JP2017031074A - Anti-microbial composition for wood - Google Patents

Abstract

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示される１種以上のグアニジン化合物および／またはその塩と、特定の１種以上の化合物を木材に処理することを特徴とする木材用抗菌組成物により目的を達成する。
【選択図】 なし
[Objective] To provide an antibacterial composition for wood that protects wood and wood products from a wide range of fungi including not only filamentous fungi but also discolored and basidiomycetes in small amounts.
SOLUTION: General formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
The object is achieved by an antibacterial composition for wood characterized by treating wood with one or more guanidine compounds and / or salts thereof represented by formula (1) and a specific one or more compounds.
[Selection figure] None

Description

The present invention relates to an antibacterial composition for wood that can protect wood and wood products from a wide range of fungi including not only filamentous fungi but also discoloring bacteria and basidiomycetes in a small amount.

Up to now, halogenated phenolic compounds and organotin compounds have been used as antibacterial compositions for wood, but these compounds have acute and chronic toxicity points and concerns about environmental pollution due to their relatively low degradability. It has been a long time since it was no longer used. For this reason, development of antibacterial compositions for wood using safer compounds has progressed, and 3-iodo-2-propynylbutyl carbamate, 4,5-dichloro-2-n-octyl-4-isothiazoline-3- ON, 2-n-octyl-4-isothiazolin-3-one, 2,4,5,6-tetrachloroisophthalonitrile, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2 -Methyl benzimidazole carbamate, 2- (4-thiocyanomethylthio) benzothiazole, Nn-butyl-1,2-benzisothiazolin-3-one, didecyldimethylammonium chloride, propiconazole, methylenebisthiocyanate, etc. Is widely used.

The use of these compounds alone is not sufficient due to the problem of the antibacterial spectrum, and a composition in which the compounds are combined is widely used due to the cost increase accompanying the increase in the amount used. For example, a microbicidal composition (Patent Document 1) containing 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and 3-iodo-2-propynylbutyl carbamate is disclosed as 3-iodo-2. -An antimicrobial composition (Patent Document 2) containing propynylbutylcarbamate and methyl 2-benzimidazolecarbamate is obtained by combining methyl 2-benzimidazolecarbamate with 5-chloro-2-methyl-4-isothiazolin-3-one or An industrial fungicide composition (Patent Document 3) containing an isothiazoline compound containing 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one has been proposed. Furthermore, an industrial fungicide composition containing 3-iodo-2-propynylbutyl carbamate, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and methyl 2-benzimidazole carbamate (Patent Document) 4) is an anti-wood fungus comprising 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, methyl 2-benzimidazolecarbamate, methylenebisthiocyanate and 3-iodo-2-propynylbutylcarbamate Anti-discoloring fungus composition (Patent Document 5) contains 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, methyl 2-benzimidazolecarbamate and one or more N-substituted triazole compounds An antiseptic composition for wood (Patent Document 6) has been proposed. Moreover, although the disinfectant composition (patent document 7) which consists of 3-isothiazolone and polyhexamethylene guanidine phosphate is proposed, the technique for microorganisms growing on wood is not disclosed.

However, most of the conventional compositions are effective only against filamentous fungi that are surface contaminants of wood, and the microorganisms that grow on wood are not only filamentous fungi, but also fungi such as discolored and basidiomycetes. As such, compositions with a broader antimicrobial spectrum are desired.

Japanese Patent Application No. 2-298735 Japanese Patent Application No. 2000-620797 Japanese Patent Application No. 2-46672 Japanese Patent Application No. 2002-250096 Japanese Patent Application No. 2002-84673 Japanese Patent Application No. 2004-237834 Japanese Patent Application No. 2000-58888

The problem to be solved by the present invention is to provide an antibacterial composition for wood that can be protected against a wide range of fungi including not only filamentous fungi but also discoloration and basidiomycetes, with respect to wood and wood products. It is to provide.

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示される１種以上のグアニジン化合物および／またはその塩と、特定の化合物を含有する木材用抗菌組成物によって、木材および木材製品を、糸状菌、変色菌および担子菌のいずれにも有効であり、これらの幅広い真菌から保護することができることを見出し、本発明を完成させたものである。
すなわち本発明は、
（１）一般式（Ｉ）

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示される１種以上のグアニジン化合物および／またはその塩と、
ａ）３−ヨード−２−プロピニルブチルカーバメート、
ｂ）２−ベンズイミダゾールカルバミン酸メチルおよび／または２−（４−チアゾリル）−ベンズイミダゾール、
ｃ）１−［［２−（２，４−ジクロロフェニル）−４−プロピル−１，３−ジオキソラン−２−イル］メチル］−１Ｈ−１，２，４−トリアゾールおよび／または（±）−α−［２−（４−クロロフェニル）エチル］−α−（１，１−ジメチルエチル）−１Ｈ−１，２，４−トリアゾール−１−エタノールおよび／または（ＲＳ）−２−（２，４−ジクロロフェニル）−１−（１Ｈ−１，２，４−トリアゾール−１−イル）ヘキサン−２−オール、
ｄ）一般式（ＩＩ）

