: AIBN = 10mmol: 10mmol: 1.0mmol
-When the molar ratio of terpenes or allylphenol and HEA is 1: 2 Terfenes or allylphenol: HEA: AIBN = 50mmol: 100mmol: 7.5mmol
When the molar ratio of terpenes or allylphenol to HEA is 1: 4 Terfenes or allylphenol: HEA: AIBN = 50mmol: 200mmol: 12.5mmol
-When the molar ratio of terpenes or allylphenol to HEA is 1: 6 Terfenes or allylphenol: HEA: AIBN = 10mmol: 60mmol: 3.5mmol

  A copolymer of allylphenol (AF) and 2-hydroxyethyl acrylate (HEA) (Example 28 (AD)) and a copolymer of eugenol (EG) and 2-hydroxyethyl acrylate (HEA) (Example) 29 (AD)) shows the average degree of polymerization and copolymerization ratio in Tables 10 and 11. The average degree of polymerization and the copolymerization ratio were determined by the same method as described above.

Test Example 1 Hard Volatility Test For citral, the citral polymer of Example 5, geraniol, and the geraniol polymer of Example 4, using a thermal analyzer (manufactured by Shimadzu Corporation, DTG60), under nitrogen flow, 10 Heat analysis was performed by heating at a rate of temperature increase of ° C./min and measuring mass change. The results are shown in FIGS.
From the results shown in FIG. 3, it can be seen that the citral polymer is less volatile than the citral, and the geraniol polymer is less volatile than the geraniol and is less volatile than the geraniol.

Test Example 2 Ant repellent test Example 27A copolymer of allylphenol and vinyl acetate (1: 4), isoeugenol and vinyl acetate copolymer of Reference Example 1A (1: 4), commercially available product (WXH). The following tests were conducted using samples.
A piece of 70 mm square cardboard sheet was placed at two locations, and a suitable amount of attractant with fruit juice mixed with granulated sugar was placed in the center. After applying the sample to the cardboard sheet piece with a brush, the repellency against ants was measured twice after 1 hour and after 3 hours. The repelling rate was calculated by setting the blank repelling rate to 0 with respect to the total of ants at the time of measurement twice. Table 12 shows the results.

Test Example 3 Antibacterial Test For the allylphenol polymer of Example 1 and the terpene compound polymers of Examples 2 to 12 synthesized by emulsion polymerization using basic hydrogen peroxide, antibacterial activity was obtained by the following procedure. A sex test was performed.

1. The components of the medium were placed in a 1000 ml beaker and adjusted to 1000 ml with pure water. Thereafter, the solution in the beaker was ground using a pH meter, and the pH was adjusted to 7.2 with a KOH / HCl solution. This liquid culture medium was divided into two test tubes, each 6 ml, and capped with a silicon stopper. 9 ml of water was taken into the sample tube. Agar was placed in two 500 ml Erlenmeyer flasks, and about 500 ml of a 1000 ml beaker solution was added. The components of Bennett's medium are as follows.
(Benette medium)
Soluble tempun 7.0 g / l
Glucose 5.0 g / l
Peptone 2.0g / l
Meat extract 1.0g / l
Yeast extract 1.0g / l
Agar 18.0g / l
2. When sterilizing and taking out with an autoclave, there is a possibility that hand germs may be accidentally touched, so the mouth of the 500 ml Erlenmeyer flask, the tips for 100 and 1000 μl, the two mouths of the test tube (1) and the sample tube Two mouths were wrapped in aluminum foil and autoclaved.
3. The Erlenmeyer flask and sterilized petri dish that had been autoclaved were placed in a clean bench, and Bennett's medium was poured into the sterilized petri dish. The petri dish lid was slightly opened and cooled, and sealed with parafilm. Thereafter, 100, 1000 μl chips sterilized with petri dish (2), two test tubes, and two sample tubes were stored in a low temperature chamber.
4). Seven types of bacteria with controlled concentrations [E. c → E. E. coli B. s → B. subtilis Bacillus subtilis, E. coli. f → E. faecalis enterococci, K. p → K. pneumoniae pneumoniae, P. pneumoniae. m → P. mirabilis proteus mirabilis (a type of enteric bacteria), S. mirabilis a → S. aureus S. aureus, S. aureus pyogenes streptococci and Streptococcus pyogenes] were used.
5. Seven types of fungi were placed in a Bennett medium with a platinum basket.
6). The synthesized product was dissolved in DMSO, and 75 μl was taken and dropped onto a paper disk (diameter 8 mm). Concentration to be examined at this time was 25 mg (monomer) of terpenes dissolved in 5 ml of DMSO (5000 ppm).
7). A paper disk was placed in the center of a sterile petri dish, covered with a parafilm, and placed in a culture room for 2 days. As a result of the antibacterial test, the antibacterial property was examined by the size of the inhibition circle from the paper disk.
Table 13 below shows the test results.

