JPH09175916A - Antiseptic for wood - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antiseptic for wood having safety for a human body, a high antiseptic effect with a small amount and excellent sticking tendency to the wood by using a specific metal complex of a troponoid compound. SOLUTION: This antiseptic for wood uses at least one kind of a troponoid metal complex expressed by the formal (R is H, a lower alkyl or a lower alkenyl; M is a metal excepting Fe; (n) is valence of the metal M; (m) is a coordination number; (m) and (n) are the same integers of 1-6). As the troponoid compound, α,β,γ-thujaplicin, α,β,γ-dolabrin or tropolone is preferably. The metal is at least one kind selected from an alkali metal of group Ia , an alkaline earth metal of group IIa , a transition metal belonging to group IVa to group VIII excepting Fe and group Ib and a metal element belonging to group IIb to group IVb in the periodic table. Especially, a metal selected from among Na, K, Ca, Ba, V, Cr, Mn, Co, Ni, Cu, Ag, Zn and Sn is preferable. A rotproof effect for wood is particularly increased by converting the troponoid compound to a metal complex excepting the complex of Fe.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a wood preservative characterized by containing at least one troponoid metal complex represented by the following formula (1) as an active ingredient.

Embedded image

(Wherein R is a hydrogen atom, a lower alkyl group,
Lower alkenyl group, M is a metal excluding Fe, n is a valence of metal M, m is a coordination number, and n and m are the same integers of 1 to 6. )

[0003]

Conventionally, the following methods have been reported as wood preservatives. (2) An oil preservative using tals such as creosate oil. (2) An oil-soluble preservative obtained by dissolving phenols, chlornaphthalene, etc. in an organic solvent. (3) A water-soluble preservative having a composition such as As compound / Cr compound / Cu compound or F compound. (4) Emulsifying preservatives such as naphthenates and versatic acid salts.

However, among the above-mentioned wood preservatives, the creosote oil, which is a typical example of (1), is used as a cheap chemical agent with good permeability and weather resistance for utility poles, sleepers, etc. However, it is no longer used due to odor, dirt, skin irritation, safety and health problems (supervised by the Forestry Agency: wood supply and demand and the present state of the wood industry (1994 version)). Most of the phenols, which are the representative example of (2), are pesticide-based compounds and have high antiseptic effects, but most of them are used because of problems with light / heat decomposability, sublimability, and safety to the human body. It is no longer done. (3)
A water-soluble wood preservative composed of As compound, Cr compound, and Cu compound, which is a typical example of JIS, is JISK1554-198.
As specified in 5, it is widely used because of its excellent adhesion to wood, antiseptic effect, and weather resistance. However, since it contains toxic As compounds and Cr compounds, it has many problems in terms of environmental pollution such as waste materials and drainage (for example, JP-A-56).
-40481), its use has been reviewed in recent years. Therefore, the development of safer drugs with less environmental pollution is underway in (4). As an example of (4), for example, naphthenic acid C
An emulsifying preservative obtained by adding an emulsifier and an organic solvent to u, Zn naphthenate, Zn versatate and the like can be mentioned. These chemicals have the advantages of high safety and less leaching from wood, but have problems such as a bad odor problem, a weak antiseptic effect, and a high concentration.

[0005]

The troponoid metal complex used in the present invention is known and is known to be obtained by the reaction of a troponoid compound and a metal compound (see, for example, H. Iinuma, J. et al. Chem. So
c. Japan, 64, 742 (1943), B.I. E. FIG.
Bryant et al. , J. et al. Am. Chem. S
oc. , 75, 3784 (1953). ). In addition, it is known that troponoid compounds are useful as wood preservatives (for example, the Chemical Dictionary 7.486-487. Kyoritsu Shuppan (1961)). On the other hand, regarding the troponoid metal complex, JP-A-64-38203 discloses a colorant patent characterized by using a reaction solution of a tropolone salt in Hiba oil and a metal salt. However, during Hiba oil, various tropolone and phenol - not only can not identify whether the coloration by reaction with any component and the metal salt for component reacts with the metal salts such as Le acids are contained a number, which component It was also not possible to identify whether the reaction product of the metal salt with the metal salt had a wood preservative function. Further, a technique in which a troponoid metal complex is applied as a bactericide is disclosed in JP-A-7-69873 as a bactericide / disinfectant for Pseudomonas aeruginosa. However, it has not been clarified whether troponoid metal complexes have an antibacterial effect against fungi of wood-destroying fungi other than bacteria. Therefore, the present invention, when the troponoid metal complex is applied to wood preservative fungi, troponoid metal complexes other than Fe solve the problems of conventional wood preservatives, and are safe for the human body and have a high antiseptic effect even in a small amount. It was discovered that it is a wood preservative with excellent stickiness.

