JP2005349625A - Water soluble wood preservative improved in permeability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal compound-containing wood preserving composition which applies sufficient permeability and fixing properties to wood inferior to permeability to impart sufficient preservative and ant-proof properties to the wood. <P>SOLUTION: The metal compound-containing wood preserving composition is constituted using a water soluble wood preservative containing polyethyleneimine having an oxygen element in its constituent elements and a metal compound. By this composition, sufficient preservative and ant-proof properties can be imparted to the wood inferior to permeability. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a water-soluble wood preservative containing polyethyleneimine having an oxygen element as a constituent element and a metal compound.

  Wood is decayed by wood-rotting fungi and mold, and is degraded by dry material-damaging insects and termites. Wood preservation agents containing metal compounds such as copper and zinc have been proposed as preservation methods. . Wood preservatives containing such metal compounds are used in wood by methods such as coating, dipping, and pressure injection.

  The metal compound can be made water-soluble by forming a complex with a lower amine such as ammonia, alkanolamine, or alkyldiamine. Wood preservatives containing these water-soluble metal complexes are not sufficiently fixed to wood and are not sufficiently permeable to wood having poor permeability. In order to improve the metal fixability, the use of polyethyleneimine having a high molecular weight instead of lower amine (see Patent Document 1) and the use of polyethyleneimine improved the permeability to wood with poor permeability. A thing (refer patent document 2) etc. are proposed.

Japanese Patent No. 3115376 Japanese Patent Laid-Open No. 2001-121512

  As described above, various improvements have been made on water-soluble wood preservatives containing metal compounds. However, wood with poor permeability, such as Ezo pine and baitsuga, does not have sufficient permeability, so that the amount of chemicals injected and the wetness do not reach satisfactory levels. Therefore, sufficient antiseptic performance, ant performance, etc. cannot be imparted to wood with poor permeability such as Ezo pine and Batesuga.

  Accordingly, an object of the present invention is to provide a metal compound-containing composition for preserving wood that imparts sufficient antiseptic performance and ant-preventive performance by imparting sufficient permeability and fixing properties to wood having poor permeability.

As a result of various investigations on methods for solving the above problems, a water-soluble wood preservative containing a polyethyleneimine having an oxygen element as a constituent element and a metal compound penetrates deeply into wood such as Ezo pine with poor permeability, It has been found that the amount of chemicals injected and the wetness can be increased to a satisfactory level, thereby imparting sufficient antiseptic performance and ant protection performance to poorly permeable wood.

  Sufficient antiseptic performance and ant repellency performance can be imparted to poorly penetrable wood by sufficiently penetrating into poorly penetrable wood and increasing the amount of chemicals injected and the wetness.

  The metal compound-containing water-soluble wood preservative of the present invention contains (A) a metal compound and (B) polyethyleneimine having an oxygen element as a constituent element.

  The metal compound in the present invention is more preferably a copper or zinc compound, and more preferably a copper compound. As the copper compound, it is preferable to use at least one compound selected from copper oxide, copper hydroxide, basic copper carbonate, basic copper sulfate, basic copper phosphate, and basic copper nitrate.

  The molecular weight of polyethyleneimine having an oxygen element as a constituent element is preferably 300 to 100,000.

  The ratio of oxygen element (atom) and nitrogen element (atom) in polyethyleneimine having an oxygen element as a constituent element in the present invention is oxygen element / nitrogen element (O / N ratio) = 0.0001 to 1.0, Preferably it is 0.001-0.5, More preferably, it is 0.004-0.2. If the O / N ratio is in the above range, the amount of chemical solution injected into the wood and the wetness can be improved, and sufficient antiseptic performance and ant proof performance can be imparted to the wood.

  The oxygen element of polyethyleneimine having an oxygen element as a constituent element in the present invention preferably constitutes a hydroxyl group, an amide group, an ether group, an ester group, a carbonyl group, or a carboxyl group.

The method for producing polyethyleneimine having an oxygen element as a constituent element in the present invention may be synthesized by copolymerizing ethyleneimine and a compound having an oxygen element under a hydrochloric acid catalyst, or a compound having an oxygen element in polyethyleneimine. You may synthesize | combine by making it react, such as addition.
As the compound having an oxygen element used for copolymerization, for example, epoxies, isocyanates, alcohols, amides, ethers, esters, ketones, and carboxylic acids are preferable.

