JP2020059162A - Wood preservation liquid and manufacturing method of wood with wood-preservative chemical agent - Google Patents

Abstract

To provide a wood preservation liquid which contains an organic solvent and a wood-preservative chemical agent and has a small environmental load due to the solvent, and to provide a manufacturing method of wood with the wood-preservative chemical agent with small environmental load using the wood preservation liquid.SOLUTION: This invention provides a wood preservation liquid containing a wood-preservative chemical agent and an organic solvent containing halogenated olefin whose boiling point is 30-65°C, and a manufacturing method of wood with the wood-preservative chemical agent in which the wood preservation liquid is brought into contact with the wood and then the organic solvent is vaporized to obtain the wood with the wood-preservative chemical agent.SELECTED DRAWING: None

Description

  The present invention relates to a wood preservation treatment liquid and a method for producing wood with a chemical for preserving wood.

  Wood is a material used in various fields, but it has the drawback that it deteriorates due to corrosion by fungi and erosion by insects, leading to a decrease in strength. Therefore, various kinds of wood preservative treatment liquids for preventing deterioration due to fungi and insects and methods for producing woods with chemicals for preserving woods have been developed.

  As a method for treating wood, for example, a wood preservation treatment liquid in which a wood preservation agent is dissolved in a volatile solvent such as hydrochlorofluorocarbon (hereinafter referred to as HCFC) or hydrofluoroether (hereinafter referred to as HFE). A method using is known. In this method, the wood is directly heated using high-frequency heating to recover the solvent from the wood (see, for example, Patent Document 1).

Japanese Patent No. 4149422

  HCFC and HFE, which have been used as solvents in conventional wood preserving liquids, have the advantage of not having a flash point. However, HCFC is planned to be completely abolished in the advanced countries at the end of 2019 due to concern about ozone depletion. Further, since HFE has a low solubility for a wood preserving agent, there is a problem that the usable wood preserving agent is limited.

  Therefore, the environmental load is small because there is no concern of ozone layer depletion, and there is a demand for wood preserving liquids and wood with chemicals for preserving wood that use solvents that have excellent solubility for various wood preserving agents. There is.

  The present invention relates to a wood preservative treatment liquid containing an organic solvent and a wood preservative chemical, with a wood preservative treatment liquid having a low environmental load due to the organic solvent and a wood preservative chemical agent using the wood preservative treatment liquid having a low environmental load. An object is to provide a method for manufacturing wood.

The present invention achieves the above object by using a halogenated olefin having a boiling point of 30 to 65 ° C as an organic solvent. The present invention provides the following wood preservation treatment liquid, wood with chemicals, and wood treatment method.
[1] A wood preserving liquid containing a wood preserving agent and an organic solvent containing a halogenated olefin having a boiling point of 30 ° C. or higher and 65 ° C. or lower.
[2] The halogenated olefin is (Z) -1-chloro-3,3,3-trifluoropropene, (E) -1-chloro-2,3,3-trifluoropropene, (Z) -1. -Chloro-2,3,3-trifluoropropene, (E) -1,3-dichloro-2,3,3-trifluoropropene and (Z) -1,3-dichloro-2,3,3-tri The wood preservation treatment liquid according to [1], which is at least one selected from the group consisting of fluoropropene.
[3] The preservation treatment liquid for wood according to [1] or [2], wherein the content of the halogenated olefin is 50% by mass or more based on the total amount of the organic solvent.
[4] The preservation of wood according to any one of [1] to [3], wherein the content of the organic solvent is 70% by mass or more and 99.998% by mass or less based on the total amount of the wood preservation treatment liquid. Processing liquid.
[5] With a wood preservative agent, which comprises contacting the wood preservative treatment liquid according to any one of [1] to [4] with wood and then volatilizing the organic solvent to obtain wood with a wood preservative agent. Wood production method.

  According to the present invention, in a wood preservation treatment liquid containing an organic solvent and a wood preservation agent, a wood preservation treatment liquid having a small environmental load due to the solvent, and a wood preservation treatment using the wood preservation treatment liquid having a small environmental load. A method of manufacturing wood with chemicals can be provided.