[0006]

In the present invention, the troponoid metal complex represented by the above formula (1) is synthesized from a tropolone compound represented by the following formula (2) and a metal compound by a known technique to obtain a troponoid compound. The antibacterial effect of wood against the wood-destroying fungus was investigated. As a result, they found that the wood preservative effect was significantly increased by using a troponoid compound as a metal complex other than Fe, compared with the troponoid compound as a raw material alone, and completed the present invention.

[0007]

Embedded image (In the formula, R is the same as the formula (1).)

In the present invention, R represented by the above formulas (1) and (2) is a hydrogen atom or a lower alkyl group or alkenyl group having about 1 to 6 carbon atoms. Specific examples of the tropolone compound represented by the above formula (2) include α, β, γ-tsuyaprisin, α, β, γ-drabulin, and tropolone. Further, as these tropolone compounds, a natural product or a synthetic product extracted from natural products such as Aomori Hiba, Taiwan cypress and the like can be used as well.

The metal used in the present invention is the periodic table Ia.
Excluding alkali metals of IIa, alkaline earth metals of IIa and Fe
It is at least one selected from transition metals belonging to IVa to Ib and metal elements belonging to IIb to IVb. When the metal is Fe, the tropolone-Fe complex formed by reacting with the tropolone compound has a significantly reduced wood preservative function than the tropolone compound as the raw material.

Specific examples of metals include Li, Na,
Alkali metal such as K, alkaline earth metal such as Be, Mg, Ca, Ti, V, Cr, Mn, Co, Ni, Cu
Examples include transition metals belonging to IVa to Ib of the periodic table excluding Fe, such as Zn, Ga and Ge, and metals belonging to IIb to IVb, such as Na, K, Ca, Ba, V and C.
Examples include metals such as r, Mn, Co, Ni, Cu, Ag, Zn, and Sn.

Further, as the metal compound, a metal inorganic salt or a metal organic salt can be used. In particular,
As the metal inorganic salt, for example, hydroxide, hydrochloride, sulfate,
Examples include sulfite, nitrate, nitrite, carbonate,
Examples of the metal organic salt include formates, acetates, propionates, oxalates, gluconates, naphthenates, etc., but are not particularly limited thereto.

The troponoid metal complex used in the present invention is a known method of reacting a troponoid compound with a metal compound (eg, H. Iinuma, J. Chem. S.
oc. Japan, 64, 742 (1943), B.I.
E. FIG. Bryant et al. , J. et al. Am. Che
m. Soc. , 75, 3784 (1953). ).

The method for synthesizing the troponoid metal complex used in the present invention is shown below. (5) When the metal is an alkali metal, the troponoid compound and the alkali metal hydroxide are heated and reacted in an equimolar aqueous solution to form a troponoid-alkali metal complex. (6) When the metal is other than an alkali metal, an aqueous solution of a metal salt is added in an equimolar amount to an aqueous solution of a troponoid-alkali metal complex, or an aqueous solution of a metal salt is added in an equivalent mole to a methanol solution of a troponoid compound to cause insolubility. Obtain the tropolone metal complex.

Specifically, in (5), for example, α, β, γ-
After heating and reacting an equimolar aqueous solution of tsuyapurisin, α, β, γ-drabulin or tropolone with KOH, water is distilled off, and each of α, β, γ-tsuyapurisin, α, β, γ-drabulin or tropolone is removed. A K metal complex can be obtained. Further, in (6), for example, α, β, γ-tsuyapurisin, α, β, γ-drabulin or tropolone each Na salt synthesized in exactly the same manner as in (5) and an equimolar aqueous solution of MgSO ₄ are mixed to produce The deposited precipitate was filtered to separate α, β, γ-
Each Mg metal complex of tsuyapricin, α, β, γ-drabulin or tropolone can be obtained. Also in (6),
For example, a solution of α, β, γ-tsuyapricin, α, β, γ-drabulin or tropolone in methanol and Zn (CH ₃
An aqueous solution of COO) ₂ is mixed and the formed precipitate is filtered to obtain each Zn (II) metal complex of α, β, γ-tsuyaprisin, α, β, γ-drabulin or tropolone. The troponoid metal complex obtained by the above method was purified by recrystallization or the like and then analyzed by elemental analysis and ICP emission spectroscopy.

