WO2006057086A1 - Terpene polymer and use thereof - Google Patents

Abstract

A terpene polymer that is practically applicable as an antibacterial agent, fungicide or pest repellant. There is provided a terpene polymer of 5 to 50 average polymerization degree consisting of a polymer of terpene compound having a hydroxyl or formyl group and a carbon to carbon double bond, or a copolymer, or hydrolyzate thereof, from the terpene compound and a vinyl ester compound, wherein when the terpene polymer is a copolymer, or hydrolyzate thereof, from the terpene compound and a vinyl ester compound, the copolymerization ratio of terpene compound and vinyl ester compound or vinyl alcohol is in the range of 1:2 to 1:25 (molar ratio).

Description

 Specification

 Terpene polymer and use thereof

 Technical field

 The present invention relates to a polymer of a terpene compound, a copolymer of a terpene compound and a butyl ester compound, a terpene polymer which is a hydrolyzate thereof, and a method for producing the same. Furthermore, the present invention relates to an antibacterial agent, an antifungal agent and a pest repellent containing the polymer.

 Background art

 Traditionally, terpene compounds have been known to have antibacterial, antifungal, and biological repellent properties (eg, Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal” Sankyo Publishing, 4-9, Showa 6 1 Published February 25, 2013; see China Regional Industry-Academia-Government Collaboration Symposium in Yamaguchi Abstracts, page 63. However, since terpene compounds are weak but volatile, there is a problem that their effects cannot be sustained over a long period of time.

On the other hand, terpene compounds can be radically copolymerized with butyl acetate using the double bond of terpene compounds, and the volatile properties of terpene compounds can be increased by copolymerization. it is known that it is possible to suppress the (for example, China regional industry-university-government collaboration symposium i _n Yamaguchi Abstracts, reference 6 3 pages). However, it has not been clarified at all what kind of the copolymer can be practically applied as an antibacterial agent, an antifungal agent, or a pest repellent.

 Disclosure of the invention

 The present invention provides a tenolepene polymer that can be practically applied as an antibacterial agent, P-strength agent, and pest repellent.

As a result of intensive studies by the inventor to solve the above problems, when the terpene polymer has an average degree of polymerization within a specific range, and the polymer is a copolymer with a butyl ester compound, It was found that when the copolymerization ratio of the terpene compound and the bull ester compound is a value within a specific range, it has an antibacterial action, an antifungal action and a pest repellent action at a practical level. Furthermore, it has also been found that the hydrolyzate of the copolymer has an antibacterial action, an antifungal action, and a pest repellent action at a practical level. That is, the present invention is as follows. [1] A polymer of a tenolepene compound having a hydroxyl group or a formyl group and having a carbon-carbon double bond, or a copolymer of the terpene compound and a vinyl ester compound or a hydrolyzate thereof. A terpene polymer having an average degree of polymerization of 5 to 50, and when the tenolepene polymer is a copolymer of a tenolepene compound and a butyl ester compound or a hydrolyzate thereof, a terpene compound and vinyl A terpene-based polymer having a copolymerization ratio of 1: 2 to 1:25 (molar ratio) with an ester-icin compound or vinyl alcohol.

[2] A copolymer of a terpene compound and a bull ester compound having an average degree of polymerization of 15 to 50, and a copolymerization ratio of a tenolepene compound and a bühlesteroleic compound is 1: 2 to The terpene polymer according to the above [1], wherein the ratio is 1:25 (monore ratio).

 [3] A hydrolyzate of a copolymer of a terpene compound and a butyl ester compound having an average degree of polymerization of 15 to 50, and a copolymerization ratio of the terpene compound and vinyl alcohol is 1: 2 to The tenolepene polymer according to the above [1], which is 1:25 (molar ratio).

 [4] The terpene polymer according to any one of the above [1] to [3], wherein the bull ester compound is vinyl acetate.

 [5] The tenolepene polymer according to the above [1], which is a polymer of a terpene compound having an average degree of polymerization of 5 to 30.

 [6] The terpene compound is composed of geraniol, citral, citronellal, citrone mouth nore, lina mouth one nore, fanolenesone nore, nero re donore, neguchi nonore, taxonore, eugenol, and isoeugenol. The terpene polymer according to any one of the above [1] to [5], which is at least one selected.

 [7] The method for producing a terpene polymer according to the above [1], wherein a terpene compound or a mixture of a terpene compound and a vinyl ester compound is reacted in the presence of a polymerization initiator.

[8] The method for producing a terpene polymer according to the above [1], wherein a mixture of the tenolepene compound and the vinyl ester compound is reacted in the presence of a polymerization initiator, and then the product is hydrolyzed.

 [9] An antibacterial agent containing the terpene polymer according to any one of [1] to [6].

[10] An antifungal agent comprising the terpene polymer according to any one of [1] to [6]. [11] A pest repellent containing the terpene polymer according to any one of [1] to [6] above.

 According to the present invention, the terpene polymer has a practical level of antibacterial action, antifungal action, and insect pest repellent action, and also eliminates the problem of volatilization due to polymerization. Will last for a long time. Furthermore, polymerization increases the local concentration of functional groups involved in antibacterial, antifungal, and pest repellent effects, and these effects increase due to their accumulation effect.

 Among the polymers, the copolymer of the terpene compound and the butyl ester compound is copolymerized with the bruesterolide compound, so that the processability is improved. Mixing into the molding material is facilitated. Furthermore, since the hydrolyzate of the copolymer is water-soluble, it can be widely applied to various uses in which an aqueous solvent is used.

 Brief Description of Drawings

 Figure 1 shows the FT-IR spectrum of isoeugenol.

 Figure 2 shows the FT—IR spectrum of isoeugenol homopolymer.

 Figure 3 shows the FT-IR spectrum of citral.

 Figure 4 shows the FT—IR spectrum of the citral homopolymer.