（式中、Ｒは炭素数１以上８以下のアルキル基を示し、Ｘ、Ｙは同一または異なり、水素もしくはハロゲンを示し、または互いに結合して芳香族環を形成しても良い）
で示されるイソチアゾリン化合物
から選ばれる１種以上の化合物を必須成分として含有することを特徴とする木材用抗菌組成物に関する。
また本発明は、
（２）一般式（Ｉ）

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示されるグアニジン化合物が、ｍ＝１で示されるポリヘキサメチレングアニジンであることを特徴とする木材用抗菌組成物に関する。また本発明は、
（３）一般式（Ｉ）

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示されるグアニジン化合物が、ｎ＝２で示されるポリヘキサメチレンビグアニジンであることを特徴とする木材用抗菌組成物に関する。また本発明は、
（４）一般式（ＩＩ）

（式中、Ｒは炭素数１以上８以下のアルキル基を示し、Ｘ、Ｙは同一または異なり、水素もしくはハロゲンを示し、または互いに結合して芳香族環を形成しても良い）
で示されるイソチアゾリン化合物が、４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オンであることを特徴とする木材用抗菌組成物に関する。 As a result of intensive studies to solve the above problems, the present inventors have found that the compound represented by the general formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
By using the antibacterial composition for wood containing one or more guanidine compounds and / or salts thereof and a specific compound, wood and wood products are effective against any of fungi, discoloration fungi and basidiomycetes. The present inventors have found that they can be protected from these broad fungi and have completed the present invention.
That is, the present invention
(1) General formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
One or more guanidine compounds and / or salts thereof represented by:
a) 3-iodo-2-propynyl butyl carbamate,
b) methyl 2-benzimidazole carbamate and / or 2- (4-thiazolyl) -benzimidazole,
c) 1-[[2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole and / or (±) -α -[2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol and / or (RS) -2- (2,4- Dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) hexan-2-ol,
d) General formula (II)

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms, X and Y are the same or different, represent hydrogen or halogen, or may be bonded to each other to form an aromatic ring)
The antibacterial composition for wood characterized by containing as an essential component at least one compound selected from the isothiazoline compounds represented by formula (1).
The present invention also provides
(2) General formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
The antibacterial composition for wood characterized in that the guanidine compound represented by the formula (I) is polyhexamethylene guanidine represented by m = 1. The present invention also provides
(3) General formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
The antibacterial composition for wood is characterized in that the guanidine compound represented by the formula (I) is polyhexamethylene biguanidine represented by n = 2. The present invention also provides
(4) General formula (II)

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms, X and Y are the same or different, represent hydrogen or halogen, or may be bonded to each other to form an aromatic ring)
The antibacterial composition for wood is characterized in that the isothiazoline compound represented by the formula is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.

By using the above composition, it becomes possible to protect wood and wood products from a wide variety of fungi such as discolored bacteria and basidiomycetes as well as filamentous fungi.

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示される１種以上のグアニジン化合物および／またはその塩と、特定の化合物を含有するものであり、これらの化合物を含有する製剤を調製するために、溶媒や界面活性剤の他、ｐＨ調整剤、消泡剤、防錆剤、粘度調整剤、金属封鎖剤、他の抗菌成分や防虫成分等を配合することが可能である。また本発明に係る必須成分を１つの製剤にするだけでなく、木材処理現場に個別に持ち込み処理前に現地で混合して所定の木材用抗菌組成物を調製することも可能である。 The antibacterial composition for wood of the present invention has the general formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
In order to prepare a preparation containing one or more guanidine compounds and / or salts thereof and a specific compound, a pH adjuster in addition to a solvent and a surfactant An antifoaming agent, a rust preventive agent, a viscosity modifier, a metal sequestering agent, other antibacterial components and insect repellent components can be blended. In addition to making the essential components according to the present invention into one preparation, it is also possible to individually bring them into a wood treatment site and mix them on site before the treatment to prepare a predetermined antibacterial composition for wood.

The target microorganisms of the antibacterial composition for wood of the present invention are wide-ranging, such as filamentous fungi, discoloration bacteria, basidiomycetes, etc., and the antibacterial composition for wood of the present invention exhibits excellent effects against such a wide range of microorganisms.

