WO2006057086A1 - Polymère terpénique et applications - Google Patents

Polymère terpénique et applications

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Publication number
WO2006057086A1
WO2006057086A1 PCT/JP2005/009827 JP2005009827W WO2006057086A1 WO 2006057086 A1 WO2006057086 A1 WO 2006057086A1 JP 2005009827 W JP2005009827 W JP 2005009827W WO 2006057086 A1 WO2006057086 A1 WO 2006057086A1
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Prior art keywords
terpene
compound
copolymer
polymer
polymerization
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PCT/JP2005/009827
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English (en)
Japanese (ja)
Inventor
Yasumasa Shigetomi
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Okayama Prefecture Industrial Promotion Foundation
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Application filed by Okayama Prefecture Industrial Promotion Foundation filed Critical Okayama Prefecture Industrial Promotion Foundation
Publication of WO2006057086A1 publication Critical patent/WO2006057086A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/04—Nitro compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/74—Synthetic polymeric materials
    • A61K31/765—Polymers containing oxygen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8129—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers or esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers, e.g. polyvinylmethylether
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/02—Local antiseptics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/02—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings containing insect repellants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D145/00—Coating compositions based on homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic system; Coating compositions based on derivatives of such polymers

Definitions

  • 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.
  • 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.
  • 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.
  • terpene compounds are weak but volatile, there is a problem that their effects cannot be sustained over a long period of time.
  • 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.
  • the present invention provides a tenolepene polymer that can be practically applied as an antibacterial agent, P-strength agent, and pest repellent.
  • the terpene polymer has an average degree of polymerization within a specific range, and the polymer is a copolymer with a butyl ester compound
  • 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.
  • 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.
  • 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).
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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)
  • 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.
  • 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.
  • geraniol, citral, citronellal, nerol, eugenol, and isoeugenol are preferable from the viewpoint of antibacterial action, and geraniol, citral, and isoeugenol are particularly preferable.
  • geraniol, eugenol, citral, citronellal, and isoeugenol are preferable, and geraniol, eugenol, and isoeugenol are particularly preferable.
  • citral, eugenol, geraniol and isoeugenol are preferred, and isoeugenol is particularly preferred.
  • One or more terpene compounds can be used.
  • 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.
  • 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.
  • 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.
  • geraniol, citral, citronellal, isoeugenol, citronellol, and linalool are preferable, and citronellal, sitol Loneroll and linalool are especially preferred.
  • citral, citronellal, eugenol, nerol and isoeugenol are preferred, and citral, eugenol and isoeugenol are particularly preferred.
  • 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.
  • bull ester compounds such as butyl propionate, vinyl butyrate, vinyl isobutyrate, pivalate butyl, benzoate butyl, valerate, bispurate, laurate, and stearate.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the polymerization method include vanolec polymerization, solution polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization and the like.
  • 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.
  • 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.
  • 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 ⁇ -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
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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,
  • the terpene polymer of the present invention is made into a solution.
  • 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.
  • the terpene polymer of the present invention is mixed with a paint. Can be mentioned.
  • terpene polymer 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.
  • 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)
  • 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.
  • 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.
  • the solution is more preferably an aqueous solution, and the use mode (E).
  • the paint is water-based paint Is more preferable.
  • 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.
  • 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 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 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).
  • Example 5a 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).
  • geraniol homopolymers having different degrees of polymerization were obtained.
  • a homopolymer of citronellal, neguchiol, nerolidol, flunesol, and eugenol was obtained in the same manner as in Example 1 or 2.
  • 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.
  • 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 / Dahl alcohol copolymer.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • a thermal analyzer TMG60, 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.
  • the citral homopolymer and the citral acetic acid butyl copolymer are more symmetric than the citral.
  • 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.
  • Test Example 2 Antibacterial test (E. coli, Bacillus subtilis)
  • the combined amount was adjusted to include 0.5 mg, 0.05 mg, and 0.05 mg in 5 ⁇ L 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: ++
  • Figure 14 shows the actual status of antibacterial evaluation in this test example.
  • Test Example 3 Antibacterial test (E. coli, Bacillus subtilis)
  • 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.
  • 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 choiruna (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.
  • 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.
  • the contact surface did not have any wrinkles: + +
  • 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.

