JPH0768508A - Timber preservative - Google Patents
Timber preservativeInfo
- Publication number
- JPH0768508A JPH0768508A JP21713493A JP21713493A JPH0768508A JP H0768508 A JPH0768508 A JP H0768508A JP 21713493 A JP21713493 A JP 21713493A JP 21713493 A JP21713493 A JP 21713493A JP H0768508 A JPH0768508 A JP H0768508A
- Authority
- JP
- Japan
- Prior art keywords
- chitosan
- metal
- salt
- copper
- preservative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、防虫・殺虫効果及び防
腐・防黴効力に優れる金属成分を含有する木材固着型の
水溶性木材保存剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wood-fixing type water-soluble wood preservative containing a metal component which is excellent in insecticidal / insecticidal effects and antiseptic / mildew efficacy.
【０００２】[0002]
【従来の技術】木材固着型の水溶性木材保存剤として
は、クロム、銅、砒素化合物系のＣＣＡ（ＪＩＳ Ｋ
１５５４）が主流を占めている。このＣＣＡは木材に注
入されると木材成分による酸化還元反応によってクロム
化合物や銅化合物、砒素化合物が化学反応を起こし、ク
ロム酸銅や砒酸銅等の錯塩を形成し、水不溶性物に変わ
って木材に固着される。従って耐水性や耐溶脱性が高
く、長期に亘って効力の持続を期待することができる。
ところがＣＣＡにはクロム（６価クロム）や砒素という
有害元素を含むために、人畜への毒性や環境汚染等が問
題になっている。2. Description of the Related Art Chromium, copper and arsenic compound-based CCA (JIS K
1554) is the mainstream. When this CCA is injected into wood, it undergoes a chemical reaction with chromium compounds, copper compounds, and arsenic compounds due to the redox reaction of wood components, forming complex salts of copper chromate, copper arsenate, etc. Stuck to. Therefore, the water resistance and the leaching resistance are high, and it can be expected that the efficacy is maintained for a long time.
However, since CCA contains harmful elements such as chromium (chromium hexavalent) and arsenic, toxicity to humans and animals and environmental pollution have become problems.
【０００３】そこでＣＣＡの代替の水溶性薬剤として、
第四級アンモニウム化合物（例えばジデシルジメチルア
ンモニウムクロライド）あるいは第四級アンモニウム化
合物と銅化合物との混合剤が、また水希釈乳化型の薬剤
として、脂肪酸の金属塩（例えばナフテン酸亜鉛、ナフ
テン酸銅等）がそれぞれ提供されている。Therefore, as an alternative water-soluble drug for CCA,
A quaternary ammonium compound (for example, didecyldimethylammonium chloride) or a mixture of a quaternary ammonium compound and a copper compound is used as a water-diluted emulsion type agent, and a metal salt of a fatty acid (for example, zinc naphthenate, copper naphthenate). Etc.) are provided respectively.
【０００４】[0004]
【発明が解決しようとする課題】しかし、第四級アンモ
ニウム化合物を主体とする薬剤は木材中に固着しないた
めに、水に溶脱され易く、水分の多い場所や土壌中に埋
設するような場合には効力の持続を期待することができ
ない。一方、脂肪酸の金属塩は金属を主成分とするため
に効力持続性はある程度期待することができる。しか
し、脂肪酸の金属塩は油溶性であるために水希釈使用に
するためには乳化型にする必要があるが、一般に油性剤
を乳化して得られた乳化液は粒子が大きく、木材中へ浸
透させるには、粒子を小さくするための特殊な技術が必
要となってコスト高になるという問題があり、また乳化
前の液は消防法上の危険物であって保管が難しいという
問題もある。さらにこの脂肪酸の金属塩をで処理した木
材を乾燥不十分な状態で使用すると再乳化現象によって
薬剤成分が水に再乳化し、溶出するおそれがあるという
問題もある。However, since the chemicals mainly composed of the quaternary ammonium compound do not adhere to the wood, they are easily leached into water, and when they are buried in a humid place or soil. Can not expect lasting effect. On the other hand, the metal salt of fatty acid has a metal as a main component, and therefore, it can be expected that the efficacy lasts to some extent. However, since metal salts of fatty acids are oil-soluble, they need to be emulsified in order to be diluted with water, but generally emulsions obtained by emulsifying an oily agent have large particles, There is a problem in that it requires a special technique to make the particles smaller to increase the permeation, which increases the cost, and the liquid before emulsification is a dangerous substance under the Fire Defense Law and difficult to store. . Furthermore, if wood treated with this metal salt of a fatty acid is used in an insufficiently dried state, the drug component may be re-emulsified in water due to the re-emulsification phenomenon and may be eluted.