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示される１種以上のグアニジン化合物および／またはその塩は、公知の技術によって製造することができる。
一般式（Ｉ）の重合数ｎについては１以上の化合物が使用可能であるが、好ましくは３〜２０の範囲、より好ましくは４〜１２の範囲のものを使用することができる。
例えば、「ＰＲＯＸＥＬ（登録商標） ＩＢ」（ポリヘキサメチレンビグアニジン（以下ＰＨＭＢと省略する）の塩酸塩を２０重量％含有）としてロンザ社から市販されているもの（ｍ＝２、ｎ＝１２の化合物に相当）、「ＢＧ−１」（ポリヘキサメチレンビグアニジンの塩酸塩を２０重量％含有）として三洋化成工業社から市販されているもの（ｍ＝２、ｎ＝１２の化合物に相当）や、「アモルデン（登録商標） ＤＳ２５Ｌ」（ポリヘキサメチレングアニジン（以下ＰＨＭＧと省略する）のリン酸塩を２５重量％含有）として大和化学工業社から市販されているもの（ｍ＝１、ｎ＝４〜７の化合物に相当）が利用可能である。 General formula (I) used in the present invention

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
One or more guanidine compounds represented by the formula (1) and / or a salt thereof can be produced by a known technique.
As for the polymerization number n of the general formula (I), one or more compounds can be used, but those having a range of 3 to 20, more preferably 4 to 12 can be used.
For example, “PROXEL® IB” (polyhexamethylene biguanidine (hereinafter abbreviated as PHMB) containing 20% by weight of hydrochloride) commercially available from Lonza Corporation (m = 2, n = 12 Equivalent to a compound), “BG-1” (containing 20% by weight of polyhexamethylene biguanidine hydrochloride), commercially available from Sanyo Kasei Kogyo Co., Ltd. (corresponding to a compound of m = 2, n = 12), , "Amorden (registered trademark) DS25L" (containing 25 wt% of polyhexamethyleneguanidine (hereinafter abbreviated as PHMG) phosphate) commercially available from Daiwa Chemical Industry Co., Ltd. (m = 1, n = 4) (Corresponding to ˜7 compounds).

The 3-iodo-2-propynyl butyl carbamate (hereinafter abbreviated as IPBC) used in the present invention can be produced by a known technique. For example, it is commercially available from Lonza as “OMACIDE (registered trademark) IPBC”. Is available.

Methyl 2-benzimidazole carbamate (hereinafter abbreviated as BCM) used in the present invention can be produced by a known technique. For example, it is commercially available from LANXESS as "PREVENTOL (registered trademark) BCM". Is available. Although 2- (4-thiazolyl) -benzimidazole (hereinafter abbreviated as TBZ) can also be produced by a known technique, for example, what is commercially available from LANXESS as “METAZOL (registered trademark) TK100SG” is used. Is possible.

1-[[2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole (hereinafter abbreviated as PCZ) used in the present invention. Can be manufactured by a known technique, for example, “WOCOSEN (registered trademark) TECHNICICAL” commercially available from JANSSEN PMP can be used. (±) -α- [2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol (hereinafter abbreviated as TCZ) is also known. For example, a product commercially available from LANXESS as “PREVENTOL A8” can be used. (RS) -2- (2,4-dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) hexan-2-ol (hereinafter abbreviated as HCZ) is also produced by a known technique. For example, what is commercially available from Arista Life Science Aggregate as “HEXACONAZOL TECHNICAL” can be used.

（式中、Ｒは炭素数１以上８以下のアルキル基を示し、Ｘ、Ｙは同一または異なり、水素もしくはハロゲンを示し、または互いに結合して芳香族環を形成しても良い）
で示されるイソチアゾリン化合物は、例えば、４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン（以下ＤＣＯＩＴと省略する）、２−ｎ−オクチル−４−イソチアゾリン−３−オン（以下ＯＩＴと省略する）、Ｎ−ｎ−ブチル−１，２−ベンズイソチアゾリン−３−オン（以下ＢＢＩＴと省略する）、５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、１，２−ベンズイソチアゾリン−３−オン、Ｎ−メチル−１，２−ベンズイソチアゾリン−３−オン、Ｎ−エチル−１，２−ベンズイソチアゾリン−３−オン、２−エチル−４−イソチアゾリン−３−オン、２−ｎ−ブチル−４−イソチアゾリン−３−オン、５−クロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン等が挙げられる。これらは公知の技術によって製造することができるが、例えばＤＣＯＩＴであれば、「ＫＡＴＨＯＮ（登録商標） ２８７Ｔ」や、ＤＣＯＩＴを２５％含有する「ＫＡＴＨＯＮ ２８７ＰＸＥ」としてダウ・ケミカル社から市販されているものが利用可能であり、ＯＩＴであれば、「ＺＯＮＥＮ（登録商標） Ｏ／１００」としてケミクレア社から市販されているものが利用可能であり、ＢＢＩＴであれば、「ＤＥＮＳＩＬ（登録商標） ＤＮ」としてロンザ社から市販されているものが利用可能である。 General formula (II) used in the present invention