Test Example 4 Antifungal Test Copolymer (1: 1) of linalool and 2-hydroxyethyl acrylate of Example 35, copolymer of geraniol and 2-hydroxyethyl acrylate (1: 2) of Example 31B, The copolymer of geraniol and 2-hydroxyethyl acrylate of Example 31C (1: 4) and the copolymer of γ-terpinene and 2-hydroxyethyl acrylate of Example 41 (1: 2) were protected by the following operation. A fertility test was performed.

  Prepare a soaked bread in water (blank) and a soaked copolymer in water (sample), cover the bread with saran wrap so that the water does not evaporate, and place it in a cardboard box. And left at about 30 ° C. and observed for wrinkles. As a result, the blanks were regenerated in 5 days. In contrast, the sample impregnated with the copolymer did not reproduce the pupa in 5 days, and the linalool copolymer sample showed pupa reproduction from the 7th day. There was no reproduction of moths.

  From the above test results, it can be seen that the terpenes and / or allylphenol-based polymers of the examples exhibit antibacterial action, antifungal action, and pest repellent action.

  The terpene and / or allylphenol polymer of the present invention can be used as an antibacterial agent, a fungicide, and a pest repellent.

FT-IR spectrum of allylphenol. FT-IR spectrum of allylphenol polymer. Thermal mass change curve of citral and citral polymer. Thermal mass change curves of geraniol and geraniol polymer.

Claims (14)

  A terpene compound having a carbon-carbon double bond and / or allylphenol, or a mixture of the terpene compound having carbon-carbon double bond or / and allylphenol and another addition-polymerizable unsaturated compound. A method for producing a terpene and / or allylphenol-based polymer, wherein polymerization is carried out under heating in basic hydrogen peroxide water.   A terpene compound having a carbon-carbon double bond and / or allylphenol, or a mixture of the terpene compound having carbon-carbon double bond or / and allylphenol and another addition-polymerizable unsaturated compound. A method for producing a terpene and / or allylphenol polymer, characterized in that it is introduced into basic hydrogen peroxide water, stirred, emulsified, and polymerized under heating.   The method of Claim 1 or 2 whose heating temperature is 50-100 degreeC.   The method according to claim 1 or 2, wherein the atmosphere surrounding the basic hydrogen peroxide solution is an air atmosphere.   Terpene compounds having a carbon-carbon double bond are citral, citronellal, citronellol, eugenol, geraniol, isoeugenol, α-ionone, limonene, terpinolene, γ-terpinene, 3-carene, perylaldehyde, β-ionone, β The method according to any one of claims 1 to 4, which is at least one selected from -pinene, alloocimene, myrcene, α-terpineol and linalool.   The method according to any one of claims 1 to 5, wherein the other addition polymerizable unsaturated compound is a vinyl ester compound or / and a (meth) acrylic compound.   An allylphenol polymer having an average degree of polymerization of 3 to 10.   A copolymer of a terpene compound or / and allylphenol having a carbon-carbon double bond and a (meth) acrylic compound, having an average degree of polymerization of 2 to 100, and having a carbon-carbon double bond A terpene or / and allylphenol polymer in which the copolymerization ratio of the terpene compound or / and allylphenol and the (meth) acrylic compound is 1: 1 to 20 (molar ratio).   The polymer according to claim 8, wherein the (meth) acrylic compound is hydroxyalkyl (meth) acrylate.   Allylphenol is a copolymer of allylphenol and a vinyl ester compound, having an average degree of polymerization of 2 to 100, and a copolymerization ratio of allylphenol and the vinyl ester compound of 1: 1 to 20 (molar ratio). Polymer.   The polymer according to claim 10, wherein the vinyl ester compound is vinyl acetate.   The antibacterial agent containing the polymer as described in any one of Claims 7-11.   An antifungal agent comprising the polymer according to any one of claims 7 to 11.   A pest repellent containing the polymer according to any one of claims 7 to 11.

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