Hereinafter, embodiments of the present invention will be described.
In the present specification, for halogenated hydrocarbons and halogenated olefins, the abbreviation of the compound is described in parentheses after the compound name, and the abbreviation is used instead of the compound name as necessary. Further, (E) attached to the name of the compound having a geometrical isomer and its abbreviation shows the E form (trans form), and (Z) shows the Z form (cis form). In the names and abbreviations of the compounds, when the E form and the Z form are not specified, the names and abbreviations mean the generic names including the E form, the Z form, and a mixture of the E form and the Z form.

Unless otherwise specified, the global warming potential (GWP) is a 100-year value in the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report, unless otherwise specified.
In the present specification, the boiling point is a value at 1 atm (= about 0.1013 MPa).
In the present specification, “to” representing a numerical range includes upper and lower limits.

  The wood preservation treatment liquid of the present invention contains a wood preservation agent and an organic solvent containing a halogenated olefin having a boiling point of 30 to 65 ° C. As the organic solvent, a solvent capable of dissolving the wood preserving agent is preferable because the wood preserving agent can be evenly and uniformly attached to the wood. In the present specification, "dissolve" means that no cloudiness or insoluble matter is generated in the wood preservation treatment liquid after 30 minutes from mixing the wood preservation agent and the organic solvent.

  The wood preservation treatment liquid of the present invention may contain only one kind of halogenated olefin having a boiling point of 30 to 65 ° C, or may contain two kinds or more.

  The halogenated olefin used in the present invention is an unsaturated hydrocarbon compound having one or more carbon-carbon double bonds in the molecule, in which one or more hydrogen atoms bonded to carbon atoms are substituted with halogen atoms. It is a compound. The halogen atom capable of substituting the hydrogen atom is fluorine, chlorine, bromine or iodine, and among them, fluorine or chlorine is preferable from the viewpoint of suppressing discoloration of wood and the like. The halogenated olefin may have only one type of the above halogen atoms or may have two or more types.

  The halogenated olefin used in the present invention has a carbon-carbon double bond in the molecule, and therefore is easily decomposed by OH radicals in the atmosphere. Therefore, the halogenated olefin has a short life in the atmosphere, has a very small GWP and ozone depletion coefficient, and has a small environmental load. Further, it has excellent solubility and volatility as a solvent for a chemical for preserving wood.

  As the halogenated olefin having a boiling point of 30 to 65 ° C., hydrofluoroolefin (HFO) or hydrochlorofluoroolefin (HCFO) is preferable. Here, hydrochlorofluoroolefin (HCFO) is a halogenated olefin composed of carbon, fluorine, chlorine and hydrogen. Further, hydrofluoroolefin (HFO) is a halogenated olefin composed of carbon, fluorine, and hydrogen.

  HCFO and HFO not only have a smaller environmental load than conventionally used solvents, but also have low surface tension and low viscosity because they have fluorine in the molecule. Therefore, it easily penetrates into fine parts such as wood structure. Further, since the heats of evaporation of HCFO and HFO are small, the temperature of the wood is less likely to decrease when drying the wood into which the HCFO and HFO have been injected. Therefore, the occurrence of dew condensation due to the temperature decrease of the wood during drying is suppressed. Therefore, the water content of the wood is unlikely to increase due to dew condensation, and the dimensional change of the wood is easily suppressed. Furthermore, HCFO and HFO have higher solubility of wood preservatives than HFC and HFE. Further, since HCFO and HFO have excellent stability, they do not decompose even if used HCFO and HFO are purified by distillation, and thus can be reused.

  As the halogenated olefin, HCFO is more preferable because it has high solubility in various chemicals for preserving wood, has no flammability, and has a small heat of vaporization during drying. Since HCFO contains one or more chlorine atoms, it is easy to improve the solubility with respect to various chemicals for preserving wood. The higher the number of chlorine atoms, the more improved the solubility for various kinds of wood preservatives. HCFO preferably has a total number of chlorine atoms and fluorine atoms larger than the number of hydrogen atoms, since it has no flammability.

  The HCFO having a boiling point of 30 to 65 ° C. preferably has 3 to 4 carbon atoms, 2 to 5 fluorine atoms, and 1 to 2 chlorine atoms.