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms, X and Y are the same or different, represent hydrogen or halogen, or may be bonded to each other to form an aromatic ring)
Examples of the isothiazoline compound represented by the formula are 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (hereinafter abbreviated as DCOIT), 2-n-octyl-4-isothiazolin-3-one ( Hereinafter abbreviated as OIT), Nn-butyl-1,2-benzisothiazolin-3-one (hereinafter abbreviated as BBIT), 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl -4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, N-methyl-1,2-benzisothiazolin-3-one, N-ethyl-1,2-benzisothiazolin-3-one, 2-ethyl-4-isothiazolin-3-one, 2-n-butyl-4-isothiazolin-3-one, 5-chloro-2-n-octyl-4-isothiazoline 3-one and the like. These can be manufactured by a known technique. For example, in the case of DCOIT, “KATHON (registered trademark) 287T” or “KATHON 287PXE” containing 25% of DCOIT is commercially available from Dow Chemical Co. Can be used, and if it is OIT, a product marketed by Chemiclear as “ZONEN (registered trademark) O / 100” can be used, and if it is BBIT, it can be used as “DENSIL (registered trademark) DN”. Those commercially available from Lonza are available.

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示される１種以上のグアニジン化合物および／またはその塩と、
ａ）３−ヨード−２−プロピニルブチルカーバメート、
ｂ）２−ベンズイミダゾールカルバミン酸メチルおよび／または２−（４−チアゾリル）−ベンズイミダゾール、
ｃ）１−［［２−（２，４−ジクロロフェニル）−４−プロピル−１，３−ジオキソラン−２−イル］メチル］−１Ｈ−１，２，４−トリアゾールおよび／または（±）−α−［２−（４−クロロフェニル）エチル］−α−（１，１−ジメチルエチル）−１Ｈ−１，２，４−トリアゾール−１−エタノールおよび／または（ＲＳ）−２−（２，４−ジクロロフェニル）−１−（１Ｈ−１，２，４−トリアゾール−１−イル）ヘキサン−２−オール、
ｄ）一般式（ＩＩ）

（式中、Ｒは炭素数１以上８以下のアルキル基を示し、Ｘ、Ｙは同一または異なり、水素もしくはハロゲンを示し、または互いに結合して芳香族環を形成しても良い）
で示されるイソチアゾリン化合物
から選ばれる１種以上の化合物との比率は、特に限定されず任意の割合で併用することが可能であるが、好ましくは一般式（Ｉ）の化合物１に対して、ａ）３−ヨード−２−プロピニルブチルカーバメート、ｂ）２−ベンズイミダゾールカルバミン酸メチルおよび／または２−（４−チアゾリル）−ベンズイミダゾール、ｃ）１−［［２−（２，４−ジクロロフェニル）−４−プロピル−１，３−ジオキソラン−２−イル］メチル］−１Ｈ−１，２，４−トリアゾールおよび／または（±）−α−［２−（４−クロロフェニル）エチル］−α−（１，１−ジメチルエチル）−１Ｈ−１，２，４−トリアゾール−１−エタノールおよび／または（ＲＳ）−２−（２，４−ジクロロフェニル）−１−（１Ｈ−１，２，４−トリアゾール−１−イル）ヘキサン−２−オール、ｄ）イソチアゾリン化合物から選ばれる化合物が０．０１〜１００であり、より好ましくは０．１〜１０である。 General formula (I) used in the present invention

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
One or more guanidine compounds and / or salts thereof represented by:
a) 3-iodo-2-propynyl butyl carbamate,
b) methyl 2-benzimidazole carbamate and / or 2- (4-thiazolyl) -benzimidazole,
c) 1-[[2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole and / or (±) -α -[2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol and / or (RS) -2- (2,4- Dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) hexan-2-ol,
d) General formula (II)

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms, X and Y are the same or different, represent hydrogen or halogen, or may be bonded to each other to form an aromatic ring)
The ratio to one or more compounds selected from the isothiazoline compounds represented by the formula (1) is not particularly limited and can be used in any ratio, but is preferably a with respect to the compound 1 of the general formula (I). ) 3-iodo-2-propynylbutyl carbamate, b) methyl 2-benzimidazole carbamate and / or 2- (4-thiazolyl) -benzimidazole, c) 1-[[2- (2,4-dichlorophenyl)- 4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole and / or (±) -α- [2- (4-chlorophenyl) ethyl] -α- (1 , 1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol and / or (RS) -2- (2,4-dichlorophenyl) -1- (1H-1,2, 4-triazol-1-yl) hexan-2-ol, d) is selected from isothiazolin compound compound is 0.01 to 100, more preferably from 0.1 to 10.