【０００５】本発明は上記の点に鑑みてなされたもので
あり、毒性や環境汚染のおそれなく、また消防法上の危
険なく、安全に使用することができると共に、水の容易
に溶解させて使用することができ、しかも木材に浸透処
理した後は長期に亘って効力を持続させることができる
木材保存剤を提供することを目的とするものである。The present invention has been made in view of the above points, and can be used safely without danger of toxicity or environmental pollution, and without danger under the Fire Service Act, and can be easily dissolved in water. It is an object of the present invention to provide a wood preservative that can be used and that can maintain its effect for a long period of time after it has been impregnated into wood.
【０００６】[0006]
【課題を解決するための手段】本発明に係る木材保存剤
は、キトサンの金属錯塩を主体として成ることを特徴と
するものである。また、上記キトサンの金属錯塩として
はキトサンと銅、亜鉛、銀から選ばれる金属との錯塩を
用いることができる。The wood preservative according to the present invention is characterized by mainly containing a metal complex salt of chitosan. As the metal complex salt of chitosan, a complex salt of chitosan and a metal selected from copper, zinc and silver can be used.
【０００７】以下、本発明を詳細に説明する。キトサン
は、カニやエビ等の甲殻類や昆虫類などの外殻に豊富に
含有される多糖類の一種であるキチンを脱アセチル化す
ることによって得られるものであり、その化学構造の骨
格は木材の繊維成分であるセルロースに非常に類似した
天然高分子物質である。本発明においてキトサンとして
は脱アセチル化度５０〜９０、分子量５００以上のもの
であれば特に制限されることなく使用することができる
が、できれば分子量５００００以下の低分子のものが望
ましく、特に分子量２００００以下のものがさらに好ま
しい。The present invention will be described in detail below. Chitosan is obtained by deacetylating chitin, which is a kind of polysaccharide that is abundantly contained in the outer shells of crustaceans such as crabs and shrimps, and in the outer shells of insects, and the skeleton of its chemical structure is wood. It is a natural polymer substance very similar to cellulose, which is a fiber component of In the present invention, chitosan can be used without particular limitation as long as it has a deacetylation degree of 50 to 90 and a molecular weight of 500 or more, but if possible, a low molecular weight of 50,000 or less is preferable, and a molecular weight of 20,000 is particularly preferable. The following are more preferable.
【０００８】このキトサンと金属錯塩を作る金属として
は、木材保存のための防虫・殺虫効力及び防腐・防黴効
力に極めて優れていると認められており、世界的にも実
証されている銅や亜鉛、銀などを用いることができる。
キトサンの金属錯塩は、キトサンとこれらの金属の水溶
性金属塩を反応させることによって調製することができ
る。水溶性金属塩として、銅塩では塩化第二銅や硫酸銅
等を、亜鉛塩では塩化亜鉛や硫酸亜鉛等を、銀塩では硝
酸銀等を用いることができるが、水溶性であるならばこ
れら以外の各種の金属塩を用いることもできる。It is recognized that the metal forming the metal complex salt with chitosan is extremely excellent in the insecticidal / insecticidal effect and the antiseptic / mildew effect for preserving wood, and copper and Zinc, silver, etc. can be used.
Metal complex salts of chitosan can be prepared by reacting chitosan with water-soluble metal salts of these metals. As the water-soluble metal salt, cupric chloride, copper sulfate, etc. can be used as the copper salt, zinc chloride, zinc sulfate, etc. can be used as the zinc salt, and silver nitrate, etc. can be used as the silver salt. Various metal salts of can also be used.