  Specifically, amide compounds, polyethylene glycols, which are reaction products of alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, organic acids such as succinic acid, glutaric acid and adipic acid and amines such as ethylenediamine and diethylenetriamine And ether compounds such as aminopropyl vinyl ether, acrylic acid esters such as ethyl acrylate and methyl acrylate, and organic acids such as acetic acid, propionic acid and acrylic acid.

  As the compound having an oxygen element used for addition, for example, epoxies, isocyanates, alcohols, amides, ethers, esters, ketones, and carboxylic acids are preferable.

  Specifically, epoxy-containing compounds such as ethylene oxide, propylene oxide, glycidol, and epichlorohydrin, isocyanate-containing compounds such as ethyl isocyanate and propyl isocyanate, acrylic acid esters such as ethyl acrylate and methyl acrylate, acrylic acid, Organic acids such as acetic acid and propionic acid can be mentioned.

  The content of polyethyleneimine having an oxygen element as a constituent element in the present invention is preferably 0.1 or more, and more preferably 0.5 or more, relative to the weight 1 of the metal element of the metal compound. The upper limit is preferably 20 or less, and more preferably 10 or less.

  Wood preservatives include monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, aminoethylethanolamine, 1,2-diaminopropane, 1,3-diaminopropane, dipropylenetriamine, tripropylenetetramine Polyamines such as neopentanediamine and water-soluble amines can be used within a range that does not impair the amount of chemicals injected into the wood and the wetness.

Also the wood preservative, aliphatic C ₅ -C ₂₀ carboxylic acids, for example hexanoic acid, heptanoic acid, octanoic acid, branched carboxylic acids, such as 2-ethylhexanoic acid, 2-ethyl heptanoic acid, 2-ethyl pentane acid, isooctanoic acid, isononanoic acid, branched carboxylic acid strength, for example, neo carboxylic acids, Berusachikku acid, di -n- alkyl acetate, di -n- alkyl acid, substituted _C 5 _{-C 20} carboxylic acids, for example halides Carboxylic acid (2-boromhexanoic acid, 2-bromooctanoic acid), ether carboxylic acid, aminocarboxylic acid, aliphatic dicarboxylic acid such as sebacic acid, cycloalkyl carboxylic acid such as cyclohexane carboxylic acid, cycloaryl carboxylic acid such as phthalate Acid, salicylic acid, 3- or 4-hydroxy-benzoic acid, Roh hydroxycarboxylic acids, such as amino salicylic acid, polycarboxylic acids, for example polyacrylic acid, may be used for the purpose of imparting storage stability to a wood preservative composition.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. Unless otherwise specified, “%” indicates “mass%” and “part” indicates “mass part”.

(Synthesis Example 1)
A separable flask was charged with 60 g of monoethanolamine and 13 g of 38% hydrochloric acid, and the temperature was raised to 85 ° C. or higher. After the temperature was raised, 930 g of ethyleneimine was continuously added and reacted in the range of 100 to 130 ° C. Synthetic product 1 was obtained as a reaction product (molecular weight 1000, O / N ratio = 0.05).

(Synthesis Example 2)
A separable flask was charged with 90 g of a reactive product of adipic acid and diethylenetriamine, 170 g of pure water, and 10 g of 38% hydrochloric acid. The temperature was raised to 85 ° C. or higher. It was made to react in the range of. Synthetic product 2 was obtained as a reaction product (molecular weight 2000, O / N ratio = 0.02).

(Synthesis Example 3)
Under a NaOH catalyst, 750 g of ethylene oxide was reacted at 150 ° C. with 250 g of polyethyleneimine (molecular weight 1800). Synthetic product 3 was obtained as a reaction product (molecular weight 1900, O / N ratio = 0.07).