  Specific examples of HCFO having a boiling point of 30 to 65 ° C. include 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd, hereinafter referred to as “1233yd”), (Z) -1-chloro-3. , 3,3-Trifluoropropene (HCFO-1233zd (Z), hereinafter referred to as "1233zd (Z)", boiling point 39.5 ° C), 1,3-dichloro-2,3,3-trifluoropropene (HCFO). -1223yd, hereinafter referred to as "1223yd") is preferable, and 1233yd is more preferable from the viewpoint of excellent solubility of the wood preserving agent.

  Note that 1233yd may be a Z-form (1233yd (Z), boiling point 54 ° C.) or an E-form (1233yd (E), boiling point 48 ° C.), or a mixture thereof. Similarly, 1223yd may be a Z-form (1223yd (Z)) or an E-form (1223yd (E)), and a mixture thereof (for example, 1223yd (Z) is 95% by mass, 1223yd (E)). May be the boiling point of the isomer mixture of 5% by mass (58 ° C.). The GWPs of 1233yd, 1233zd (Z), and 1223yd are all less than 10.

  HFO having a boiling point of 30 to 65 ° C. typically has 3 to 4 carbon atoms and 2 to 5 fluorine atoms. Specific examples of the HFO having a boiling point of 30 to 65 ° C. include 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz, hereinafter referred to as “1336mzz”). 1336mzz is preferably a Z-form (1336mzz (Z), boiling point 33 ° C., GWP2). The 1336 mzz E form (1336 mzz (E)) has a boiling point of 7.5 ° C. and cannot be used alone in the present invention, but the boiling point is adjusted to 30 ° C. or higher, and a mixture of 1336 mzz (E) and 1336 mzz (Z). Can be used in the present invention.

The content of the organic solvent is preferably 70 to 99.998% by mass, and more preferably 80 to 99.99% by mass based on the total amount of the wood preservation treatment liquid.
The organic solvent preferably has a GWP of 100 or less, more preferably 50 or less, from the viewpoint of reducing the environmental load. From the viewpoint of volatility, the boiling point of the organic solvent is preferably 30 to 100 ° C, more preferably 30 to 65 ° C.

  In the wood preservative treatment liquid of the present invention, the organic solvent is a range that does not impair the effects of the present invention, in addition to the above-mentioned halogenated olefin having a boiling point of 30 to 65 ° C., other organic solvents conventionally used as solvents for wood preserving agents. It may contain a solvent.

  Other solvents include chlorinated hydrocarbons other than the above-mentioned halogenated olefins, hydrocarbons, alcohols, ketones, ethers, esters, HCFOs or HFOs having a boiling point of less than 30 ° C, and a boiling point of 65 ° C. These include super-HCFOs or HFOs. The other solvent can be appropriately selected in consideration of the compatibility with the halogenated olefin having a boiling point of 30 to 65 ° C. so that the GWP, the boiling point, and the like of the organic solvent fall within the above range, for example.

  From the above viewpoint, regarding the organic solvent contained in the wood preservation treatment liquid of the present invention, considering the contents of halogenated olefins having a boiling point of 30 to 65 ° C. and other solvents, the following contents are preferable. . That is, the content of the halogenated olefin is preferably 50% by mass or more, and more preferably 70% by mass or more with respect to the total amount of the organic solvent from the viewpoint of excellent solubility of the wood preserving agent and reducing the environmental load. It is particularly preferred that the organic solvent is composed solely of halogenated olefins having a boiling point of 30 to 65 ° C.

  Further, when the wood preservation treatment liquid of the present invention contains other solvent, the content of the other solvent is 50 with respect to the total amount of the organic solvent from the viewpoint of improving the solubility of the wood preservation agent and reducing the environmental load. The content is preferably not more than mass%, more preferably not more than 30 mass%, further preferably not more than 10 mass%, particularly preferably not more than 5 mass%.

  As the chlorinated hydrocarbons used as the other solvent, saturated chlorinated hydrocarbons having 1 to 6 carbon atoms are preferable, and specifically, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, Examples include 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, and 1,2-dichloropropane.

  The hydrocarbons are preferably chain or cyclic saturated or unsaturated hydrocarbons having 5 to 15 carbon atoms, and specifically, n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane. Is more preferable.