【０００９】そしてまず、水溶性金属塩を塩濃度として
３〜１０重量％程度になるように水に溶解させて金属塩
水溶液を準備する。次に、金属塩水溶液を攪拌しながら
金属塩と同重量から半分程度の重量のキトサンを添加
し、攪拌を続けて反応させる。そしてガラス製のフィル
ター等でろ別して十分に水洗することによって、金属濃
度４〜２０重量％程度のキトサンの金属錯塩を得ること
ができる。このようにしてキトサンの金属錯塩を調製す
ることができるが、勿論この方法に限定されるものでな
く任意の方法を採用することができるものであり、例え
ば３〜１０重量％の金属塩水溶液の代わりに金属塩の飽
和溶液を使用してもよく、またろ過材としてガーゼや布
等の目の荒い繊維製品を使用することもできる。First, a water-soluble metal salt is dissolved in water to a salt concentration of about 3 to 10% by weight to prepare an aqueous metal salt solution. Next, while stirring the metal salt aqueous solution, chitosan of the same weight to about half the weight of the metal salt is added, and stirring is continued to react. Then, a metal complex salt of chitosan having a metal concentration of about 4 to 20% by weight can be obtained by filtering with a glass filter or the like and thoroughly washing with water. The metal complex salt of chitosan can be prepared in this manner, but it is of course not limited to this method, and any method can be adopted. For example, 3 to 10% by weight of an aqueous metal salt solution can be used. Alternatively, a saturated solution of a metal salt may be used, and a coarse fiber product such as gauze or cloth may be used as the filter material.
【００１０】上記のようにして得られたキトサンの金属
錯塩は、有機酸あるいは無機酸の存在下、水に溶解させ
て水溶液として使用することができるものであり、キト
サンの金属錯塩の水溶液を木材に浸透させることによっ
て、キトサンの金属錯塩に含有される金属の作用で優れ
た防虫・殺虫効力や防腐・防黴効力を発揮させることが
でき、またキトサンは上記のようにセルロースに非常に
類似した化学骨格構造を有すると共に、セルロースが電
気的にマイナス（負の電荷）を持つポリアニオン物質で
あるのに対してキトサンはプラス（正の電荷）を持つポ
リカチオンであるために、キトサンは木材繊維との固着
性が高く、金属を木材に高く固着させることができる。
従って耐水性、耐溶脱性が高く、長期に亘って効力を持
続させることができるものである。そして、キトサンの
金属錯塩は、クロムや砒素のような有害元素を含有する
必要がなく、人畜への毒性や環境汚染等のおそれはな
く、また脂肪酸の金属塩のような消防法上の問題もない
ものである。The metal complex salt of chitosan obtained as described above can be used as an aqueous solution by dissolving it in water in the presence of an organic acid or an inorganic acid. An aqueous solution of the metal complex salt of chitosan is used as a wood. The effect of the metal contained in the metal complex salt of chitosan can exert excellent insecticidal / insecticidal effect and antiseptic / antifungal effect, and chitosan is very similar to cellulose as described above. In addition to having a chemical skeletal structure, cellulose is a polyanion substance that has an electrical negative (negative charge), whereas chitosan is a polycation that has a positive (positive charge). The metal has a high adhesiveness and can highly adhere metal to wood.
Therefore, it has high water resistance and leaching resistance, and can maintain its efficacy over a long period of time. And, the metal complex salt of chitosan does not need to contain harmful elements such as chromium and arsenic, and there is no fear of toxicity to human livestock or environmental pollution. There is no such thing.