 Figure 5 shows the FT-IR spectrum of geraniol.

 Figure 6 shows the FT—IR spectrum of geraniol homopolymer.

 Fig. 7 shows the FT—IR spectrum of geraniol-Zu acetate acetate copolymer.

 Figure 8 shows the Citral TG curve.

 Figure 9 is a TG curve of citral homopolymer.

 Figure 10 is a TG curve of a citral / butyl acetate copolymer.

 Figure 11 shows the TG curve for geraniol.

 Figure 12 is a TG curve of geraniol homopolymer.

 Figure 13 shows the TG curve of geraniol / butyl acetate copolymer.

 Figure 14 is a photograph showing the actual state of antibacterial evaluation in Test Example 2.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a terpene polymer having an average degree of polymerization of 5 to 50, and (1) a tenolepene compound having a hydroxy group or a formyl group and having a carbon-carbon double bond (hereinafter simply referred to as a terpene compound). (2) Copolymer of the terpene compound and vinyl ester compound (copolymerization ratio of terpene compound and vinyl ester compound is 1: 2 to 1:25 (molar ratio)) ) Or (3) The hydrolyzate (the copolymerization ratio of the terpene compound and vinyl alcohol is 1: 2 to 1:25 (molar ratio)), and there are three modes, each of which will be described below. .

 (1) A polymer of a tenolepene compound having a hydroxy group or a formyl group and having a carbon-carbon double bond (hereinafter also simply referred to as a polymer of a terpene compound)

 In the present invention, the polymer of the terpene compound means a polymer in which the monomer is composed only of the terpene compound. The terpene compound is not only a single polymer (that is, a homopolymer) but also two terpene compounds. The above copolymer is also included. The terpene compound polymer is preferably a terpene compound homopolymer.

 In the present invention, a terpene compound having a hydroxy group or a formyl group and having a carbon-carbon double bond is a hydroxyl group or a group of unsaturated hydrocarbon compounds present in plants or essential oils. It has a formyl group, and it is considered that the hydroxy group or formyl group exhibits antibacterial, antifungal and pest repellent effects. Examples of the tenolepenic compounds having a hydroxy group or a formyl group and having a carbon-carbon double bond used in the present invention include geraniol, citral, citronellor nore, citronellol, linalonore, farnesol, neroli donorre, nerol, taxi Sole, eugenol, isoeugenol and the like.

In the polymer of the tenolepen compound, geraniol, citral, citronellal, nerol, eugenol, and isoeugenol are preferable from the viewpoint of antibacterial action, and geraniol, citral, and isoeugenol are particularly preferable. From the viewpoint of antifungal action, geraniol, eugenol, citral, citronellal, and isoeugenol are preferable, and geraniol, eugenol, and isoeugenol are particularly preferable. From the viewpoint of pest repellent action, citral, eugenol, geraniol and isoeugenol are preferred, and isoeugenol is particularly preferred. One or more terpene compounds can be used.

 It is essential that the average degree of polymerization of the terpene compound polymer is 5 to 50. If the average degree of polymerization is within this range, the polymer has excellent antibacterial activity, antifungal activity, and insect pest life. Has an evasive action. Furthermore, from the viewpoints of low volatility and sustained effect, the average degree of polymerization is preferably 5 to 30 and more preferably 7 to 8.

 In the present invention, the average degree of polymerization is determined by quantifying and calculating the content of nitrogen at the end of the polymer using an elemental analyzer (Perkin Elmer model 240, 00, C HNS / O). The average degree of polymerization.

 (2) Copolymers of terpene compounds and butyl ester compounds

 In the present invention, the copolymer is a copolymer of one or two or more terpene compounds and one or two or more butyl ester compounds, preferably one terbene compound. This is a copolymer of a compound and one kind of buleresteric compound.

 Examples of the terpene compound used in the copolymer include the same terpene compounds as described above. From the viewpoint of antibacterial action, geraniol, citral, citronellal, isoeugenol, citronellol, and linalool are preferable, and citronellal, sitol Loneroll and linalool are especially preferred. From the viewpoint of antifungal action, citral, citronellal, eugenol, nerol and isoeugenol are preferred, and citral, eugenol and isoeugenol are particularly preferred. From the viewpoint of pest repellent action, isoeugenol, geraniol, linalool and citronellol are preferable, and geraniol and citronellol are particularly preferable.

 One or more terpene compounds can be used.

The bull ester compound used in the copolymer is not particularly limited as long as it is a bull ester compound that can be radically copolymerized with the terpene compound, and examples thereof include vinyl formate and butyl acetate. And bull ester compounds such as butyl propionate, vinyl butyrate, vinyl isobutyrate, pivalate butyl, benzoate butyl, valerate, bispurate, laurate, and stearate. Of these, a bullestenole compound having 4 to 9 carbon atoms is preferred, and in particular, from the viewpoint of easy availability of raw materials, bull acetate and benzoate are preferred. Also, with terpene compounds From the viewpoint of ease of application to film applications, it is preferable to use vinyl acetate.

 One or two or more of these butyl ester compounds can be used.

It is essential that the average degree of polymerization of the copolymer is 50 to 50. If the average degree of polymerization is within this range, the copolymer has excellent antibacterial action, antifungal action, pest organisms. Has repellent action. Furthermore, sparingly volatile, from the standpoint of ease of sustained and filming effects, it is preferred that the average polymerization degree is 1 5 to 5 0, more preferably ² 5-5 0. The measuring method of the average degree of polymerization here is the same as the above.