  The alcohols are preferably chain or cyclic saturated or unsaturated alcohols having 1 to 16 carbon atoms, and more preferably methanol, ethanol or isopropyl alcohol.

  As the ketones, chain or cyclic saturated or unsaturated ketones having 3 to 9 carbon atoms are preferable, and specifically, acetone and methyl ethyl ketone are more preferable.

  As the ethers, chain or cyclic saturated or unsaturated ethers having 2 to 8 carbon atoms are preferable, and specifically, diethyl ether, diisopropyl ether, dimethoxymethane, dioxane and tetrahydrofuran are more preferable.

As the esters, chain or cyclic saturated or unsaturated esters having 2 to 19 carbon atoms are preferable, and specifically, methyl acetate and ethyl acetate are more preferable.
The other solvent may be one kind or two or more kinds.

  The wood preservative agent used in the present invention is a fungicide or insecticide that removes fungi that corrode wood and insects such as termites that erode wood, and is used as an antiseptic agent, a termiticide, and a fungicide. It may be one. The wood preserving agent is mixed with the halogenated olefin and injected into the wood, and then the halogenated olefin is volatilized to remain in the wood. As the wood preservation chemical, for example, a conventionally used wood preservation chemical can be used. Further, as the wood preserving agent, a wood preserving agent having the same wood preservability as that of a conventionally used wood preserving agent and having low toxicity to the human body can be used.

  The halogenated olefin used in the present invention has a halogen atom, particularly a chlorine atom, in the molecule, and thus exhibits excellent solubility in the above wood preservative agent. The halogenated olefin is considered to have polarity in the molecule because it further has an unsaturated bond (carbon-carbon double bond). Therefore, among the conventionally used wood preserving agents, ammonium-based, triazole-based, neonicotinoid-based, phenylpyrazole-based, phenylpyrrole-based, benzoylphenylurea-based, anthranilic diamide-based, and fatty acid-containing nitrogen atoms have been used. It is considered that the solubility of the fatty acid having an aromatic ring in wood preserving agents such as copper and zinc salts is particularly excellent.

  Specific examples of the ammonium-based wood preservative agent used in the present invention include didodecyldimethylammonium chloride and N, N-didecyl-N-methyl-polyoxyethyl-ammonium propionate.

  Specific examples of the triazole-based wood preserving agent include (2RS, 3RS; 2RS, 3SR) -2- (4-chlorophenyl) -3-cyclopropyl-1- (1H-1,2,4-triazole-1. -Yl) butan-2-ol, (RS) -1-p-chlorophenyl-4,4-dimethyl-3- (1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol, 1- [[2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole may be mentioned.

  Specific examples of neonicotinoid-based wood preserving agents include (E) -N1-[(6-chloro-3-pyridyl) methyl] -N2-cyano-N1-methylacetamidine, 1-[(6- Chloro-3-pyridinyl) methyl] -4.5-dihydro-N-nitro-1H-imidazol-2-amine, (E) -1- (2-chloro-1,3-thiazol-5-ylmethyl) -3 -Methyl-2-nitroguanidine, (EZ) -3- (2-chloro-1,3-thiazol-5-ylmethyl) -5-methyl-1,3,5-oxadiazinane-4-ylidene (nitro) amine Can be mentioned.

  Specifically as a phenylpyrazole-based agent for preserving wood, 5-amino-1- [2,6-dichloro-4- (trifluoromethyl) phenyl] -4-[(trifluoromethyl) sulfonyl] -1H- Pyrazole-3-carbonitrile may be mentioned.

  Specific examples of the phenylpyrrole-based compound for preserving wood include 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile. Specific examples of the benzoylphenyluric acid-based chemicals for preserving wood include 1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2. 6-difluorobenzoyl) urea, (RS) -1- [3-chloro-4- (1,1,2-trifluoro-2-trifluoromethoxyethoxy) phenyl] -3- (2,6-difluorobenzoyl) Urea is mentioned.