【００１１】また、キトサンの金属錯塩は、キトサンが
木材組織の空隙に充満することによって、木材収縮や膨
張を緩和して寸法安定化を図ることができるものであ
る。尚、上記のようにして調製したキトサンの金属錯塩
は、キトサン単独のものよりも溶解性に優れていると共
に、また粘度測定から推定するとキトサンの分子量が反
応当初のものから１／２〜１／３程度に減少しており、
この結果木材中に浸透し易い形態に変化している。この
キトサンの分子量の減少は、反応操作中に生成される塩
酸等の酸による加水分解に起因すると推定される。Further, the metal complex salt of chitosan is capable of reducing the shrinkage and expansion of wood and stabilizing the size by filling the voids of the wood structure with chitosan. In addition, the metal complex salt of chitosan prepared as described above is superior in solubility to that of chitosan alone, and the molecular weight of chitosan is 1/2 to 1 / from that of the initial reaction estimated from viscosity measurement. Has decreased to about 3,
As a result, it has changed into a form that allows it to easily penetrate into wood. It is presumed that the decrease in the molecular weight of chitosan is due to the hydrolysis by an acid such as hydrochloric acid generated during the reaction operation.
【００１２】[0012]
【実施例】次に、本発明を実施例によって例証する。 （実施例１）水道水９５５ｇに塩化第二銅（純度９５
％）を４５ｇ投入し、攪拌しながら４５〜５０℃に加熱
して完全溶解させて４．５重量％濃度の塩化第二銅水溶
液を調製した。次に、塩化第二銅水溶液を加熱したまま
攪拌しながらキトサン（分子量１００００〜２０００
０、脱アセチル化度８７）を５０ｇ投入して２時間反応
させた。この後、生成物をろ別し、水で十分に洗浄して
５０℃の循環式オーブン内で４８時間乾燥させてキトサ
ンの銅塩を得た。このようにして得たキトサンの銅塩の
一部を採って原子吸光分析法にて銅金属の含有率を分析
したところ、６．６７重量％であった。The invention will now be illustrated by the examples. (Example 1) Cupric chloride (purity 95
%) Of 45%, and heated to 45 to 50 ° C. with stirring to completely dissolve it to prepare an aqueous solution of cupric chloride having a concentration of 4.5% by weight. Then, while stirring the aqueous cupric chloride solution while heating, chitosan (molecular weight of 10,000 to 2000 is stirred).
50 g of 0 and deacetylation degree 87) were added and reacted for 2 hours. Then, the product was filtered off, washed thoroughly with water and dried in a circulating oven at 50 ° C. for 48 hours to obtain a chitosan copper salt. A part of the copper salt of chitosan thus obtained was sampled and analyzed for the content of copper metal by atomic absorption spectrometry. As a result, it was 6.67% by weight.
【００１３】（実施例１−２、１−３）また、キトサン
と反応させる塩化第二銅の量を表１のように変え、あと
は実施例１と同様にしてキトサンの銅塩を得た。このキ
トサンの銅塩における銅金属の含有率は表１の通りであ
った。(Examples 1-2, 1-3) Further, the amount of cupric chloride reacted with chitosan was changed as shown in Table 1, and the copper salt of chitosan was obtained in the same manner as in Example 1. . The content of copper metal in the copper salt of chitosan is shown in Table 1.
【００１４】[0014]
【表１】 [Table 1]
【００１５】（実施例２）水道水９５５ｇに塩化亜鉛
（純度９６％）を４５ｇ投入し、攪拌しながら４５〜５
０℃に加熱して完全溶解させて４．５重量％濃度の塩化
亜鉛水溶液を調製した。次に、塩化亜鉛水溶液を加熱し
たまま攪拌しながらキトサン（分子量１００００〜２０
０００、脱アセチル化度８７）を５０ｇ投入して２時間
反応させた。この後、生成物をろ別し、水で十分に洗浄
して５０℃の循環式オーブン内で４８時間乾燥させてキ
トサンの亜鉛塩を得た。このようにして得たキトサンの
亜鉛塩の一部を採って原子吸光分析法にて亜鉛金属の含
有率を分析したところ、８．６２重量％であった。(Example 2) 45 g of zinc chloride (purity 96%) was added to 955 g of tap water, and the mixture was stirred at 45-5.
It was heated to 0 ° C. and completely dissolved to prepare a 4.5 wt% concentration zinc chloride aqueous solution. Next, while stirring the zinc chloride aqueous solution while heating, chitosan (molecular weight of 10,000 to 20) is stirred.
