JP7095540B2 - How to manufacture wood with wood preservation treatment liquid and wood preservation chemicals - Google Patents

Description

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

Wood is a material used in various fields, but it has a drawback that it deteriorates due to corrosion by fungi and erosion by insects, resulting in a decrease in strength. Therefore, various wood preservation treatment liquids for preventing deterioration due to fungi and insects, and methods for producing wood with a wood preservation chemical using the same have been conventionally 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). Is known as a method using. In this method, the wood is directly heated by using high frequency heating, and the solvent is recovered from the wood (see, for example, Patent Document 1).

Japanese Patent No. 4149422

HCFCs and HFEs used as solvents in conventional wood preservation treatment liquids have an advantage that they do not have a flash point. However, HCFC is scheduled to be completely abolished at the end of 2019 in developed countries due to concerns about ozone layer depletion. Further, since HFE has a low solubility of a wood preservation agent, there is a problem that the wood preservation agent that can be used is limited.

Therefore, there is a demand for a wood preservative treatment solution and wood with a wood preservative, which use a solvent that has a small environmental load and has excellent solubility in various wood preservatives because there is no concern about ozone layer depletion. There is.

The present invention includes a wood preservation treatment liquid containing an organic solvent and a wood preservation treatment liquid, a wood preservation treatment liquid having a small environmental load due to the organic solvent, and a wood preservation treatment liquid having a small environmental load using the wood preservation treatment liquid. It is intended to provide a method for producing 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 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.
[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 solution according to [1], which is at least one selected from the group consisting of fluoropropene.
[3] The wood preservation treatment liquid according to [1] or [2], wherein the content of the halogenated olefin is 50% by mass or more with respect to the total amount of the organic solvent.
[4] The wood preservation 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 with respect to the total amount of the wood preservation treatment liquid. Treatment liquid.
[5] After the wood preservation treatment liquid according to any one of [1] to [4] is brought into contact with wood, the organic solvent is volatilized to obtain wood with a wood preservation agent, with a wood preservation agent. How to make wood.

According to the present invention, in a wood preservation treatment liquid containing an organic solvent and a wood preservation chemical, a wood preservation treatment liquid having a small environmental load due to the solvent and a wood preservation treatment liquid using the wood preservation treatment liquid having a small environmental load are used. A method for producing a wood with a chemical 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 geometric isomer and its abbreviation indicates an E form (trans form), and (Z) indicates a Z form (cis form). When the E-form and Z-form are not specified in the name and abbreviation of the compound, the name and abbreviation mean an E-form, a Z-form, and a general term including a mixture of E-form and Z-form.

In this specification, the Global Warming Potential (GWP) is a 100-year value of 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, "-" representing a numerical range includes an upper and lower limit.

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 from the viewpoint that the wood preserving agent can be uniformly and evenly adhered to the wood. As used herein, "dissolving" means that there is no cloudiness or formation of insoluble matter in the wood preservation treatment liquid 30 minutes after 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 or more kinds.

In the halogenated olefin used in the present invention, one or more hydrogen atoms bonded to carbon atoms of an unsaturated hydrocarbon compound having one or more carbon-carbon double bonds in the molecule are replaced with halogen atoms. It is a compound. The halogen atom that can replace the hydrogen atom is fluorine, chlorine, bromine, and 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 kind of the above-mentioned halogen atom, or may have two or more kinds.

Since the halogenated olefin used in the present invention has a carbon-carbon double bond in the molecule, it 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 potential, and has a small environmental load. In addition, it is excellent in solubility and volatility as a solvent for wood preservation chemicals.