  Specifically as an anthranilic diamide-based agent for preserving wood, 3-bromo-N- [4-chloro-2-methyl-6- (methylcarbamoyl) phenyl] -1- (3-chloropyridine-2- Il) -1H-pyrazole-5-carboxamide. Methyl = {2- [1- (4-chlorophenyl) pyrazol-3-yloxymethyl] phenyl} (methoxy) carbamate as a strobilurin-based wood preservative, and (±) -as a pyrethroid-based wood preservative. α-Cyano-3-phenoxybenzyl (+)-cis, trans-chrysanthemate, 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether, 4-ethoxyphenyl [3- (4- Fluoro-3-phenoxyphenyl) propyl] dimethylsilane, 2-methylbiphenyl-3-ylmethyl (Z)-(1RS, 3RS) -3- (2-chloro-3,3,3-trifluoroprop-1-enyl) ) -2,2-Dimethylcyclopropanecarboxylate, (Z)-(S) -2-methyl-4-oxo-3- (Penta-2,4-dienyl) cyclopent-2-enyl = (1R) -trans-2,2-dimethyl-3- (2-methylprop-1-enyl) cyclopropanecarboxylate or (Z)-(S) 2-Methyl-4-oxo-3- (penta-2,4-dienyl) cyclopent-2-enyl = (+)-trans-chrysanthemate, 3-phenoxybenzyl = 2- (2,2-dichlorovinyl) ) -3,3-Dimethyl-1-cyclopropanecarboxylate.

  In addition, copper and zinc salts of fatty acids and fatty acids having an aromatic ring, specifically zinc naphthenate, copper naphthenate, zinc oxide, cupric oxide, cupric oxide, cupric oxide, and secondary hydroxide. Copper, zinc versatate, 4-bromo-2- (4-chlorophenyl) -1-ethoxymethyl-5- (trifluoromethyl) pyrrole-3-carbonitrile, (EZ) -2 '-[2- (4- Cyanophenyl) -1- (α, α, α-trifluoro-m-tolyl) ethylidene] -4- (trifluoromethoxy) carbanilohydrazide, (RS) -1-methyl-2-nitro-3- (tetrahydro Examples include -3-furylmethyl) guanidine, 3-iodo-2-propynylbutyl carbamate, 2-phenylphenol, and creosote oil containing coal tar as a main component.

  Among the above-mentioned wood preservative agents, for example, triazole-based wood preservative agents (2RS, 3RS; 2RS, 3SR) -2- (4-chlorophenyl) -3-cyclopropyl-1- (1H-1, 2,4-triazol-1-yl) butan-2-ol (for example, cyproconazole commercially available from Fumakiller Total Systems Co., Ltd.), a neonicotinoid-based wood preservative agent 1-[(6-chloro- 3-pyridinyl) methyl] -4.5-dihydro-N-nitro-1H-imidazol-2-amine (for example, imidacloprid commercially available from LANXESS CORPORATION), a pyrethroid-based wood preservative agent 2- (4- Ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether (e.g. commercially available from Mitsui Chemicals Agro, Inc. Enburokkusu), commercially available product from copper naphthenate (for example, Showa Chemical Co., Ltd.) and the like are preferable. The wood preserving agents may be used alone or in combination of two or more.

  The content of the wood preservation agent is preferably 0.002 to 30% by mass, and more preferably 0.01 to 20% by mass, based on the total amount of the wood preservation treatment liquid.

  The wood preservation treatment liquid contains additives such as stabilizers and dispersants, which are usually contained in the wood preservation treatment liquid, in addition to the above-mentioned wood preservation agent and organic solvent which are the bactericidal / insecticide components. Good. The content of such an additive is, for example, 1% by mass or less based on the total amount of the wood preservation treatment liquid.

<Method of manufacturing wood with chemicals for preserving wood>
Next, a method for producing wood with a chemical for preserving wood of the present invention will be described.
The method for producing a wood with a chemical for preserving wood of the present invention comprises contacting the wood preservative treatment liquid of the present invention described above with wood, and then volatilizing an organic solvent from the preservative treatment liquid for wood to give wood with the chemical preservative for wood preservation. It is a manufacturing method.