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Abstract

La présente invention a pour objet un polymère terpénique pouvant être employé en tant qu’agent antibactérien, fongicide et pesticide. La présente invention décrit notamment un polymère terpénique de degré de polymérisation moyen compris entre 5 et 50, qui est constitué d’un polymère issu d’un monomère terpénique portant un groupement hydroxy ou formyle et une double liaison carbone-carbone. Alternativement, ledit polymère peut être un copolymère ou un copolymère hydrolysé dudit monomère terpénique et d’un dérivé d’ester vinylique. Lorsque ledit polymère terpénique est un copolymère, ou un copolymère hydrolysé, issu dudit monomère terpénique et d’un composé de type ester vinylique, le rapport molaire de copolymérisation de ces deux composés, ou dudit monomère terpénique et d’un dérivé d’alcool vinylique, est compris entre 1:2 et 1:25.
PCT/JP2005/009827 2004-11-25 2005-05-24 Polymère terpénique et applications WO2006057086A1 (fr)

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Cited By (4)

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EP3186217A4 (fr) * 2014-08-29 2018-01-24 P2 Science, Inc. Polyéthers, polyamines, polythioéthers, et leurs procédés de fabrication
US10844169B2 (en) 2017-07-31 2020-11-24 P2 Science, Inc. Polyether derivatives, uses, and methods of making the same
EP3762444A4 (fr) * 2018-03-07 2021-11-24 P2 Science, Inc. Dérivés de polyéther, leurs utilisations et leurs procédés de préparation
US11872300B2 (en) 2020-03-05 2024-01-16 P2 Science, Inc. Cosmetic compositions comprising polyether polymers

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JP2006273796A (ja) * 2005-03-30 2006-10-12 Okayamaken Sangyo Shinko Zaidan 日和見病原体に対する抗菌剤
JP5365883B2 (ja) * 2011-05-26 2013-12-11 コニカミノルタ株式会社 トナー及びトナーの製造方法

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JPH02216612A (ja) * 1989-02-16 1990-08-29 Nippon Zeon Co Ltd 磁気記録媒体

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JPH0220503A (ja) * 1988-07-09 1990-01-24 Ito Seiyu Kk 耐加水分解性重合物の製造法
JPH02216612A (ja) * 1989-02-16 1990-08-29 Nippon Zeon Co Ltd 磁気記録媒体

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SHIGETOMI Y. ET AL: "Citral no Radical Hanno o Mochiita Nanki Hakka to sono Kokin Bobaisei", THE SOCIETY FOR ANTIBACTERIAL AND ANTIFUNGAL AGENTS, JAPAN DAI 31 KAI NENJI TAIKAI YOSHISHU, 25 May 2004 (2004-05-25), pages 35, XP003006200 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3186217A4 (fr) * 2014-08-29 2018-01-24 P2 Science, Inc. Polyéthers, polyamines, polythioéthers, et leurs procédés de fabrication
US10059801B2 (en) 2014-08-29 2018-08-28 P2 Science, Inc. Polyethers, polyamines, polythioethers, and methods for making same
US10844169B2 (en) 2017-07-31 2020-11-24 P2 Science, Inc. Polyether derivatives, uses, and methods of making the same
US11518850B2 (en) 2017-07-31 2022-12-06 P2 Science, Inc. Polyether derivatives, uses, and methods of making the same
US11827746B2 (en) 2017-07-31 2023-11-28 P2 Science, Inc. Polyether derivatives, uses, and methods of making the same
EP3762444A4 (fr) * 2018-03-07 2021-11-24 P2 Science, Inc. Dérivés de polyéther, leurs utilisations et leurs procédés de préparation
US12084543B2 (en) 2018-03-07 2024-09-10 P2 Science, Inc. Polyether derivatives, uses, and methods of making the same
US11872300B2 (en) 2020-03-05 2024-01-16 P2 Science, Inc. Cosmetic compositions comprising polyether polymers

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