 Copolymerization ratio of terpene compound and vinyl ester compound (ratio of terpene compound unit and vinyl esteranol compound unit in copolymer. That is, one or more terpene compound units: 1 The ratio of the species or the two or more types of vinyl ester compound units) must be in the molar ratio of 1: 2 to 1:25, and if the copolymerization ratio is within this range, Combined has excellent antibacterial, antifungal, and pest repellent effects. Furthermore, the copolymerization ratio is preferably in the range of 1: 4 to: L: 25 in terms of molar ratio from the viewpoint of the functional group accumulation effect, and in the range of 1: 4 to 1:10. Is more preferable, and most preferably within the range of 1: 4 to 1: 6.

 In the present invention, the copolymerization ratio is obtained by quantifying and calculating the carbon content (%) of the copolymer using an elemental analyzer (Perkin Elmer 1240 type, CHNS / O). The copolymerization ratio.

 When two or more terpene compounds are used, the copolymerization ratio between the terpene compounds is not limited. Similarly, when two or more types of bull ester compounds are used, there is no restriction on the copolymerization ratio between each bull ester compound.

(3) Hydrolyzate of copolymer of terpene compound and butyl ester compound The hydrolyzate is obtained by hydrolyzing the copolymer of the tenolepene compound of (2) and burestenoleich compound. Is a copolymer in which vinyl ester units are converted to vinyl alcohol units, and is preferably a hydrolyzate of a copolymer of one kind of tenolepenic compound and one kind of buresterol compound. All of the butyl ester units need not be converted to vinyl alcohol units, but to ensure the water solubility of the hydrolyzate. For this reason, it is preferable that the vinyl ester unit is converted into a butyl alcohol unit by 70% or more, particularly preferably 90% or more.

 It is essential that the average degree of polymerization of the hydrolyzate is 5 to 50. If the average degree of polymerization is within this range, the copolymer has excellent antibacterial action, antifungal action, and pest repellent. Has an effect. Furthermore, from the viewpoints of low volatility (odorlessness) and sustained effect, the average degree of polymerization is more preferably 15 to 50, and more preferably 25 to 50.

 The method for measuring the average degree of polymerization here is the same as in (1) above.

 Copolymerization ratio of the hydrolyzate (ratio of terpene compound unit and vinyl alcohol unit (including vinyl ester compound unit if not completely hydrolyzed), that is, 1 type or 2 types The ratio of the above terpene compound units: butyl alcohol units)) must be in a molar ratio of 1: 2 to 1:25, and if the copolymerization ratio is within this range, the copolymer is excellent. Has antibacterial, antifungal and pest repellent effects. Further, the copolymerization ratio is preferably in the range of 1: 4 to: I: 25 from the viewpoint of the functional group accumulation effect and water solubility, and in the range of 1: 4 to 1:10. Is more preferable, and most preferably within the range of 1: 4 to 1: 6.

 The method for measuring the copolymerization ratio here is the same as in (2) above.

 The conversion rate of the hydrolyzate from the butyl ester unit to the bial alcohol unit can be determined by quantifying the amount of addition using acetylation with acetic anhydride dissolved in pyridine.

 Next, the manufacturing method of the terpene polymer of this invention is demonstrated.

 (I) Method for producing polymer of terpene compound

 The polymer is produced by radical polymerization of one or more tenolepenic compounds using a polymerization initiator.

The method of radical polymerization is not particularly limited as long as the polymerization reaction proceeds, and can be performed according to a conventional method. Examples of the polymerization method include vanolec polymerization, solution polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization and the like. As the polymerization method, bulk polymerization and emulsion polymerization are preferable because the reaction time can be shortened. The polymerization initiator can be used without particular limitation as long as it is a polymerization initiator used in ordinary radical polymerization. Examples thereof include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobisone. 2-Methylbutyronitrile, 2, 2, 1-azobis _ 2,4 1-dimethylolevereronitrile, 1, 1, 1-azobiscyclohexane 1-carbonitryl, 2,2'-azobis-1-2-amidinopropane hydrochloride 2, 2'-azobisisobutyric acid dimethinole, 2, 2, monoazobisisobutylamidine hydrochloride, 4,4'-azobis-4-cyanovaleric acid, etc .; benzoyl peroxide, 2 , 4-Dichloroperoxide benzoyl, lauroyl peroxide, acetyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, p- Menthane dropperoxide, Pinan dropperoxide, Methylethylketone peroxide, Cyclohexanone peroxide, Diisopropylperoxydidecanolate, tert-Butinorepenoleoxylaurate, Gee tert-Butinorepenoleoxyphthalate, Di Peroxide sulfates such as benzyloxide, 2,5-dimethinorehexane _ 2,5-dihydroperoxide; peroxosulfuric acid systems such as ammonium peroxodisulfate, sodium peroxonisulphate, and peroxodisulfuric acid Initiators: redox initiators such as benzoyl peroxide N, N-dimethylaniline, sodium peroxodisulfate monohydrogensulfite, and the like. Of these, azo initiators and peroxosulfate initiators are preferable, and 2,2, monoazobisisoptyronitrile and ammonium peroxodisulfate are more preferable. These radical polymerization initiators can be used alone or in combination of two or more simultaneously or sequentially.

 The amount of the polymerization initiator used is appropriately determined according to the reaction conditions and the desired degree of polymerization of the polymer, but is usually from 1/20 to 1/100 mol per 1 mol of the terpene compound. Preferably, it is 1 Z20 to lZ50 mol. In particular, when the amount of the initiator is within this range in the Balta polymerization, a polymer having an average degree of polymerization of 5 to 50 is easily obtained.