Solvents that can be incorporated in the preparation of the antibacterial composition for wood of the present invention include water, monohydric alcohols such as ethanol, isopropanol, phenoxyethanol, and benzyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, and propylene glycol. , Glycol solvents such as dipropylene glycol, polypropylene glycol, butylene glycol, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and derivatives thereof, glycerin solvents such as glycerin and diglycerin and the like Derivatives, cyclic organic solvents such as dimethyl sulfoxide, N-methylpyrrolidone, γ-butyrolactone, Ester solvents such as tartrate, adipic acid, and sebacic acid, aromatic solvents such as methylnaphthalene, phenylxylylethane, and alkylbenzene, aliphatic hydrocarbon solvents such as normal paraffin and isoparaffin, rapeseed oil, cottonseed oil, large Bean oil, castor oil, etc. can be used. These solvents may be used alone or in combination of two or more.

Examples of surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene allyl phenyl ether, block copolymer of polyoxyethylene and polyoxypropylene, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene curing Nonionic surfactants such as castor oil, alkyl sulfate salts, alkyl ether sulfate salts, alkyl sulfosuccinate salts, alkyl sulfonate salts, alkyl allyl sulfonate salts, fatty acid amide sulfonate salts, lignin sulfonate salts, alkyl naphthalene sulfonate salts, Anionic surface activity such as alkyl phosphate salt, alkyl ether phosphate salt, naphthalenesulfonic acid formaldehyde condensate salt Agents and alkylamine salts, and cationic surfactants such as alkylammonium salts, glycine type, betaine type, can be used amphoteric surfactants imidazoline type. These surfactants may be used alone or in combination of two or more.

As the pH adjuster, organic acids such as succinic acid, citric acid, tartaric acid and acetic acid and salts thereof, inorganic acids such as phosphoric acid, polyphosphoric acid and boric acid and salts thereof can be used, and antifoaming agents As the anti-foaming agent such as mineral oil, silicone, and polyether, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, sodium hydrogenphosphate, ammonium hydrogenphosphate, etc. Xanthan gum, carboxymethyl cellulose, hydroxyethyl cellulose, gum arabic, gellan gum, pullulan, etc. can be used as the viscosity modifier, and ethylenediaminetetraacetic acid or a salt thereof, nitrilotriacetic acid or a salt thereof as a metal sequestering agent. Salt, diethylenetriaminepentaacetic acid or its salt, hydroxyethyl Ethylenediaminetriacetic acid or salt thereof, triethylenetetraminehexaacetic acid or salt thereof, 1,3-propanediaminetetraacetic acid or salt thereof, 1,3-diamino-2-hydroxypropanetetraacetic acid or salt thereof, 1-hydroxyethylidene-1 , 1-diphosphonic acid or its salt, hydroxyethyliminodiacetic acid or its salt, dihydroxyethylglycine or its salt, glycol etherdiamine tetraacetic acid or its salt, dicarboxymethylglutamic acid or its salt, nitrilotrismethylene phosphoric acid or its salt Etc., and two or more of these may be used in combination.
Other antibacterial components include methylene bis thiocyanate, 2- (4-thiocyanomethylthio) benzothiazole, ± 1- [2- (2,4-dichlorophenyl) -2- (2-propenyloxy) ethyl] -1H— Imidazole, 2-bromo-nitropropane-1,3-diol, 2,2-dibromo-2-nitroethanol, 2,3,3-triiodoallyl alcohol, diiodomethyl-p-tolylsulfone, 2,3,5 6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5,6-tetrachloroisophthalonitrile, zinc bis- (2-pyridylthio-1-oxide), o-phenylphenol, isopropylmethylphenol, parachloro Metaxylenol, p-oxybenzoic acid alkyl ester, benzalkonium chloride, chloride Methyl didecyl ammonium, benzethonium chloride, cetyl pyridinium chloride, cetyl trimethyl ammonium chloride, dimethyl didecyl ammonium carbonate / bicarbonate, dimethyl didecyl ammonium propionate, 1,4-bis (3,3 '-(1-decyl) Pyridinium) methyloxybutane) bromide, etc. can be used. Insect repellents include allethrin, imiprothrin, etofenprox, eminence, empentrin, silafluophene, deltamethrin, tralomethrin, transfluthrin, pyrethrin, phenothrin, praretrin, promethrin, permethrin , Pyrethroid compounds such as resmethrin, organophosphorus compounds such as diazinon, fenitrothion, DDVP, carbaryl, fenocarb, propox , Metoxadiazone, carbamate compounds such as NAC, acetamiprid, imidacloprid, clothianidin, dinotefuran, thiacloprid, thiamethoxam, nitenpyram and the like can be used.