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

HCFOs and HFOs not only have a smaller environmental load than conventionally used solvents, but also have low surface tension and low viscosity due to having fluorine in the molecule. Therefore, it easily penetrates into small parts such as wood tissue. Further, since HCFO and HFO have a small heat of vaporization, the temperature of the wood is unlikely to decrease when the wood in which the HCFO and HFO are injected is dried. Therefore, the generation of dew condensation due to the decrease in the temperature of the wood during drying is suppressed. Therefore, it is difficult for the water content of the wood to increase due to dew condensation, and it is easy to suppress the dimensional change of the wood. Furthermore, HCFOs and HFOs have higher solubility of wood preservatives than HFCs and HFEs. Further, since HCFO and HFO have excellent stability, they can be reused because they do not decompose even if the used HCFO and HFO are distilled and purified.

As the halogenated olefin, HCFO is more preferable because it has high solubility in various wood preservation agents, is not flammable, and has a small heat of vaporization during drying. Since HCFO contains one or more chlorine atoms, it is easy to improve the solubility in various wood preservation chemicals. The higher the number of chlorine atoms, the better the solubility in a wider variety of wood preservatives. In HCFO, the total number of chlorine atoms and fluorine atoms is preferably larger than the number of hydrogen atoms in that it does not have flammability.

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

Specifically, 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd, hereinafter referred to as "1233yd"), (Z) -1-chloro-3 as HCFO having a boiling point of 30 to 65 ° C. , 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 preservation agent.

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

An HFO having a boiling point of 30 to 65 ° C. typically has 3 to 4 carbon atoms and 2 to 5 fluorine numbers. 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-1336 mzz, hereinafter referred to as "1336 mzz"). The 1336 mzz is preferably Z-form (1336 mzz (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 is a mixture of 1336 mzz (E) and 1336 mzz (Z) having a boiling point adjusted to 30 ° C. or higher. Can be used in the present invention.

The content of the organic solvent is preferably 70 to 99.998% by mass, 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 preservation treatment liquid of the present invention, the organic solvent is not only the above-mentioned halogenated olefin having a boiling point of 30 to 65 ° C., but also other solvents conventionally used as a solvent for wood preservation agents, as long as the effect of the present invention is not impaired. 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. Super HCFOs or HFOs and the like. The other solvent can be appropriately selected in consideration of compatibility with a halogenated olefin having a boiling point of 30 to 65 ° C. so that the GWP, boiling point, etc. of the organic solvent are in the above range, for example.

From the above viewpoint, the organic solvent contained in the wood preservation treatment liquid of the present invention preferably has the following contents in consideration of the contents of the halogenated olefin having a boiling point of 30 to 65 ° C. and other solvents. .. That is, the content of the halogenated olefin is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total amount of the organic solvent, from the viewpoint of excellent solubility of the chemical for preserving wood and reducing the environmental load. It is particularly preferable that the organic solvent is composed only of a halogenated olefin having a boiling point of 30 to 65 ° C.

When the wood preservation treatment liquid of the present invention contains other solvents, the content of the other solvents 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. It is preferably 0% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

As the chlorinated hydrocarbons used as other solvents, saturated chlorinated hydrocarbons having 1 to 6 carbon atoms are preferable, and specifically, methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, and the like. Examples thereof 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, 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 preservation agent used in the present invention is a bactericidal / insecticide that removes fungi that corrode wood and insects such as termites that erode wood, and is used as a preservative, an anti-termite agent, and an antifungal agent. It may be one. The wood preservation 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 preserving agent, for example, a conventionally used wood preserving agent can be used. Further, as the wood preservation agent, a agent having the same wood preservation property as the conventionally used wood preservation 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-mentioned wood preservation agent. Halogenated olefins are considered to have intramolecular polarity because they have an unsaturated bond (carbon-carbon double bond). Therefore, among the conventionally used wood preservation agents, ammonium-based, triazole-based, neonicotinoid-based, phenylpyrazole-based, phenylpyrrole-based, benzoylphenylurea-based, anthranilic diamide-based, fatty acids and fatty acids having nitrogen atoms It is considered that the fatty acid having an aromatic ring is particularly excellent in solubility in wood preservation chemicals such as copper and zinc salts.