When the reaction is carried out by other than Barta polymerization, the solvent used is not particularly limited as long as it does not inhibit the reaction. Examples include water; acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone. , Ketones such as γ-butyrolactone; n-propyl alcohol, isopropyl alcohol record, n-butanolanol record, tert-butyranol record Nole, n-octinoreal alcohol, n-dodecyl alcohol, etc .; alcoholols; ethylene glycol, propylene glycol, glycols such as diethylene glycol, etylene glycol, resin methinoreatenore, ethylene glycol Ethers such as etherol, jetylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc .; ethylene glycol-monomono methinore ethenore, ethylene glycol eno-mono eno eno eno-nore, propylene dalicono eno mono-mono eno eno-enore, diethylene glycol eno-mono methino Alcohol ethers such as methanol; n-propyl formate, isopropyl formate, n-butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetate Esters such as chinole, n-hexyl acetate, methyl propionate, ethyl propionate, and methyl butyrate; methyl 2-oxypropionate, ethyl 2-oxypropionate, n-propyl 2-oxypropionate, Monooxycarboxylic esters such as 2-isopropylpropionate and 2-oxyethyl-2-ethylpropionate; methoxyethyl acetate, ethoxyethyl acetate, methyl 3-methylpropionate, 3-methylpropionate Toxyl propionate, methyl 3-ethoxypropionate and other alkoxycarboxylic acid esters; cellosolve acetate, methyl solvate sorbacetate, cetylsulfate solvate, cellosolve esters such as ptylcetol solvate acetate; benzene, toluene, Aromatic hydrocarbons such as xylene; Halogenated hydrocarbons such as chloroethylene, black-opened benzene, and di-open-ended benzene; such as dimethylacetamide, dimethylformamide, N-methylacetamide, N-methylpyrrolidone, N, N'-dimethylimidazolidinone, etc. Examples include amides. These solvents may be used alone or in combination of two or more. Of these, the preferred solvent is water.

 The amount of solvent used is a force that is determined appropriately depending on the polymerization method, the reactivity of the monomers used, the type of polymerization initiator, etc. The amount is 0.5 to 4 L, preferably 1 to 3 L, per kg of compound.

The radical polymerization initiation reaction can be carried out by heat, light, radiation, or the like according to a conventional method depending on the kind of the polymerization initiator. From the viewpoint of easy reaction operation, it is preferable to initiate polymerization by heat. The reaction temperature may be at least the temperature necessary for the polymerization reaction to proceed, and is appropriately selected according to the decomposition temperature of the polymerization opening agent, the reaction time, the boiling points of the solvent and the monomer, and the like. A preferable reaction temperature is 50 to 70 ° C, and a more preferable reaction temperature is 60 to 70 ° C.

 The reaction time is appropriately selected according to the reaction temperature, the type of polymerization initiator used, the type and concentration of the terpene compound, and the like. A preferable reaction time is 12 to 500 hours, and a more preferable reaction time is 12 to 240 hours.

 After completion of the reaction, the desired polymer of the terpene compound can be obtained by isolation from the reaction mixture by a conventional method. Isolation methods include, for example, a method in which the reaction temperature is once increased to completely decompose the initiator, and then the solvent and residual monomers are distilled off under reduced pressure. The reaction mixture is added to a large amount of poor solvent for the polymer. And a method of collecting the precipitate by filtration.

 (II) Method for producing a copolymer of a terpene compound and a bull ester compound

 A copolymer of a terpene compound and a vinyl ester compound is produced by radical polymerization of one or more tenolepenic compounds and one or more biester compounds using a polymerization initiator. The

 The radical polymerization can be carried out by employing the same polymerization method as in the above (I), such as Balta polymerization, solvent polymerization, etc. The types of polymerization initiator and solvent used are the same as those in (I) above. It is the same.

 In the radical polymerization, the amount of the polymerization initiator is appropriately determined according to the reaction conditions and the desired degree of polymerization of the polymer, but is usually based on 1 mol of the total of the terpene compound and the bull ester compound. , 0.01 to 0.1 mol, preferably 0.01 to 0.05 mol. In particular, when the amount of the initiator is within this range in the Balta polymerization, a copolymer having an average degree of polymerization of 5 to 50 is easily obtained.

In the radical polymerization, the amount of solvent used is determined appropriately depending on the polymerization method, the reactivity of the monomers used, the type of polymerization initiator, etc., since the concentration affects the degree of polymerization. Is 1 to 5 L, preferably 1 to 2 L with respect to a total of 1 kg of the tenolepenic compound and the Bühlesterich compound. The initiation reaction can be performed by heat, light, radiation, etc., as in (I) above, and is preferably performed by heat.

 The reaction temperature may be higher than the temperature necessary for the polymerization reaction to proceed, and is appropriately selected according to the decomposition temperature of the polymerization initiator, the reaction time, the boiling points of the solvent and the monomer, and the like. A preferable reaction temperature is 40 to 70 ° C, and a more preferable reaction temperature is 60 to 70 ° C.

 The reaction time is appropriately selected according to the reaction temperature, the polymerization initiator used, and the type and concentration of the terpene compound and vinyl ester compound. A preferable reaction time is 12 to 500 hours, and a more preferable reaction time is 12 to 240 hours. After completion of the reaction, it can be isolated in the same manner as in the above (I) to obtain a copolymer of the desired terpene compound and vinyl ester compound.

 (III) Method for producing hydrolyzate of copolymer of terpene compound and butyl ester compound

 The hydrolyzate can be produced by hydrolyzing a copolymer of a terpene compound obtained by the method (II) and a Büster compound with an alkali. As a hydrolysis method, for example, a method generally used when converting polyvinyl acetate into polyvinyl alcohol (for example, a copolymer of a terpene compound and vinyl estero hydrate compound is dissolved in a solvent such as methanol. And a method of adding a methanol solution of sodium hydroxide, a method of adding the copolymer to a methanol solution of sodium hydroxide, and the like.

 The terpene polymer of the present invention is useful as an antibacterial agent, an antifungal agent and a pest repellent. The target bacteria when used as an antibacterial agent are spoilage bacteria such as Escherichia coli and Bacillus subtilis, and in particular, exhibit excellent antibacterial action against Escherichia coli and Bacillus subtilis.