The dosage form of the antibacterial composition for wood according to the present invention is not particularly limited, and can be provided by an emulsion, a solubilizer, a flowable preparation, a suspoemulsion preparation, a wettable powder, and the like. It is also possible to combine two or more types of dosage forms, such as a combination of preparations and a combination of solubilizer and flowable preparation. In consideration of actual usage scenes at a lumbering company or the like, it is preferable that the dosage form be dilutable in water. Moreover, it is also possible to process a predetermined active ingredient with respect to wood as a two-component addition as needed.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these Examples. Unless otherwise specified, “%” represents “% by weight”.
(Antimicrobial composition example for wood)

Example 1 was prepared by mixing and dissolving 5 parts of IPBC, 60 parts of diethylene glycol mono-n-butyl ether, 10 parts of Emulgen (registered trademark) LS114 (Kao Corporation, polyoxyethylene polyoxypropylene alkyl ether) and 25 parts of PROXEL IB. (PHMB 5%, IPBC 5%).

5 parts of BCM, 1 part of New Calgen CP-120 (Takemoto Yushi Co., Ltd., polyoxyalkylene allyl phenyl ether), 10 parts of ion-exchanged water, pulverized and dispersed in a bead mill for 30 minutes, 25 parts of PROXEL IB, Ion A mixture of 59 parts of exchange water was designated as Example 2 (PHMB 5%, BCM 5%).

TBZ 5 parts, New Calgen CP-120 (Takemoto Yushi Co., Ltd., polyoxyalkylene allyl phenyl ether) 1 part, ion-exchanged water 10 parts mixed and pulverized and dispersed in a bead mill for 30 minutes, PROXEL IB 25 parts, ion A mixture of 59 parts of exchanged water was designated as Example 3 (PHMB 5%, TBZ 5%).

Example 4 was prepared by mixing and dissolving 5 parts of PCZ, 60 parts of diethylene glycol mono-n-butyl ether, 10 parts of Emulgen LS114, and 25 parts of PROXEL IB (PHMB 5%, PCZ 5%).

Example 5 was prepared by mixing and dissolving 5 parts of TCZ, 60 parts of diethylene glycol mono-n-butyl ether, 10 parts of Emulgen LS114, and 25 parts of PROXEL IB (PHMB 5%, TCZ 5%).

Example 6 was prepared by mixing and dissolving 5 parts of HCZ, 60 parts of diethylene glycol mono-n-butyl ether, 10 parts of Emulgen LS114, and 25 parts of PROXEL IB (PHMB 5%, HCZ 5%).

Example 7 was prepared by mixing and dissolving 5 parts of KATHON 287T, 60 parts of diethylene glycol-n-butyl ether, 10 parts of Emulgen LS114, and 25 parts of PROXEL IB (PHMB 5%, DCOIT 5%).

ZONEN O / 100 5 parts, diethylene glycol-n-butyl ether 60 parts, Emulgen LS114 10 parts, PROXEL IB 25 parts were mixed and dissolved in Example 8 (PHMB 5%, OIT 5%).

Example 9 (PHMB 5%, BBIT 5%) was prepared by mixing and dissolving 5 parts of DENSIL DN, 60 parts of diethylene glycol-n-butyl ether, 10 parts of Emulgen LS114, and 25 parts of PROXEL IB.

Example 10 was prepared by mixing and dissolving 5 parts of IPBC, 60 parts of diethylene glycol mono-n-butyl ether, 10 parts of Emulgen LS114, and 20 parts of Amorden DS25L (PHMG 5%, IPBC 5%).

Example 11: 5 parts of BCM, 1 part of Neukalgen CP-120, 10 parts of ion-exchanged water, pulverized and dispersed in a bead mill for 30 minutes, and 20 parts of Amorden DS25L and 64 parts of ion-exchanged water were mixed. (PHMG 5%, BCM 5%).

Example 12 (PHMG 5%, DCOIT 5%) was prepared by mixing and dissolving 5 parts of KATHON 287T, 65 parts of diethylene glycol-n-butyl ether, 10 parts of Emulgen LS114, and 20 parts of Amorden DS25L.

IPBC 3 parts, Nisseki Hyzol (registered trademark) SAS296 (JX Nippon Mining & Energy Corporation) 18 parts, Newkalgen CP-120 2 parts, sodium dioctylsulfosuccinate 0.2 parts mixed and dissolved in ion-exchanged water 18 parts Then, 3 parts of BCM, 1 part of Newkargen CP-120 and 10 parts of ion-exchanged water are mixed and pulverized in a bead mill for 30 minutes, and 20 parts of PROXEL IB and ion-exchanged water are mixed. A mixture of 8 parts was designated as Example 13 (PHMB 4%, IPBC 3%, BCM 3%).

IPBC 3 parts, KATHON 287PXE 12 parts, Nisseki Hyzol SAS296 8 parts, Neukalgen CP-120 2 parts, dioctylsulfosuccinate 0.2 part mixed and dissolved 18 parts of ion-exchanged water is added dropwise to emulsify. , 20 parts of PROXEL IB and 36.8 parts of ion-exchanged water were used as Example 14 (PHMB 4%, IPBC 3%, DCOIT 3%).