  As a method of contacting the wood preservation treatment liquid with the wood, a method of applying the wood preservation treatment liquid to the wood surface with a brush, a method of spraying onto the wood surface, a method of dipping the wood in the wood preservation treatment liquid, a wood preservation treatment liquid There is a contact method such as applying pressure while the wood is immersed in. The wood preservation chemical in the wood preservation treatment liquid is preferably dissolved in the above-mentioned organic solvent. Therefore, due to the above-mentioned contact, the wood treating chemical adheres to the surface of the wood together with the organic solvent, and further penetrates from the surface of the wood to the inside. Then, the organic solvent is volatilized and removed by heating the wood or leaving it at room temperature.

  Among the above-mentioned contact methods, for example, the method disclosed in Patent Document 1 can be used as a contact method in which wood is soaked in a wood preservation treatment liquid and pressure is applied to allow the wood treatment liquid to penetrate into the wood. Even when used in the processing apparatus as described in Patent Document 1, the halogenated olefin having a boiling point of 30 to 65 ° C., particularly HCFO used in the present invention is a volatile liquid at room temperature and atmospheric pressure. Therefore, it is suitable for recovery by evaporation and condensation. Further, the method for preserving wood as shown in Patent Document 1 is generally performed in a closed system, but there is an organic solvent released when the wood is taken out of the apparatus in the processing step. Since the halogenated olefin used in the present invention has little influence on the environment, it is possible to reduce the environmental load caused by the organic solvent released without being recovered.

Next, examples will be described. The present invention is not limited to the examples below.
Each substance used in the examples was obtained by using a commercially available product or was prepared by synthesis, as described below.

1233yd was synthesized by the method described in WO 2017/018412. That is, 1-chloro-2,2,3,3-tetrafluoropropane (CHF ₂ —CF ₂ —CHFCl, HCFC-244ca) was defluorinated at a temperature of 50 to 80 ° C. using potassium hydroxide as a reactant. By reacting with hydrogen, 10 kg of a reaction product containing 1233yd at a purity of 99.5% was obtained. The obtained 1233yd was an isomer mixture in which the Z isomer (1233yd (Z)) was 95% by mass and the E isomer (1233yd (E)) was 5% by mass.

  The Z-form of 1233zd (1233zd (Z)) was synthesized by the method described in JP2013-87066A. That is, 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa), 2-chloro-1,1,1,3,3-pentafluoropropane (HCFC-235da) and 1233zd (Z). Crude 1233zd (Z) containing was mixed with triethylamine and reacted at 150 ° C. for 3 hours to obtain a reaction product containing 1233zd (Z). The reaction product was further purified to obtain purified 1233zd (Z) having a purity of 99.5%. In the following tests, the purified 1233zd (Z) is referred to as 1233zd (Z).

  1223yd was synthesized by the method described in GB7099887. Specifically, granular zinc (39 g) was placed in a flask equipped with a reflux condenser, and the surface was covered with 50 cc of absolute ethanol. 1,1,2,3-Tetrachloro-2,3,3-trifluoropropane (118 g) was dissolved in 75 cc absolute ethanol and the resulting solution was added dropwise to the zinc / ethanol mixture in the flask. The drip rate was controlled to prevent vigorous reflux. After the addition was complete, the reaction mixture was refluxed for about 90 minutes. Excess ethanol was dissolved in water, the organic phase was separated from the aqueous phase, and dried with anhydrous calcium chloride to obtain 1223yd. The obtained 1223yd was an isomer mixture in which the Z isomer (1223yd (Z)) was 95 mass% and the E isomer (1223yd (E)) was 5 mass%.

  HCFC-225 is a commercially available mixture of 1,1-dichloro-2,2,3,3,3-heptafluoropropane and 1,3-dichloro-1,2,2,3,3-heptafluoropropane. Manufactured by AGC Co., Ltd., AK-225 was used.

  An agent for preserving wood is cyproconazole ((2RS, 3RS; 2RS, 3RS) -2- (4-chlorophenyl-3-cyclocyclopropyl-1- (1H-1,2,4-triazol-1-yl ) Butan2-ol, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. and imidacloprid (1-[(6′-chloro-3′-pyridyl) methyl] imidazolidine-2- (N-nitro) imine, Fuji Film Wako Pure. Yaku Co., Ltd.) was used.