 The target soot when used as an antifungal agent is a mold, black mold, etc., and in particular, exhibits an excellent fungicidal action against blue mold and black mold.

Target pests for use as pest repellents include slugs, snails, termites, ants, moths, ticks, protozoa (eg, amoeba, paramecium, amid) It has an excellent pest repellent effect especially on slugs, ants and protists.

 When used as an antibacterial agent, antifungal agent, or pest repellent, there are no particular restrictions on the form of use. Examples of use forms include: (A) The terpene polymer of the present invention in a molded product. (B) to form or film the terpene polymer of the present invention,

(C) The terpene polymer of the present invention is made into a solution. (D) The terpene 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 applied. It is immersed in a solution of the tenolepene polymer of the present invention and dried, and the surface of the substrate is coated with the terpene polymer of the present invention. (E) The terpene polymer of the present invention is mixed with a paint. Can be mentioned.

 Specific examples of these use modes include: applying a solution of the terpene polymer of the present invention to a catheter; drying and coating the antibacterial catheter; tissue is immersed in the terpene polymer solution of the present invention and dried. The terpene polymer solution of the present invention is applied to a sterilized tissue tape, dried and coated with a slug repellent tape and a repellent tape, a ship bottom antifouling paint in which the terpene polymer of the present invention is mixed with a paint, An antifouling material net which is coated by immersing the net in the tenolepene polymer solution of the present invention, a disinfectant or lotion containing an aqueous solution of the terpene polymer of the present invention, and a wrapping paper of the terpene polymer of the present invention Examples thereof include fruit wrapping paper soaked in a solution and dried, and a drain pipe formed from the terpene polymer of the present invention.

When the terpene polymer of the present invention is (1) a polymer of a terpene compound, the tenolepene compound polymer is a viscous oil, and therefore, the use of the above (C) to (E) (2) In the case of a copolymer of a terpene compound and a vinyl ester compound, the copolymer is oil-soluble, and the effect of improving the moldability by the Bühlesterich compound is effective. Therefore, the use forms (A) to (E) above are preferable. (3) When the hydrolyzate is a copolymer of a terpene compound and a vinyl ester compound, the hydrolyzate is water-soluble. Therefore, the use modes (C) to (E) above are preferred. In this case, in the use modes (C) and (D), the solution is more preferably an aqueous solution, and the use mode (E). In the case that the paint is water-based paint Is more preferable. Example

 EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. First, examples of the synthesis of the polymer of the present invention will be described.

Example 1 Synthesis of Isoeugenol Homopolymer

 Isoeugenol 32.86 g (20 Ommo 1) and peroxodisulfuric acid ammonium 0.896 g (4 mmo 1) were dissolved in 30 mL of water. This was heated in a 60 ° C. water bath with stirring for 7 days. After the reaction, an appropriate amount of water was added and stirred well, and then water was removed by decantation to remove unreacted initiator. Further, by concentrating under reduced pressure, water and unreacted monomers were removed to obtain an isoeugenol homopolymer (yield 85%). Confirmation of polymer formation was performed with FT-IR. Figures 1 and 2 show the results of FT-IR measurement of isoeugenol and isoeugenol homopolymer.

Example 2 Synthesis of citral homopolymer

 Sitranole 30.4 g (20 Omm o 1) with A I BN (4 mm o 1)! ] 6

The reaction was carried out at 0 ° C for 14 hours. After washing with water, the mixture was heated to 120 ° C to release A I BN. Unreacted monomers were removed by a rotary evaporator to obtain a citral homopolymer (yield 81%). Confirmation of polymer formation was performed with FT-IR. Figures 3 and 4 show the results of FT-IR measurement of citral and citral homopolymer.

Example 2 Synthesis of a-2c citral homopolymer

 The charge molar ratio of citral to AI BN was set to 1: 0.005 (Example 2a), 1: 0.01 (Example 2b), and 1: 0.02 (Example 2c). In the same manner, citral homopolymers having different degrees of polymerization were obtained.

Example 3 Synthesis of Lina Mole Homopolymer

 Add 1 I BN (4 mmo 1) to 30.5 g (20 Ommo 1)

The reaction was carried out at ~ 70 ° C for 7 minutes. The same recovery operation as in Example 2 was performed to obtain a linalool homopolymer (yield 50%).

Example 4 Synthesis of Citronellol Homopolymer AI BN (4 mmo 1) was added to citronellol 30 g (20 Ommo 1), and polymerization was carried out at 60 to 70 ° C. for 14 days. The same collection operation as in Example 2 was performed to obtain a citronellol homopolymer (yield 60%).

Example 5 Synthesis of Geraniol Homopolymer

 A mixture of 30.5 g (20 Ommo 1) of geranionore and 0.92 g (4 mmo 1) of penoleoxonisulfate was reacted at 70 ° C. for 7 days. The same recovery operation as in Example 1 was performed to obtain a geraniol homopolymer (yield 85%). Confirmation of polymer formation was performed by FT-IR. Figures 5 and 6 show the results of FT-IR measurements of geraniol and gera-ol homopolymers.

Examples 5a-5b Synthesis of Geraniol Homopolymer

 Example 5 where the charged molar ratio of geraniol and AI BN was 1: 0.07 (Example 5a) and the charged molar ratio of geraniol and ammonium peroxodisulfate was 1: 0.02 (Example 5b). In the same manner as above, geraniol homopolymers having different degrees of polymerization were obtained.

Examples 6 to 10 Synthesis of homopolymers of other tenolepenic compounds

 A homopolymer of citronellal, neguchiol, nerolidol, flunesol, and eugenol was obtained in the same manner as in Example 1 or 2.