12 parts of KATON 287PXE, 8 parts of Nisseki Hyzol SAS296, 2 parts of New Calgen CP-120, 0.2 part of sodium dioctylsulfosuccinate were mixed and dissolved in 18 parts of ion-exchanged water, and emulsified, and 3 parts of BCM In Example 15, a mixture of 1 part of Neukalgen CP-120 and 10 parts of ion-exchanged water and pulverized with a bead mill for 30 minutes was mixed with 20 parts of PROXEL IB and 25.8 parts of ion-exchanged water. (PHMB 4%, DCOIT 3%, BCM 3%).

IPBC 3 parts, KATHON 287PXE 12 parts, Nisseki Hyzol SAS296 8 parts, Neukalgen CP-120 2 parts, dioctylsulfosuccinate 0.2 part mixed and dissolved 18 parts of ion-exchanged water is added dropwise to emulsify. A mixture of 16 parts of Amorden DS25L and 40.8 parts of ion-exchanged water was used as Example 16 (PHMG 4%, IPBC 3%, DCOIT 3%).

IPBC 5 parts, KATHON 287PXE 16 parts, Nisseki Hyzol SAS296 16 parts, New Calgen CP-120 4 parts, dioctyl sulfosuccinate sodium 0.4 parts mixed and dissolved 36 parts of ion-exchanged water is added dropwise and emulsified. A mixture of 4 parts of Amorden DS25L and 18.6 parts of ion-exchanged water was used as Example 17 (PHMG 1%, IPBC 5%, DCOIT 4%).

IPBC 2 parts, KATHON 287PXE 8 parts, Nisseki Hyzol SAS296 10 parts, Newkalgen CP-120 2 parts, dioctyl sulfosuccinate 0.2 part mixed and dissolved 18 parts of ion-exchanged water are added dropwise and emulsified. , 2 parts of BCM, 1 part of Neukalgen CP-120, 7 parts of ion-exchanged water and mixed for 30 minutes with a bead mill are mixed, and 20 parts of PROXEL IB and 29.8 parts of ion-exchanged water are mixed. Example 18 was adopted (PHMB 4%, IPBC 2%, DCOIT 2%, BCM 2%).

Example 19 (PHMG 4%, IPBC 2) was prepared by mixing and dissolving 2 parts IPBC, 2 parts KATHON 287T, 2 parts TCZ, 68 parts diethylene glycol mono-n-butyl ether, 10 parts Emulgen LS114, and 16 parts Amorden DS25L. %, DCOIT 2%, TCZ 2%).

[Comparative Example 1]
What mixed and dissolved 50 parts of PROXEL IB and 50 parts of ion-exchange water was made into the comparative example 1 (PHMB 10%)

[Comparative Example 2]
A mixture of 40 parts of Amorden DS25L and 60 parts of ion-exchanged water was used as Comparative Example 2 (PHMG 10%).

[Comparative Example 3]
IPBC 5 parts, KATHON 287T 5 parts, diethylene glycol mono-n-butyl ether 75 parts and Emulgen LS114 15 parts were mixed and dissolved to make Comparative Example 3 (IPBC 5%, DCOIT 5%).

[Comparative Example 4]
5 parts of IPBC, 30 parts of Nisseki Hyzol SAS296, 4 parts of Neukalgen CP-120, 0.4 parts of sodium dioctylsulfosuccinate are mixed and dissolved in 49.6 parts of ion-exchanged water and emulsified, and BCM 3 Part, Neukalgen CP-120 1 part, and 7 parts of ion-exchanged water were mixed and pulverized and dispersed in a bead mill for 30 minutes to prepare Comparative Example 4 (IPBC 5%, BCM 5%).

[Comparative Example 5]
Comparative Example 5 was prepared by mixing 5 parts of BCM, 5 parts of TCZ, 3 parts of Neukalgen CP-120, 15 parts of ion-exchanged water, and pulverizing and dispersing for 30 minutes in a bead mill and 72 parts of ion-exchanged water. (BCM 5%, TCZ 5%).

[Comparative Example 6]
20 parts of KATHON 287PXE, 3 parts of New Calgen CP-120, 0.3 part of sodium dioctyl sulfosuccinate were mixed and dissolved in 18 parts of ion-exchanged water and emulsified, and 5 parts of BCM, New Calgen CP-120 1 .5 parts and 10 parts of ion exchange water were mixed, and the mixture was pulverized and dispersed in a bead mill for 30 minutes, and 42.2 parts of ion exchange water was further mixed to make Comparative Example 6 (DCOIT 5%, BCM 5 %).