[Examples 1 to 24]
As shown in Table 1 for cyproconazole and as shown in Table 2 for imidacloprid, the above wood-preserving agents were dissolved in the respective HCFO and AK-225 produced by the above-mentioned methods to prepare a wood preservation treatment solution. Prepared. Examples 1 to 12 and 17 to 22 are Examples, and Examples 13 to 16, 23 and 24 are Comparative Examples.

(Solubility test)
The solubility of the wood preserving agents in organic solvents was compared when preparing the wood preserving treatment liquid in each of the above examples. Solubility is determined by visually observing the state of the wood preservation treatment liquid immediately after mixing the wood preserving agent and the organic solvent and after 30 minutes from mixing the wood preserving agent and the organic solvent. The state in which the use chemicals were dissolved was evaluated as ◯ (good solubility), and the presence of an insoluble matter for the wood preserving agent or cloudiness was evaluated as x (poor solubility). The results are shown in Tables 1 and 2.

  From Table 1 and Table 2, it was found that each of the above HCFOs had a higher solubility for wood preserving agents than AK-225, and an excellent solubility after 30 minutes from mixing. Among them, it was found that 1233yd had the best solubility for the wood preserving agent and that the wood preserving agent could be dissolved immediately after mixing.

[Examples 25 to 28]
<Preparation of wood preservation solution>
Cyproconazole and imidacloprid were dissolved in the respective organic solvents of 1233yd, 1233zd (Z), 1223yd, and AK-225 to prepare four types of wood preservative treatment solutions of Examples 25 to 28 shown in Table 3. The content of diproconazole was 0.02% by mass and the content of imidacloprid was 0.01% by mass with respect to the total amount of the wood preservation treatment liquid. Examples 25 to 27 are examples and Example 28 is a comparative example.

<Production of wood with chemicals for wood preservation>
Using the obtained four types of wood preservation treatment liquids of Examples 25 to 28, wood was treated by the following method.
2.35 g of Japanese cedar wood pieces cut out from a 5 mm-thick wood board were placed in a pressure-resistant airtight container and subjected to a pressure-reducing treatment at -0.097 MPaG for 20 minutes until the pressure-reduced state reached equilibrium with atmospheric pressure. The wood preservation treatment liquid was sucked into the container. In a nitrogen gas atmosphere, the pressure was increased to 0.76 MPaG and the mixture was allowed to stand for 30 minutes. Then, after releasing the pressure in the container to atmospheric pressure, the wood treatment solution in the container was extracted to obtain wood with a chemical agent for preserving wood before drying.

  The wood with the chemicals for preserving wood obtained by the above method was dried at 50 ° C. for 12 hours. After that, when the wood was cut at the center and 1,5-diphenylcarbazone was applied to the cross section, a red color was obtained, confirming that the wood preservative could be injected into the wood. The results are shown in Table 3 in which the case where the wood preserving agent could be injected into the wood was marked as "○".

  From Examples 25 to 27, which are the above Examples, wood was treated with a wood preservative treatment solution obtained by dissolving a wood preserving agent in the above HCFO, thereby treating wood in the same manner as in Comparative Example 28. It has been found that it is possible to produce medicated wood.

Claims (5)

  A wood preservation treatment liquid containing a wood preservation agent and an organic solvent containing a halogenated olefin having a boiling point of 30 ° C. or higher and 65 ° C. or lower.   The halogenated olefin is (Z) -1-chloro-3,3,3-trifluoropropene, (E) -1-chloro-2,3,3-trifluoropropene, (Z) -1-chloro- From 2,3,3-trifluoropropene, (E) -1,3-dichloro-2,3,3-trifluoropropene and (Z) -1,3-dichloro-2,3,3-trifluoropropene The wood preservation treatment liquid according to claim 1, which is at least one selected from the group consisting of:   The wood preservation treatment liquid according to claim 1 or 2, wherein the content of the halogenated olefin is 50% by mass or more based on the total amount of the organic solvent.   The wood preservation treatment liquid according to any one of claims 1 to 3, wherein the content of the organic solvent is 70% by mass or more and 99.998 wt% or less with respect to the total amount of the wood preservation treatment liquid.   A method for producing wood with a chemical agent for preserving wood, which comprises obtaining the wood with the chemical agent for preserving wood by contacting the treatment solution for preserving wood according to any one of claims 1 to 4 with the wood and then volatilizing the organic solvent. Method.