The troponoid metal complex used in the present invention is
Troponoid compounds of the same number as the valence of the metal of the metal compound coordinate to form a complex. It is known that when the troponoid compound is metal-complexed in this manner, the raw material troponoid compound becomes more insoluble in water, or has a very high melting point, resulting in changes in physical properties (for example, W. von.
E. FIG. Doering et al. , J. et al. Am. Che
m. Soc. , 72, 2305 (1950). ).

The troponoid metal complex is basically insoluble in water when the metal is a metal complex other than an alkali metal. Therefore, when the troponoid metal complex is used as a wood preservative, it is applied to wood by using a suitable organic solvent or by dispersing it in water, pressurizing transparent injection and vacuum injection. As an organic solvent, there is no adverse effect such as decomposition of troponoid metal complex,
The solvent is not particularly limited as long as it is a low-flammability, low-toxicity and inexpensive solvent, and for example, petroleum-based solvents such as methanol, ethanol, ethylene glycol and kerosene are used.
When used by dispersing in water, a suitable dispersant or a surfactant is used. For example, as the surfactant, a nonionic type such as polyoxyethylene stearate, an anionic type such as dioctylsulfosuccinic acid ester, or the like is used. Used. Further, if necessary, a filler, a stabilizer and a potency enhancer may be added to prepare a preparation.

[0017]

[Synthesis Example] Hereinafter, a synthesis example of a troponoid metal complex will be described.

Synthesis Example 1. KOH, 1.68 g (0.03
(Mol) was dissolved in 150 ml of water, and 3.66 g (0.03 mol) of tropolone was added thereto and dissolved by heating. Evaporation of the water under reduced pressure leaves a yellow solid. This solid was
It was recrystallized from diethyl ether and the crystals were separated by filtration.
After drying under reduced pressure at 0 ° C., 3.61 g of yellow solid (yield 75%)
I got This solid was subjected to elemental analysis and ICP emission spectroscopic analysis. The results are shown in Table 1.

Table 1 Analysis results of (tropolone) -K complex C H N K analysis value 52.09 3.60 0.2> 23 ───────────────────── ───────────── Theoretical value 52.48 3.15 0 24.4 ────────────────────────── ─────── From Table 1, the analytical value and the theoretical value are in good agreement, (Tropolone)
It was confirmed that the -K complex was synthesized.

Synthesis Example 2. β-tsuyaprisin (also known as hinokitiol) (5.00 g, 0.03 mol) was dissolved in 50 ml of methanol, and Zn (CH ₃ COO) ₂ .2H ₂ O was dissolved.
Was dissolved in 150 ml of water and mixed to form a pale yellow precipitate. Methylene chloride 50
After extraction with ml three times and evaporation of the solvent and acetic acid under reduced pressure,
A pale yellow individual remained. This solid was recrystallized from ethanol, filtered, and dried under reduced pressure at 100 ° C. to obtain 5.02 g of a pale yellow solid (yield 84%). This solid was subjected to elemental analysis and ICP emission spectroscopic analysis. The results are shown in Table 2.

Table 2 Results of analysis of (β-tiapricin) _2- Zn complex C H N Zn analysis value 60.75 5.70 0.2> 16 ───────────────── ─────────────── Theoretical value 61.31 5.66 0 16.7 From Table 2, the analytical value and the theoretical value are in good agreement, and the (β-tiapricin) ₂ -Zn complex is It was confirmed that it was synthesized.

Synthesis Example 3 5.00 g (0.0 g) of Na salt of α-drabulin synthesized by a known method (for example, Japanese Examined Patent Publication No. 49-28747).
27 mol) was dissolved in 150 ml of water.
An aqueous solution of 1.62 g (0.014 mol) of O ₄ and 50 ml of water was mixed to produce a white precipitate. The precipitate was separated by filtration, washed with water, and dried under reduced pressure at 100 ° C. to obtain 3.23 g (yield: 69%) of a white solid. This solid was subjected to elemental analysis and ICP emission spectroscopic analysis. The results are shown in Table 3.

Table 3 Results of analysis of (α-drabulin) ₂ -Mg complex C H N Mg analysis value 61.95 5.30 0.2> 7 ───────────────── ─────────────── Theoretical value 62.30 5.23 6.6 ─────────────────────── ──────── From Table 3, it was confirmed that the analytical value and the theoretical value were in good agreement, and that the (α-drabulin) ₂ -Mg complex was synthesized.

[0024]

The present invention will be described below in detail with reference to examples.