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

Specifically, as a triazole-based wood preservation agent, (2RS, 3RS; 2RS, 3SR) -2- (4-chlorophenyl) -3-cyclopropyl-1- (1H-1,2,4-triazole-1) -Il) Butan-2-ol, (RS) -1-p-chlorophenyl-4,4-dimethyl-3- (1H-1,2,4-triazole-1-ylmethyl) pentane-3-ol, 1- [[2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole can be mentioned.

Specifically, as a neonicotinoid-based wood preservation agent, (E) -N1-[(6-chloro-3-pyridyl) methyl] -N2-cyano-N1-methylacetamidine, 1-[(6-- Chloro-3-pyridinyl) methyl] -4.5-dihydro-N-nitro-1H-imidazole-2-amine, (E) -1- (2-chloro-1,3-thiazole-5-ylmethyl) -3 -Methyl-2-nitroguanidine, (EZ) -3- (2-chloro-1,3-thiazole-5-ylmethyl) -5-methyl-1,3,5-oxadiadinane-4-iriden (nitro) amine Can be mentioned.

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

Specific examples of wood preservation agents for phenylpyrrole compounds include 4- (2,2-difluoro-1,3-benzodioxole-4-yl) pyrrole-3-carbonitrile. Specifically, 1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2) as a benzoylphenyl uric acid-based wood preservative. 6-Difluorobenzoyl) urea, (RS) -1- [3-chloro-4- (1,1,2-trifluoro-2-trifluoromethoxyethoxy) phenyl] -3- (2,6-difluorobenzoyl) Urea can be mentioned.

Specifically, 3-bromo-N- [4-chloro-2-methyl-6- (methylcarbamoyl) phenyl] -1- (3-chloropyridin-2-) as an anthranilic diamide-based wood preservation agent. Il) -1H-pyrazole-5-carboxamide. Methyl = {2- [1- (4-chlorophenyl) pyrazole-3-yloxymethyl] phenyl} (methoxy) carbamate as a struvyllin-based wood preservation agent, (±)-as a pyrethroid-based wood preservation agent α-Cyano-3-phenoxybenzyl (+)-cis, trans-crisantemate, 2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether, 4-ethoxyphenyl [3- (4- (4-ethoxyphenyl) Fluoro-3-phenoxyphenyl) propyl] dimethylsilane, 2-methylbiphenyl-3-ylmethyl (Z)-(1RS, 3RS) -3- (2-chloro-3,3,3-trifluoropropa-1-enyl) ) -2,2-Dimethylcyclopropanecarboxylate, (Z)-(S) -2-Methyl-4-oxo-3- (pent-2,4-dienyl) Cyclopent-2-enyl = (1R) -trans -2,2-dimethyl-3- (2-methylpropa-1-enyl) cyclopropanecarboxylate or (Z)-(S) -2-methyl-4-oxo-3- (penta-2,4-dienyl) Cyclopenta-2-enyl = (+)-trans-crisantemate, 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, cupric hydroxide. Copper, zinc versaticate, 4-bromo-2- (4-chlorophenyl) -1-ethoxymethyl-5- (trifluoromethyl) pyrrole-3-carbonitrile, (EZ) -2'-[2- (4- (4- (4-) Cyanophenyl) -1- (α, α, α-trifluoro-m-tolyl) ethylidene] -4- (trifluoromethoxy) carbanilohydrazide, (RS) -1-methyl-2-nitro-3- (tetrahydro) Examples thereof include -3-furylmethyl) guanidine, 3-iodo-2-propynylbutylcarbamate, 2-phenylphenol, and creosote oil containing coltal as a main component.