000, 50 g of deacetylation degree 87) was added and reacted for 2 hours. Then, the product was filtered off, washed thoroughly with water, and dried in a circulating oven at 50 ° C. for 48 hours to obtain a zinc salt of chitosan. A part of the thus obtained zinc salt of chitosan was sampled and analyzed for the content of zinc metal by an atomic absorption spectrometry, and it was found to be 8.62% by weight.
【００１６】（実施例２−２、２−３、２−４）また、
キトサンと反応させる塩化亜鉛の量を表１のように変
え、あとは実施例２と同様にしてキトサンの亜鉛塩を得
た。このキトサンの亜鉛塩における亜鉛金属の含有率は
表１の通りであった。(Examples 2-2, 2-3, 2-4) Also,
The amount of zinc chloride reacted with chitosan was changed as shown in Table 1, and the zinc salt of chitosan was obtained in the same manner as in Example 2. The content of zinc metal in the zinc salt of chitosan is shown in Table 1.
【００１７】[0017]
【表２】 [Table 2]
【００１８】（キトサンの金属錯塩の粘度測定）実施例
１で得たキトサンの銅塩を１ｇ採り、酢酸０．５ｇと共
に水９８．５ｇに４５℃の条件で溶解させた。また比較
のために未処理のキトサンを１ｇ採り、同様にして酢酸
と共に水に溶解させた。これらの完全溶解時間と溶解後
の粘度をそれぞれ測定した。(Viscosity measurement of metal complex salt of chitosan) 1 g of the copper salt of chitosan obtained in Example 1 was taken and dissolved in 0.5 g of acetic acid in 98.5 g of water at 45 ° C. For comparison, 1 g of untreated chitosan was taken, and similarly dissolved in water together with acetic acid. The complete dissolution time and the viscosity after dissolution were measured.
【００１９】結果は、未処理キトサンの場合は、完全溶
解に３７分を要し、粘度は１８センチポイズ（４５℃）
であったが、一方、実施例１のキトサンの銅塩の場合
は、２１分で完全に溶解し、粘度は８センチポイズ（４
５℃）であった。キトサンの粘度−分子量関係のグラフ
から分子量を推定すると、１８センチポイズは約４８０
００、８センチポイズは約３００００であり、実施例１
のものは未処理キトサンよりも分子量が小さくなってい
ることが確認される。実施例２のキトサンの亜鉛塩にお
いても同様な傾向がみられる。As a result, in the case of untreated chitosan, it took 37 minutes to completely dissolve it, and the viscosity was 18 centipoise (45 ° C.).
However, in the case of the copper salt of chitosan of Example 1, it completely dissolved in 21 minutes and the viscosity was 8 centipoise (4
5 ° C.). Estimating the molecular weight from the viscosity-molecular weight relationship graph of chitosan, 18 centipoise is about 480.
00,8 centipoise is about 30,000, and Example 1
It is confirmed that the product has a lower molecular weight than untreated chitosan. A similar tendency is observed in the zinc salt of chitosan of Example 2.
【００２０】（キトサンの金属塩の溶脱試験）実施例１
で得たキトサンの銅塩、実施例２で得たキトサンの亜鉛
塩、及び比較のために塩化第二銅、硫酸銅、塩化亜鉛を
それぞれ用い、ＪＩＳ Ａ ９２０１に準じて溶脱試験
をおこなった。まず、実施例１で得たキトサンの銅塩
（銅含有量６．６７重量％）、塩化第二銅（純度９５
％、銅含有量４７．３重量％）、硫酸銅（純度９９％、
銅含有量２５．５重量％）については、それぞれ銅金属
濃度が０．２９重量％になるように水に溶解して水溶液
を調製して木材保存剤として使用した。尚、このとき実
施例１のキトサンの銅塩は同量の酢酸を溶解補助剤とし
て添加した。(Leaching test of metal salt of chitosan) Example 1
A leaching test was performed according to JIS A 9201 using the copper salt of chitosan obtained in 1., the zinc salt of chitosan obtained in Example 2, and cupric chloride, copper sulfate, and zinc chloride for comparison, respectively. First, the copper salt of chitosan (copper content 6.67% by weight) obtained in Example 1 and cupric chloride (purity 95
%, Copper content 47.3% by weight), copper sulfate (purity 99%,
Regarding the copper content of 25.5% by weight), each was dissolved in water to have a copper metal concentration of 0.29% by weight to prepare an aqueous solution and used as a wood preservative. At this time, the same amount of acetic acid as the copper salt of chitosan of Example 1 was added as a solubilizing agent.