(Test for filamentous fungi using wood specimens)
The antibacterial compositions for wood of Examples and Comparative Examples were diluted with water to a predetermined concentration, and bay sapwood (2 cm × 5 cm × 0.3 cm) was immersed in this solution for 30 seconds and then air-dried. This test piece was placed on a potato dextrose agar medium, sprayed with 1 ml of a mixed spore suspension of the test bacteria, and cultured for 28 days in an environment of 26 ° C. and 95% relative humidity. Four strains of Aspergillus niger, Penicillium pinophilum, Aureobasidium pullulans, and Cladospodium clasporioides were used as test bacteria.

(Test for discoloration bacteria using wood specimens)
A pine sapwood specimen subjected to ethylene oxide sterilization treatment was placed on a potato dextrose agar medium, and 1 ml of a mixed spore suspension of the test bacteria was added dropwise thereto, and precultured at 26 ° C. and 95% relative humidity for 14 days. Test specimens obtained by diluting the antibacterial compositions for wood of Examples and Comparative Examples to a predetermined concentration with water, immersing bay sapwood (2 cm × 5 cm × 0.3 cm) in this solution for 30 seconds, and then air-drying Was placed on the test specimen that had been pre-cultured and cultured for 28 days in an environment of 26 ° C. and 95% relative humidity. Two strains, Pesotum fragrances and Marianna elegans, were used as test bacteria.

(Test for basidiomycetes using wood specimens)
A pine sapwood specimen subjected to ethylene oxide sterilization treatment was placed on a potato dextrose agar medium, and 1 ml of a mixed spore suspension of the test bacteria was added dropwise thereto, and precultured at 26 ° C. and 95% relative humidity for 14 days. Test specimens obtained by diluting the antibacterial compositions for wood of Examples and Comparative Examples to a predetermined concentration with water, immersing bay sapwood (2 cm × 5 cm × 0.3 cm) in this solution for 30 seconds, and then air-drying Was placed on the test specimen that had been pre-cultured and cultured for 28 days in an environment of 26 ° C. and 95% relative humidity. As the test bacterium, Fomitopsis palustris was used.

The test results are shown in Table 1. From these results, it can be seen that the antibacterial composition for wood of the present invention exhibits good antibacterial properties in any of filamentous fungi, discoloration bacteria, and basidiomycetes.

表中の数字は以下の判定基準による木材試験片３枚の生育スコア
０：試験片上に供試菌の発育を認めない。
１：試験片上の供試菌の発育面積は全面積の１／３未満である。
２：試験片上の供試菌の発育面積は全面積の１／３以上である。

The numbers in the table are growth scores of three wood specimens according to the following criteria: 0: no growth of test bacteria on the specimen.
1: The growth area of the test bacteria on the test piece is less than 1/3 of the total area.
2: The growth area of the test bacteria on the test piece is 1/3 or more of the total area.

（式中、ｍは１または２を示し、ｎは１以上の整数）
で示される１種以上のグアニジン化合物および／またはその塩と、特定の１種以上の化合物を木材に処理することを特徴とするものであり、糸状菌だけでなく変色菌や担子菌を含む幅広い真菌から、少ない使用量で木材および木材製品を保護することが可能であるため産業の発展に寄与するものである。


The antibacterial composition for wood of the present invention has the general formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
It is characterized by treating wood with one or more guanidine compounds and / or salts thereof, and a specific one or more compounds, and includes a wide variety including discolored bacteria and basidiomycetes Since it is possible to protect wood and wood products from fungi with a small amount of use, it contributes to industrial development.

Claims (4)

Formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
One or more guanidine compounds and / or salts thereof represented by:
a) 3-iodo-2-propynyl butyl carbamate,
b) methyl 2-benzimidazole carbamate and / or 2- (4-thiazolyl) -benzimidazole,
c) 1-[[2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole and / or (±) -α -[2- (4-Chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol and / or (RS) -2- (2,4- Dichlorophenyl) -1- (1H-1,2,4-triazol-1-yl) hexan-2-ol,
d) General formula (II)

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms, X and Y are the same or different, represent hydrogen or halogen, or may be bonded to each other to form an aromatic ring)
An antibacterial composition for wood, comprising as an essential component at least one compound selected from the isothiazoline compounds represented by the formula: Formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
The antibacterial composition for wood according to claim 1, wherein the guanidine compound represented by the formula (I) is polyhexamethylene guanidine represented by m = 1. Formula (I)

(In the formula, m represents 1 or 2, and n is an integer of 1 or more)
The antibacterial composition for wood according to claim 1, wherein the guanidine compound represented by the formula (I) is polyhexamethylene biguanidine represented by n = 2. Formula (II)

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms, X and Y are the same or different, represent hydrogen or halogen, or may be bonded to each other to form an aromatic ring)
The antibacterial composition for wood according to any one of claims 1 to 3, wherein the isothiazoline compound represented by the formula (4) is 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one.