Examples Example 1 1-16 Synthesis of isoeugenol vinyl acetate copolymer and isoeugenol vinyl alcohol copolymer

 Add 1.552 g (6.66 lmmo 1) ammonium peroxodisulfate to 3 g (18. 27 mmo 1) isoeugenol and 27 g (313.6 mmo 1) oxalate (molar ratio 1: 1: 7) Polymerization was performed at 60 ° C for 7 S. Purification was performed by dissolving the reaction product in tetrahydrofuran (THF), adding water while stirring vigorously, and collecting the precipitating soy sauce. This operation was repeated 2 to 3 times to obtain isoeugenol Z vinyl acetate copolymer (yield 85%).

In order to hydrolyze a part of the obtained copolymer, 1 g of isoeugenol / butyl acetate copolymer was dissolved in 5 OmL of methanol, and a saturated methanol solution of sodium hydroxide was added in excess. Let stand for several hours, separate the resulting white precipitate with a centrifuge, and remove the supernatant. Threw away. The precipitate was transferred to a Soxhlet extractor, methanol was circulated, and extraction was performed for 5 hours to obtain an isoeugenol / vinyl alcohol copolymer. The yield in this case was about 95% of the theoretical amount.

 In order to obtain isoeugenol Z vinyl acetate copolymer and isoeugenol nobu alcohol alcohol copolymer with different copolymerization ratio, the molar ratio of isoeugenol to vinyl acetate was set to 1: 1: 1 and 1: 5.7. The amount of the initiator was set to 1/50 monore to the total of isoeugenol and butyl acetate, and the same reaction as described above was performed.

Examples 17 to 22 Synthesis of citral Z oxalate bur copolymer and citral Z bur alcohol mono copolymer

 Add 1.550 g (6.66 lmmo 1) of ammonium peroxodisulfate to 3 g (19.45 mmo 1) of citral and 27 g (31 3.6 mm o 1) of vinylol acetate (molar ratio 1:16). Polymerization was carried out at ° C for 14 days. The same recovery operation as described above was performed to obtain a citral Z-butyl acetate copolymer (yield 73%).

 In order to hydrolyze a part of the obtained copolymer, citral Z butyl acetate copolymer 1 g was dissolved in 5 OmL of methanol saturated with sodium hydroxide and allowed to stand. The precipitate was separated with a centrifuge to obtain a citral / Viel alcohol copolymer.

 In order to obtain citral / acetic acid butyl copolymers and citral / ^ butyl alcohol copolymers with different copolymerization ratios, the molar ratio of citral to butyl acetate was set to 1: 1.1 and 1: 5.2. The reaction was carried out in the same manner as described above, except that the amount of the agent was 1Z50 mol with respect to the total of citral and butyl acetate.

Examples 23-28 Synthesis of Lina Mouth / Vinyl Acetate Copolymer and Lina Mouth Z Bier Alcohol Copolymer

 Linaguchi Ichinole 3 g (19.4 mmo 1) and 27 g (313.6 mm o 1) acetate (molar ratio 1: 16.4) peroxodisulfuric acid ammonium 1.520 g (6.66 lmmo 1) And polymerization was carried out at 60 ° C for 7 days. The same recovery operation as described above was performed to obtain a single liner / vinyl acetate copolymer (yield 80%).

In order to hydrolyze a part of the resulting copolymer, 1 g of linalool Z-butyl acetate copolymer was dissolved in 25 mL of methanol saturated with sodium hydroxide, and then at 60 ° C for several hours. I left it alone. The produced precipitate was separated with a centrifuge and washed with methanol to obtain a linalool-nobu alcohol alcohol copolymer.

 In order to obtain linalole Z-vinyl acetate copolymer and linalole Z-bull alcohol copolymer with different copolymerization ratios, the molar ratio of linalool to butyl acetate was set to 1: 10.7 and 1: 5. The reaction was carried out in the same manner as described above, except that the amount of the initiator was 1Z50 mol with respect to the total of linalool and butyl acetate.

Examples 29-34 Synthesis of Citronellol / Vinyl Acetate Copolymer and Citronellol Z Vinyl Alcohol Copolymer

 Add citronellol 3 g (19.19 mmo 1) and oxalate bulle 27 g (313.6 mmo 1) (molar ratio 1: 1.6) with peroxodisulfuric acid ammonium 1.5 5 g (6.656 mm o 1) Polymerization was carried out at 60 to 70 ° C for 14 days. The same recovery operation as described above was performed to obtain citronellol Z vinyl acetate copolymer (yield 86%).

 In order to hydrolyze a part of the obtained copolymer, the same operation as in Examples 23 to 28 was performed to obtain a citronellol / bule alcohol copolymer.

 In order to obtain citronellol / vinyl acetate copolymers and citronellol Z vinyl alcohol copolymers with different copolymerization ratios, the molar ratio of citronellol to butyl acetate was 1: 1.

The reaction was carried out in the same manner as described above, with 0.8 and 1: 5.4, and with an initiator amount of 150 mol based on the total of citronellol and butyl acetate.

Examples 35 to 40 Synthesis of Geraniol Z-Butyl Acetate Copolymer and Geraniol Z Vinyla Noreco Monore Copolymer

 Add 1.520 g (6.6 6 lmmo 1) of peroxodisulfate to 3 g (18. 27 mmo 1) of geraniol and 27 g (313.6 mm o 1) of acetic acid acetate (monore ratio 1: 16) Polymerization was carried out at 65 ° C for 7 days. The same recovery operation as described above was performed to obtain a geraniol Z vinyl acetate copolymer (yield 80%).

 In order to hydrolyze a part of the obtained copolymer, the same operation as in Examples 23 to 28 was carried out to obtain a geraniolsbier alcohol copolymer.

In order to obtain geraniol Z butyl acetate copolymers and geraniol Z butyl alcohol copolymers with different copolymerization ratios, the molar ratio of geraniol to butyl acetate was 1:10 and The reaction was carried out in the same manner as above except that the amount of the initiator was 1: 5.3 and the amount of the initiator was 1/50 of the total of geraniol and butyl acetate. Copolymer formation was confirmed by FT-IR for a geraniol to butyl acetate molar ratio of 1: 5.3. Figure 7 shows the results of FT-IR measurement.