【００２１】また、実施例２で得たキトサンの亜鉛塩
（亜鉛含有量８．６２重量％）、塩化亜鉛（純度９６
％、亜鉛含有量４８．０重量％）については、それぞれ
亜鉛金属濃度が０．３３重量％になるように水に溶解し
て水溶液を調製して木材保存剤として使用した。尚、こ
のとき実施例２のキトサンの亜鉛塩は同量の酢酸を溶解
補助剤として添加した。Further, the zinc salt of chitosan (zinc content: 8.62% by weight) obtained in Example 2 and zinc chloride (purity: 96
%, And a zinc content of 48.0% by weight) were dissolved in water so that the zinc metal concentration was 0.33% by weight to prepare an aqueous solution, which was used as a wood preservative. At this time, the zinc salt of chitosan of Example 2 was added with the same amount of acetic acid as a solubilizing agent.
【００２２】上記のように調製した木材保存剤を２ｃｍ
×２ｃｍ（木口）×１ｃｍ（厚さ）のスギ試験材に減圧
注入し、これを供試材料とし、半分をＪＩＳ Ａ ９２
０１に準じて耐候操作をして溶脱試験した。そして溶脱
試験をおこなう前の残りの半分と、この溶脱試験をした
半分の供試材料についてそれぞれ原子吸光分析法によっ
て銅金属や亜鉛金属の濃度を測定し、金属の溶脱率を求
めた。結果を表３に示す。2 cm of wood preservative prepared as described above
It was vacuum-injected into a cedar test material measuring 2 cm (x 2 cm) and 1 cm (thickness), and this was used as a test material.
According to No. 01, weathering operation was performed and a leaching test was performed. Then, the concentration of copper metal and zinc metal was measured by atomic absorption spectrometry for the remaining half before the leaching test and for the half of the test material subjected to the leaching test, and the leaching rate of the metal was obtained. The results are shown in Table 3.
【００２３】[0023]
【表３】 [Table 3]
【００２４】表３にみられるように、水溶性の金属塩で
ある塩化第二銅、硫酸銅、塩化亜鉛では溶脱率が３５％
を超えるのに対して、キトサンの金属錯塩である実施例
１，２のものは溶脱率が７％以下であり、キトサンの金
属錯塩中の金属は木材に固着していることが確認され
る。 （防腐効力試験）上記「キトサンの金属塩の溶脱試験」
の項で作成した木材保存剤及びスギ試験材を使用し、Ｊ
ＩＳ Ａ ９２０１に準拠して、金属含有量として銅金
属ではほぼ１．２ｋｇ／ｍ3 、亜鉛金属ではほぼ２．２
ｋｇ／ｍ3 となるように、スギ試験材に木材保存材を注
入処理して、耐候操作をおこなった後、この試験材をオ
オウズラタケ及びカワラタケの菌そうに３ヵ月放置して
腐朽させてその際の質量減少率を求める防腐効力試験を
実施した。また比較のためにＣＣＡ３号（ＪＩＳＫ １
５５４）を用いて処理したもの、無処理のものについて
も同様に試験した。結果を表４に示す。As shown in Table 3, the water-soluble metal salts of cupric chloride, copper sulfate and zinc chloride have a leaching rate of 35%.
On the other hand, the leaching rate of the metal complex salts of chitosan of Examples 1 and 2 is 7% or less, and it is confirmed that the metal in the metal complex salt of chitosan is fixed to the wood. (Preservative efficacy test) Above "Leaching test of metal salt of chitosan"
Using the wood preservative and cedar test material prepared in the section
According to IS A 9201, the metal content is about 1.2 kg / m 3 for copper metal and about 2.2 for zinc metal.