Examples 1 to 23 The preservative performance of wood preservatives is JIS A 9201-1991.
Tested according to. The test bacteria are Tyromyces palustris FFPRI.
0507), Coriorus ver.
sicolor FFPRI 1030) was used. The test piece used was a cedar bilateral selvage wood with a 20 x 20 mm opening and a height of 10 mm. As a reagent agent, a metal complex of α, β, γ-tsuyaprisin is selected, in the case of a troponoid metal complex in which the metal is an alkali metal, as an aqueous solution, in the case of a troponoid metal complex in which the metal is other than an alkali metal,
Specimens were treated at various concentrations as a methanol solution. Then, half of the treated test body was used as it was for the antiseptic test, and the other half was subjected to a predetermined weather resistance operation and then subjected to the antiseptic test. In addition to these treated specimens, untreated specimens were also tested at the same time. Furthermore, commercially available products treated with Cu naphthenate and Zn versatate were also tested to compare their antiseptic effects. For the evaluation of the antiseptic performance, the test specimens with an average mass reduction rate of 3% or less for Pleurotus cornucopiae and Pleurotus cornucopiae passed. Further, an effective test was carried out when the average mass reduction rate of the untreated test body, which was performed at the same time as the treated test body, was 30% in the case of Pleurotus cornucopiae and 15% or more in the case of Pleurotus cornucopiae. Table 4 shows the results. From Table 4, it can be seen that the antiseptic effect is remarkably increased when the raw material α, β, γ-tsuyapurisin is used as a metal complex except for Fe metal. Further, it can be seen that even when compared with typical commercial products, it exhibits a remarkable antiseptic effect. Further, it is understood that metal complexes other than the alkali metal complexes of α, β, γ-tsuyaprisin have excellent adhesion to wood. Further, in Table 4, the metal is α of Na, Cu, Zn, Ag, Ba, Ca, Mg,
The β, γ-tsuyaprisin metal complex was tested for its mutagenicity by the AMES method, oral acute toxicity in rats, and safety test for primary skin irritation in rabbits.
It was as safe as Tsuyaprisin.

[0026] Table 4 Oousu Bu Ratake result of Coriolus versicolor (alpha-Tsuyafu °: alpha-Tsuyafu ° stands for lysine) (○ Pass × fail) implementation Tsuyafu ° lysine weather operation 0 times weather operation 10 times Example metal complex treatment concentration (ppm × 1000) treated Concentration (ppm × 1000) No 0.1 0.2 1.5 12 24 0.1 0.2 1.5 12 24 ────────────────────────────────── 1 (α-Twist) -K + × ○ ○ ○ ○ × × × × ○ 2 (α-Twist) ₂ -Cu2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 3 (α-Twist) ₂ -Zn2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 4 (α-Twist) ₂ -Ba2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 5 (α-Twit) ₃ -Fe3 + × × × × × × × × × × 6 (β-Twit) -Na + × ○ ○ ○ ○ × × × × ○ 7 (β-Twist) ₂ -Cu2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 8 (β-Twist) ₂ -Zn2 + × ○ ○ ○ ○ × ○ ○ ○ ○ ○ 9 (β- gloss) -Ag + × ○ ○ ○ ○ × ○ ○ ○ 10 (beta-Tsuyafu _{°) 2 -Ba2 + × ○ ○ ○} ○ × ○ ○ ○ ○ 11 (β- Tsuyafu _{°) 2 -Ca2 + × ○ ○ ○} ○ × ○ ○ ○ ○ 12 (β- Tsuyafu °) ₂ -Mg2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 13 (β-gloss) ₃ -Fe3 + × × × × × × × × × × 14 (γ-gloss) -K + × ○ ○ ○ ○ × × × × ○ 15 (γ- ₂ -Cu2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 16 (γ- gloss) ₂ -Zn2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 17 (γ- gloss) ₂ -Ba2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 18 (γ-Tweak) ₃ -Fe3 + × × × × × × × × × × 19 α-Tuber × × ○ ○ ○ × × ○ ○ ○ ○ 20 β-Tuber × × ○ ○ ○ × × ○ ○ ○ 21 γ-Tujax × × ○ ○ ○ ○ × × ○ ○ ○ 22 Naphthenic acid Cu × × × × ○ × × × × ○ ○ 23 Ba-satic acid Zn × × × × ○ × × × × ○

Examples 24 to 46 α, β and γ-drabulin were selected as the test reagents, and the other conditions were the same as those in Examples 1 to 23. Table 5 shows the results. From Table 5, the raw material α excluding Fe metal,
It can be seen that the antiseptic effect remarkably increases when β, γ-drabulin is used as a metal complex. Further, it can be seen that even when compared with typical commercial products, it exhibits a remarkable antiseptic effect.