Examples 41 to 70 Other terpene compounds, butyl acetate copolymers and other tenoleven compounds, synthesis of vinyl alcohol copolymers

 For citronellanol, nerolinore, nerolidol, fanolenesol, and eugnolene, a copolymer with butyl acetate and a copolymer with bur alcohol were obtained in the same manner as in Examples 11-40.

 The average degree of polymerization of the polymer of the present invention obtained in the above examples was determined by the following method. Further, the copolymerization ratio of the copolymer of the terpene compound and butyl acetate and the copolymerization ratio of the copolymer of the terpene compound and butyl alcohol were determined by the following methods. Table 1 shows the measurement results for the homopolymer and Table 2 shows the measurement results for the copolymer.

 [Average polymerization degree]

 Using an elemental analyzer (Perkin Elmer model 1400, CHNS / O), the content of nitrogen at the end of the polymer was quantified and calculated.

 [Copolymerization ratio]

Using an elemental analyzer (Perkin Elma model 1400, CHNSZO), the carbon content (%) of the copolymer was quantified and calculated.

table 1

Table 2— 1

表 2— 2

Table 2— 2

* Copolymerization component (vinyl ester compound) remains as vinyl acetate units, and those that have been converted to vinyl alcohol units are described as `` Vinyl acetate J, and further vinyl acetate units in the copolymer hydrolyzed to vinyl alcohol units. '' It is written as VAJ. In order to confirm that the polymer of the present invention is hardly volatile, the following test was conducted.

Test Example 1 Difficult volatility test

 Citral, Citral homopolymer of Example 2, Example 1 Citral / vinyl acetate copolymer of 9, Geraniol, Geraniol homopolymer of Example 5, Geraniol // Butyl acetate copolymer of Example 37 Using a thermal analyzer (DTG60, manufactured by Shimadzu Corporation), heat analysis was performed by heating at a rate of temperature increase of 10 ° CZ in a nitrogen stream and measuring the mass change. The results are shown in Figs.

 From the results in FIGS. 8 to 10, the citral homopolymer and the citral acetic acid butyl copolymer are more symmetric than the citral. From the results in FIGS. 11 to 13, the geranol homopolymer and the geraniol-vinyl acetate copolymer It can be seen that the polymer has less weight loss with increasing temperature and is less volatile.

 Next, the antibacterial action, antifungal action, and pest repellent action of the polymer of the present invention were evaluated as in the following test examples.

Test Example 2 Antibacterial test (E. coli, Bacillus subtilis)

Example 2 a to 2 c and 5 a to _c concentration when the polymerization degree of the different homopolymer of citral and geraniol homopolymer dissolved in dimethyl sulfoxide (DMSO) obtained in 5 b, each heavy The combined amount was adjusted to include 0.5 mg, 0.05 mg, and 0.05 mg in 5 μL of DMSO. This solution was dropped into a solid medium inoculated with Escherichia coli or Bacillus subtilis and cellophane was placed thereon to examine antibacterial properties. Antibacterial evaluation was performed according to the following criteria. The results are shown in Table 3.

 Bacterial growth is not recognized at all: +++ Bacterial growth is slightly observed on part of cellophane rim: ++

 Slight growth of fungi was observed at the cellophane edges: +

 Bacterial growth observed at the bottom of cellophane: 1

Figure 14 shows the actual status of antibacterial evaluation in this test example. Table 3

表 3の結果より、 シトラールの単独重合体及びゲラニオールの単独重合体は、 大腸 菌、 枯草菌に対して抗菌作用を示すことがわかる。

From the results in Table 3, it can be seen that the homopolymer of citral and the homopolymer of geraniol show an antibacterial action against Escherichia coli and Bacillus subtilis.

Test Example 3 Antibacterial test (E. coli, Bacillus subtilis)

5 mg of the terpene polymer of the example was dissolved in 1 ΟL of dimethyl sulfoxide, 5 of this solution was dropped on cellophane (1 cm ² ) and dried. Escherichia coli or Bacillus subtilis was applied to the agar medium, cellophane coated with the polymer of the present invention was placed, and left at 25 ° C. for 3 S, and antibacterial properties were evaluated according to the following criteria. The results are shown in Table 4.

 Cellophane and its surroundings have no growth of bacteria: + + + Cellophane has a slight growth on the part of cellophane: + + Bacterial growth has been observed at some places on cellophane What was born: + Bacteria were found growing under the cellophane: One Test Example 4 Antibacterial test (miscellaneous bacteria)

1-5% DM SO solution of the terpene compound homopolymer of the example, 1-5% DM SO solution of the terpene compound vinyl acetate copolymer of the example, and the terpene compound Z of the example Z vinyl alcohol A 1-5% aqueous solution of the copolymer was prepared, and an industrial wiper (trade name: Kimwipe (registered trademark)) was immersed therein. After drying, wipe a finger wiped with the industrial wiper, a finger wiped with an untreated industrial wiper, or a finger that does nothing on the agar medium and leave it for 2 days. We investigated the propagation of germs when a finger wiped with an industrial wiper treated with an aqueous solution was rubbed on an agar medium. Antibacterial evaluation was performed according to the following criteria. The results are shown in Table 4. No growth of germs: + + + A slight growth of germs: + + Rub fingers with an untreated industrial wiper on an agar medium

 Those with as many germs as were admitted: +

 Proliferation of miscellaneous bacteria when a finger that does nothing is rubbed on an agar medium

 The degree of breeding: One

Test Example 5 Slug repellent test

 A terpene polymer of the example was prepared in a 500-1000-ppm tetrahydrofuran solution, cellophane paper was immersed in the solution, and dried. The cellophane paper prepared in this way was affixed to the top of the inner surface of the beaker, and a slug was placed on the bottom of the beaker to see if it crawls out. The slug repellency was evaluated according to the following criteria. The results are shown in Table 4.