Among the above-mentioned wood preservation agents, for example, triazole-based wood preservation agents (2RS, 3RS; 2RS, 3SR) -2- (4-chlorophenyl) -3-cyclopropyl-1- (1H-1, 2,4-Triazole-1-yl) Butan-2-ol (for example, cyproconazole commercially available from Fumakiller Total System Co., Ltd.), a neonicotinoid wood preservation agent 1-[(6-chloro-) 3-Pyridinyl) Methyl] -4.5-dihydro-N-nitro-1H-imidazol-2-amine (for example, imidazole chloride commercially available from Rankses Co., Ltd.), a pyrethroid-based wood preservation agent 2- (4-) Ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether (for example, etofenblocks commercially available from Mitsui Kagaku Agro Co., Ltd.), copper naphthenate (for example, a product commercially available from Showa Kagaku Co., Ltd.) and the like are preferable. As the wood preservation agent, one type may be used alone, or two or more types may be used in combination.

The content of the wood preservation chemical is preferably 0.002 to 30% by mass, more preferably about 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 wood preservation chemicals and organic solvents which are the above-mentioned bactericidal and insecticide components. It is also good. The content of such an additive is, for example, 1% by mass or less with respect to the total amount of the wood preservation treatment liquid.

<Manufacturing method of wood with chemicals for wood preservation>
Next, the method for producing the wood with a chemical for wood preservation of the present invention will be described.
In the method for producing wood with a chemical for wood preservation of the present invention, after the above-mentioned wood preservation treatment liquid of the present invention is brought into contact with wood, an organic solvent is volatilized from the wood preservation treatment liquid to obtain wood with a chemical for wood preservation. It is a manufacturing method to obtain.

As a method of contacting the wood preservation treatment liquid with wood, a method of applying the wood preservation treatment liquid to the wood surface with a brush, a method of applying the wood surface with a spray, a method of immersing the wood in the wood preservation treatment liquid, a method of immersing the wood in the wood preservation treatment liquid, a wood preservation treatment liquid. There is a contact method such as a method of applying pressure while the wood is immersed in the wood. The wood preserving agent in the wood preserving treatment liquid is preferably dissolved in the above-mentioned organic solvent. Therefore, due to the above-mentioned contact, the wood treatment agent adheres to the surface of the wood together with the organic solvent, and further penetrates from the surface of the wood to the inside. After that, 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 shown in Patent Document 1 can be used as the contact method in which the wood is immersed in the wood preservation treatment liquid and pressure is applied to allow the wood treatment liquid to permeate the wood. Even when used in a 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 normal temperature and pressure. Therefore, it is suitable for recovery by evaporation and condensation. Further, although the wood preservation treatment method as shown in Patent Document 1 is generally performed in a closed system, there is an organic solvent released when the wood is taken out from the apparatus in the treatment step. Since the halogenated olefin used in the present invention has little influence on the environment, it is possible to reduce the environmental load due to the organic solvent released without being recovered.

Next, an embodiment will be described. The present invention is not limited to the following examples.
Each substance used in the examples was prepared by obtaining a commercially available product or synthesizing it as described below.

1233yd was synthesized by the method described in International Publication No. 2017/01/8412. That is, 1-chloro-2,2,3,3-tetrafluoropropane (CHF2 _- CF2 _- CHFCl, HCFC-244ca) is defluorinated at a temperature of 50 to 80 ° C. using potassium hydroxide as a reactant. By hydrogen reaction, 10 kg of a reaction product containing 1233 yd with a purity of 99.5% was obtained. The obtained 1233yd was an isomer mixture having a Z-form (1233yd (Z)) of 95% by mass and an E-form (1233yd (E)) of 5% by mass.

The Z-form (1233zd (Z)) of 1233 zd 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 1233 zd (Z) containing 1233 zd (Z) was mixed with triethylamine and reacted at 150 ° C. for 3 hours to obtain a reaction product containing 1233 zd (Z). Further, the reaction product was purified to obtain purified 1233 zd (Z) having a purity of 99.5%. In the following tests, the purified 1233zd (Z) will be referred to as 1233zd (Z).