[0028] Table 5 Oousu Bu Ratake result of Coriolus versicolor (alpha-drab: alpha-draft Bu stands for phosphorus) (○ Pass × fail) implementation drafts Bu phosphorus weather operation 0 times weather operation 10 times Example metal complex treatment concentration (ppm × 1000) treated Concentration (ppm × 1000) No 0.1 0.2 1.5 12 24 0.1 0.2 1.5 12 24 ────────────────────────────────── 24 (α-Draft) -K + × ○ ○ ○ ○ × × × × ○ ○ 25 (α-Draft) ₂ -Cu2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 26 (α-Draft) ₂ -Zn2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 27 (α-draft) ₂ -Ba2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 28 (α-draft) ₃ -Fe3 + × × × × × × × × × × 29 (β-draft) -Na + × ○ ○ ○ ○ × × × × ○ 30 (β-Draft) ₂ -Cu2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 31 (β-Draft) ₂ -Zn2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 32 (β-draft)- Ag + × ○ ○ ○ ○ × ○ ○ ○ ○ 33 (β-Draft) ₂ -Ba2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 34 (β-Draft) ₂ -Ca2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 35 (β-Draft) ₂ -Mg2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 36 (β-Draft) ₃ -Fe3 + × × × × × × × × × × × 37 (γ-Draft) -K + × ○ ○ ○ ○ × × × × ○ 38 (γ-draft) ₂ -Cu2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 39 (γ-draft) ₂ -Zn2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 40 (γ-draft) ₂ -Ba2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 41 (γ-draft) ₃ -Fe3 + × × × × × × × × × × 42 α-draft × × ○ ○ ○ × × × ○ ○ 43 β-draft × × ○ ○ ○ × × × ○ ○ 44 γ-Draft × × ○ ○ ○ × × × ○ ○ 45 Naphthenic acid Cu × × × × ○ × × × × × ○ 46 Basatic acid Zn × × × × ○ × × × × ○

Examples 47 to 57 Tropolone was selected as the reagent to be tested, and otherwise, Example 1
It carried out exactly like -23. Table 6 shows the results. It can be seen from Table 6 that the antiseptic effect is remarkably increased when the raw material tropolone is made into a metal complex except for Fe metal.
Further, it can be seen that even when compared with typical commercial products, it exhibits a remarkable antiseptic effect.

[0030] Table 6 Oousu Bu Ratake result of Coriolus versicolor (○ pass × fail) implementation Toroho ° Ron weather operation 0 times weather operation 10 times Example metal complex treatment concentration (ppm × 1000) treatment concentration (ppm × 1000 No 0.1 0.2 1.5 12 24 0.1 0.2 1.5 12 24 ───────────────────────────────── 47 (Tropholone) -K + × ○ ○ ○ ○ × × × × ○ 48 (Tropolone) ₂ -Cu2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 49 (Tropolone) ₂ -Zn2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 50 (Tropolone) -Ag + × ○ ○ ○ ○ × ○ ○ ○ ○ 51 (Tropholone) ₂ -Ba2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 52 (Tropholon) ₂ -Ca2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 53 (Tropholon) ₂ -Mg2 + × ○ ○ ○ ○ × ○ ○ ○ ○ 54 (Tropholone) ₃ -Fe3 + × × × × × × × × × × × 55 Trophorone × × ○ ○ ○ × × × ○ ○ 56 Naphthenic acid Cu × × × × ○ × × × × ○ 57 Basatic acid Zn × × × × ○ × × × × ○

[0031]

INDUSTRIAL APPLICABILITY According to the present invention, the troponoid metal complex other than Fe solves the problems of the conventional wood preservatives, is safe for the human body and has a high antiseptic effect even in a small amount, and has excellent adhesion to wood. It was found to be a wood preservative.

Claims (4)

[Claims] 1. A wood preservative containing one or more troponoid metal complexes represented by the following formula (1) as an active ingredient. Embedded image (In the formula, R is a hydrogen atom, a lower alkyl group, a lower alkenyl group, M is a metal excluding Fe, n is a valence of the metal M, m is a coordination number, and n and m are the same integers of 1 to 6. Is shown.) 2. The wood preservative according to claim 1, wherein the troponoid compound is α, β, γ-tsuyaprisin, α, β, γ-drabulin or tropolone. 3. The metal is an alkali metal of the periodic table Ia, II.
The wood preservative according to claim 1, which is at least one selected from alkaline earth metals a, transition metals belonging to IVa to Ib other than Fe, and metal elements belonging to IIb to IVb. 4. The metal is Na, K, Ca, Ba, V, Cr,
The wood preservative according to claim 1, which is at least one metal element selected from Mn, Co, Ni, Cu, Ag, Zn, and Sn.