 A slug that is stuck in front of cellophane paper: +

 The slug crawls out of the beaker ： One

Test example 6

 The same cellophane paper used for the slug repellent test was wrapped around the base of the chopsticks and soaked with strawberry syrup. The chopsticks were inserted into the ground where many ants were seen, and it was examined whether Ali gathered over the paper that had been soaked in the chopped syrup. For comparison, the same test was performed using uncoated cellophane paper. The repellent effect was evaluated according to the following criteria. The results are shown in Table 4.

 What did not exist beyond cellophane paper: +

 Over the cellophane paper soaked with strawberry syrup

 A collection of applications (equivalent to the comparison test): One

Test Example 7 Protozoa Repellent Test

The solution used for the slug repellent test was applied to the inside of a sample tube having an internal volume of 5 O mL. Water was added to this, and nazuna (penpensa) cut into 15 cm was added and left at 25 ° C for 2 weeks. I investigated the condition of the deadness of Nazuna and the amount of water. Uncoated sample tube Compared to the tests performed using. Protozoa were also examined with a microscope. Protozoa The repellent effect was evaluated according to the following criteria. The results are shown in Table 4.

 Nazuna did not wither and water did not stay: +

 Nazuna withered, and there is dust at the bottom between samples

 What was there (equivalent to the comparison test):

Test Example 8 Antifungal test

 The solution used in the slug repellent test was soaked in an industrial wiper (trade name: Kimwipe (registered trademark)) and dried. A 3 cm square bread moistened with water was placed in the center of this industrial wiper, covered with a wrap to prevent the bread from drying, and allowed to stand for a week before observing the growth of the mold on the surface of the bread.

 For black mold, the collected black mold was applied to an industrial wiper and the same test was performed. Antibacterial properties were evaluated according to the following criteria. The results are shown in Table 4.

(However, the antifungal test of the terpene-based compound Z-buhl alcohol copolymer against cacao was evaluated by the following Test Example 9.)

 Even the top of the bread did not fold: + + +

 The top of the bread was speared, but industrial wipers and bread

 The contact surface did not have any wrinkles: + +

 Wrinkles on the surface of the bread, contact between the industrial wiper and the bread

 Slightly wrinkled on the surface: +

 A cocoon on the entire surface of bread and industrial wipers: ―

Test Example 9 Antifungal test

 To the 10% rice paste 5 !! 1 1 ^, the terpene compound novinyl alcohol copolymer of the example was added to a concentration of 0.0 1 to 2%. After standing for about 1 month, the surface moldiness was compared with that without vinyl alcohol copolymer. Antibacterial evaluation was performed according to the following criteria. The results are shown in Table 4.

 I couldn't get any fungus

 Slightly fizzled in 2 weeks

Slightly fizzled mold in a week The ones that had been bred in one week (equivalent to the comparative study): 1 Table 4

 * The blanks in Table 4 are not measured. From the results in Table 4, it can be seen that the terpene polymers of the examples show antibacterial action, P-force action, and pest repellent action.

Industrial applicability The polymer of the terpene compound of the present invention, the copolymer with a vinyl ester compound and the hydrolyzate thereof can be used as an antibacterial agent, a fungicide, and a pest repellent. This application is based on Japanese Patent Application No. 2 0 4 4 3 4 1 2 2 2 filed in Japan, the contents of which are incorporated in full herein.

Claims

The scope of the claims  1. A polymer of a terpene compound having a hydroxyl group or a formyl group and having a carbon-carbon double bond, or a copolymer of the terpene compound and a butyl ester compound or a hydrolyzate thereof. A terpene polymer having a degree of polymerization of 5 to 50, and when the terpene polymer is a copolymer of a terpene compound and a bull ester compound or a hydrolyzate thereof, a terpene compound and a bull ester A terpene polymer having a copolymerization ratio with a compound or butyl alcohol of 1: 2 to 1:25 (molar ratio). 2. A copolymer of a terpene compound and a bull ester compound having an average degree of polymerization of 15 to 50, and a copolymer ratio of the terpene compound and the bull ester compound is 1: 2. The terpene polymer according to claim 1, which is ˜1: 25 (molar ratio). 3. A hydrolyzate of a copolymer of a terpene compound and a vinyl ester compound having an average degree of polymerization of 15 to 50, and a copolymerization ratio of the terpene compound and vinyl alcohol is 1: 2 to 1 The terpene polymer according to claim 1, wherein the terpene polymer is 25 (molar ratio). 4. The tenolepene polymer according to any one of claims 1 to 3, wherein the bull ester compound is a bull acetate. 5. The terpene polymer according to claim 1, which is a polymer of a terpene compound having an average degree of polymerization of 5 to 30. 6. The terpene compound is at least one selected from geraniol, citral, citronellal, citronellol, linalool, farnesol, nerolidol, nerol, taxonole, eugenol, and isoeugenol. A terpene polymer according to claim 1. 7. The method for producing a terpene polymer according to claim 1, wherein the terpene compound or a mixture of the terpene compound and the vinyl esteranol compound is reacted in the presence of a polymerization initiator. 8. The method for producing a terpene polymer according to claim 1, wherein a mixture of the tenolepene compound and the Bühlestenoleich compound is reacted in the presence of a polymerization initiator, and then the product is hydrolyzed. 9. An antibacterial agent containing the terpene polymer according to any one of claims 1 to 6. 10. Antifungal agent containing the terpene polymer according to any one of claims 1 to 6. 11. A pest repellent containing the terpene polymer according to any one of claims 1 to 6.