After the wood preservative was injected into the cedar test material so that it would be kg / m 3, and the weathering operation was performed, the test material was left to stand for 3 months in the fungus of Pleurotus cornucopiae and Pleurotus cornucopiae, which was then allowed to decay. A preservative efficacy test was carried out to determine the mass reduction rate of. For comparison, CCA 3 (JISK 1
The same test was carried out for those treated with 554) and those not treated. The results are shown in Table 4.
【００２５】[0025]
【表４】 [Table 4]
【００２６】表４にみられるように、水溶性金属塩であ
る塩化第二銅、硫酸銅、塩化亜鉛では、質量減少率がい
ずれも１３％以上であり、合格値の３．０％以下に比べ
て極めて悪い結果を示したが、キトサンの金属錯塩であ
る実施例１，２のものは質量減少率がいずれも１．８％
以下であり、ＣＣＡ３号を使用する場合と同等の良好な
結果が得られるものであった。As can be seen from Table 4, in the case of the water-soluble metal salts of cupric chloride, copper sulfate and zinc chloride, the mass reduction rate is 13% or more, which is 3.0% or less of the passing value. The results were extremely poor in comparison, but the mass reduction rate of the metal complex salts of chitosan of Examples 1 and 2 was 1.8%.
The following was obtained, and good results equivalent to the case of using CCA No. 3 were obtained.
【００２７】（野外効力試験）実施例１のキトサンの銅
塩、実施例２のキトサンの亜鉛塩、硫酸銅、塩化亜鉛を
用いて上記「キトサンの金属塩の溶脱試験」の項で作成
した木材保存剤と、木口３ｃｍ×３ｃｍ、長さ３５ｃｍ
の寸法の先端を尖らせたアカマツ辺材を用い、金属含有
量として銅金属ではほぼ１．２ｋｇ／ｍ3 、亜鉛金属で
はほぼ２．２ｋｇ／ｍ3 となるように、アカマツ辺材に
木材保存剤を加圧注入処理した。そして各木材保存剤に
ついて５本づつ鹿児島県日置郡上浜の国有林内にて５年
間の野外試験効力試験を実施した。結果を表５に示す。(Field Efficacy Test) Wood prepared by using the copper salt of chitosan of Example 1, the zinc salt of chitosan, copper sulfate, and zinc chloride of Example 2 in the above-mentioned "leaching test of metal salt of chitosan". Preservative, wood mouth 3cm x 3cm, length 35cm
Tip with red pine sapwood having a pointed dimensions, approximately 1.2 kg / m 3 in the copper metal as metal content, to be substantially 2.2 kg / m 3 in the zinc metal, wood preservative Pinus densiflora sapwood The agent was pressure injected. Then, five of each wood preservative was tested in a national forest in Kamehama, Hioki-gun, Kagoshima prefecture for 5 years. The results are shown in Table 5.
【００２８】[0028]
【表５】 [Table 5]
【００２９】表５にみられるように、水溶性金属塩であ
る硫酸銅や塩化亜鉛では、表面に明らかな腐朽及び食害
が観察されたが、キトサンの金属錯塩である実施例１，
２のものは５年経過した現在でも全く腐朽やシロアリに
よる食害を受けていないものであった。As can be seen from Table 5, with water-soluble metal salts such as copper sulfate and zinc chloride, obvious decay and feeding damage were observed on the surface, but Example 1, which is a metal complex salt of chitosan, was observed.
No. 2 had no decay or termite damage even after 5 years.
【００３０】[0030]
【発明の効果】上記のように本発明に係る木材保存剤
は、キトサンの金属錯塩を主体とするものであるから、
酸と共に水に容易に溶解させて水溶液として使用するこ
とができると共に、キトサンの金属錯塩に含有される金
属の作用で防虫・殺虫効力や防腐・防黴効力を発揮させ
ることができるものであり、またキトサンは木材繊維と
の固着性が高く、この金属を木材に高く固着させること
ができるものであって、長期に亘って効力を持続させる
ことができるものである。しかもキトサンの金属錯塩
は、クロムや砒素のような有害元素を含有する必要がな
く、人畜への毒性や環境汚染等のおそれがないと共に、
また脂肪酸の金属塩のような消防法上の問題もないもの
である。As described above, since the wood preservative according to the present invention is mainly composed of a metal complex salt of chitosan,
It can be easily dissolved in water together with an acid and used as an aqueous solution, and can exhibit insecticidal / insecticidal efficacy and antiseptic / mildew efficacy by the action of the metal contained in the metal complex salt of chitosan. Further, chitosan has a high adhesiveness to wood fibers, and is capable of strongly adhering this metal to wood, and can maintain its efficacy for a long period of time. Moreover, the metal complex salt of chitosan does not need to contain harmful elements such as chromium and arsenic, and there is no risk of toxicity to human livestock or environmental pollution.