1223yd was synthesized by the method described in GB709887. 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 of absolute ethanol and the resulting solution was added dropwise to the zinc / ethanol mixture in the flask. The dropping rate was controlled to prevent violent 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 1223 yd. The obtained 1223yd was an isomer mixture having a Z-form (1223yd (Z)) of 95% by mass and an E-form (1223yd (E)) of 5% by mass.

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

As a wood preservation agent, cyproconazole ((2RS, 3RS; 2RS, 3RS) -2- (4-chlorophenyl-3-cicyclopropyl-1- (1H-1,2,4-triazole-1-yl)-) ) Butan 2-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 Jun Yaku Co., Ltd.) was used.

[Examples 1 to 24]
Each of the above wood preservatives is dissolved in each HCFO and AK-225 produced by the above method as shown in Table 1 for cyproconazole and as shown in Table 2 for imidacloprid, respectively, 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 wood preservatives in organic solvents was compared during the preparation of the wood preservative treatment liquids in each of the above examples. The solubility is determined by visually observing the state of the wood preservation treatment solution immediately after mixing the wood preservation agent and the organic solvent and 30 minutes after mixing the wood preservation agent and the organic solvent, and storing the wood. The state in which the chemicals were dissolved was evaluated as ◯ (good solubility), and the presence or absence of insoluble substances in the wood preservation chemicals was evaluated as x (poor solubility). The results are shown in Tables 1 and 2.

From Tables 1 and 2, it was found that both of the above HCFOs have higher solubility of wood preservatives than AK-225 and are superior in solubility 30 minutes after mixing. Among them, it was found that 1233yd has the best solubility in wood preservation agents and can dissolve wood preservation agents immediately after mixing.

[Examples 25 to 28]
<Preparation of wood preservation treatment liquid>
Ciproconazole and imidacloprid were dissolved in the organic solvents of 1233yd, 1233zd (Z), 1223yd, and AK-225 to prepare four kinds of wood preservation treatment solutions of Examples 25 to 28 shown in Table 3. The content of diproconazole is 0.02% by mass and the content of imidacloprid is 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.

<Manufacturing of wood with chemicals for wood preservation>
The wood was treated by the following method using the obtained four kinds of wood preservation treatment liquids of Examples 25 to 28.
2.35 g of wood pieces of Sugi cut out from a 5 mm thick wood board are placed in a pressure-resistant airtight container, decompressed at -0.097 MPaG for 20 minutes, and then from a depressurized state to equilibrium with atmospheric pressure. The wood preservation treatment liquid was sucked into the container. After pressurizing to 0.76 MPaG under a nitrogen gas atmosphere, 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 withdrawn to obtain wood with a chemical for wood preservation before drying.

Each wood with a wood preservation agent obtained by the above method was dried at 50 ° C. for 12 hours. After that, when 1,5-diphenylcarbazone was cut at the center of the wood and the cross section was coated with 1,5-diphenylcarbazone, the color turned red, confirming that the wood preserving agent could be injected into the wood. Table 3 shows the results as "○" when the wood preservation agent could be injected into the wood.

From Examples 25 to 27 of the above-mentioned Examples, by treating wood with a wood preservation treatment liquid obtained by dissolving a wood preservation agent in the above HCFO, the wood can be preserved in the same manner as in Example 28 which is a comparative example. It turned out that it is possible to produce wood with chemicals.

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 olefins are (Z) -1-chloro-3,3,3-trifluoropropene, (E) -1-chloro-2,3,3-trifluoropropene, and (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. The wood preservation treatment liquid according to claim 1 or 2, wherein the content of the halogenated olefin is 50% by mass or more with respect to 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% by mass or less with respect to the total amount of the wood preservation treatment liquid. Manufacture of wood with wood preservation chemicals, wherein the wood preservation treatment liquid according to any one of claims 1 to 4 is brought into contact with wood and then the organic solvent is volatilized to obtain wood with a wood preservation chemical. Method.