(Example 1)
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Synthetic product 1 15 parts Monoethanolamine 10 parts Copper content 50% basic copper carbonate (II) 10 parts Pure water 65 parts

(Example 2)
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Synthetic product 2 15 parts Monoethanolamine 10 parts Copper content 50% basic copper (II) carbonate 10 parts Pure water 65 parts

(Example 3)
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Synthetic 3 15 parts Monoethanolamine 10 parts Copper content 50% basic copper carbonate (II) 10 parts Pure water 65 parts

Example 4
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Synthetic product 1 15 parts Monoethanolamine 10 parts 2-Ethylhexanoic acid 25 parts Copper content 50% basic copper carbonate (II) 10 parts Pure water 40 parts

(Example 5)
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Synthetic product 2 15 parts Monoethanolamine 10 parts 2-ethylhexanoic acid 25 parts Copper content 50% basic copper carbonate (II) 10 parts Pure water 40 parts

(Example 6)
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Synthetic product 3 15 parts Monoethanolamine 10 parts 2-ethylhexanoic acid 25 parts Copper content 50% basic copper carbonate (II) 10 parts Pure water 40 parts

(Comparative Example 1)
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Polyethyleneimine (molecular weight 5000) 15 parts Monoethanolamine 10 parts Basic copper carbonate (II) 50% copper content 10 parts Pure water 65 parts

(Comparative Example 2)
The following composition was stirred at 75 ° C. for 30 minutes to obtain a uniform solution.
Polyethyleneimine (molecular weight 5000) 15 parts Monoethanolamine 10 parts 2-ethylhexanoic acid 25 parts Copper content 50% basic copper carbonate (II) 10 parts Pure water 40 parts (Test chemical)
The chemical solutions prepared in Examples 1 to 6 and Comparative Examples 1 and 2 were diluted 50 times with pure water to obtain test chemical solutions.

(Test pieces)
A test piece was prepared by applying a silicone resin to both ends of Ezo pine having a water content of 20% or less and having a length of 3 cm, a width of 3 cm, and a length of 5 cm and dried and sealed overnight.

(Treatment of test specimens with test chemicals)
Four test pieces were placed in a small pressure vessel with a capacity of 4 L, and the test pieces were fixed to a weight so that they would not float when a test chemical solution was placed. The small pressure vessel was sealed, and the inside of the vessel was depressurized for 1 hour in a state of 90 kPa, and then the adjusted test chemical 2L was sucked into and returned to atmospheric pressure. After confirming that the test piece was immersed in the test chemical, the small pressure vessel was sealed and pressurized at 1.0 MPa for 3 hours. After returning the inside of the container to atmospheric pressure, the chemical solution was extracted, and the inside of the container containing the test piece was depressurized at 90 kPa for 1 hour. Then, the test piece was taken out and the weight was measured.

(Evaluation of permeability)
Injection amount (kg / m ³ ) = (weight after treatment−weight before treatment) / volume of test piece × 1000
(Evaluation of wetness)
In order to measure the wetness to the test piece, the treated test piece was dried for 5 days, and then the central part of the test piece was cut and a mixed aqueous solution of Chromazurol S / sodium acetate was applied to the cut surface. The portion where the test chemical was wet developed a dark green color. The wetness of the test chemical solution was determined from this colored portion.
Wetness (%) = wet area / cross-sectional area of test piece × 100
The test results are shown in Table 1.

  As is clear from Table 1, the chemical solution for wood preservation of the examples is improved in both the chemical solution injection amount and the wetness as compared with the chemical solution for wood preservation of the comparative example.

Water-soluble wood preservatives containing polyethyleneimine, which contains oxygen as the constituent elements, and metal compounds can provide sufficient antiseptic and ant-proofing performance to poorly permeable wood, so they can be used effectively in the same applications. can do.

Claims (4)

A water-soluble wood preservative comprising a polyethyleneimine and a metal compound, wherein the polyethyleneimine is a polyethyleneimine having an oxygen element as a constituent element. The water-soluble wood preservative according to claim 1, wherein the oxygen element constitutes a hydroxyl group, an amide group, an ether group, an ester group, a carbonyl group, or a carboxyl group. The water-soluble wood preservative according to claim 1 or 2, wherein the molecular weight of polyethyleneimine having an oxygen element as a constituent element is 300 to 100,000. The ratio of oxygen element and nitrogen element of polyethyleneimine having an oxygen element as the constituent element is oxygen element / nitrogen element (O / N ratio) = 0.0001 to 1.0. 3. The water-soluble wood preservative according to 3.