In addition, it does not have the problem under the Fire Service Law like metal salts of fatty acids.
Claims (2)
とを特徴とする木材保存剤。1. A wood preservative, which is mainly composed of a metal complex salt of chitosan.
鉛、銀から選ばれる金属との錯塩であることを特徴とす
る請求項１に記載の木材保存剤。2. The wood preservative according to claim 1, wherein the metal complex salt of chitosan is a complex salt of chitosan and a metal selected from copper, zinc and silver.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5217134A JPH07118970B2 (en) | 1993-09-01 | 1993-09-01 | Wood preservative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5217134A JPH07118970B2 (en) | 1993-09-01 | 1993-09-01 | Wood preservative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0768508A true JPH0768508A (en) | 1995-03-14 |
| JPH07118970B2 JPH07118970B2 (en) | 1995-12-20 |
Family
ID=16699394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5217134A Expired - Lifetime JPH07118970B2 (en) | 1993-09-01 | 1993-09-01 | Wood preservative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118970B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1144492A4 (en) * | 1998-11-24 | 2002-09-18 | Safescience Inc | Chitosan metal complexes and method controlling microbial growth on plants using same |
| WO2003060003A1 (en) * | 2001-12-21 | 2003-07-24 | E.I. Du Pont De Nemours And Company | Antimicrobial solid surface materials containing chitosan-metal complexes |
| JP2007526139A (en) * | 2003-06-17 | 2007-09-13 | フィブロ−テック，インコーポレイテッド | Fine particle wood preservative and method for producing the same |
| WO2012153760A1 (en) | 2011-05-11 | 2012-11-15 | 日本曹達株式会社 | Construction material preservative |
| CN107571360A (en) * | 2017-10-30 | 2018-01-12 | 四川行之智汇知识产权运营有限公司 | Timber preservative with biocidal efficacies |
| CN111516080A (en) * | 2020-04-29 | 2020-08-11 | 三裕化工(深圳)有限公司 | Wood preservative and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06170810A (en) * | 1992-12-02 | 1994-06-21 | Tadamoro Inoue | Wood preservative, wood preserved against decay and improvement of wood |
-
1993
- 1993-09-01 JP JP5217134A patent/JPH07118970B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06170810A (en) * | 1992-12-02 | 1994-06-21 | Tadamoro Inoue | Wood preservative, wood preserved against decay and improvement of wood |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1144492A4 (en) * | 1998-11-24 | 2002-09-18 | Safescience Inc | Chitosan metal complexes and method controlling microbial growth on plants using same |
| WO2003060003A1 (en) * | 2001-12-21 | 2003-07-24 | E.I. Du Pont De Nemours And Company | Antimicrobial solid surface materials containing chitosan-metal complexes |
| JP2007526139A (en) * | 2003-06-17 | 2007-09-13 | フィブロ−テック，インコーポレイテッド | Fine particle wood preservative and method for producing the same |
| WO2012153760A1 (en) | 2011-05-11 | 2012-11-15 | 日本曹達株式会社 | Construction material preservative |
| KR20130135390A (en) | 2011-05-11 | 2013-12-10 | 닛뽕소다 가부시키가이샤 | Construction material preservative |
| US9433216B2 (en) | 2011-05-11 | 2016-09-06 | Nippon Soda Co., Ltd. | Construction material preservative |
| CN107571360A (en) * | 2017-10-30 | 2018-01-12 | 四川行之智汇知识产权运营有限公司 | Timber preservative with biocidal efficacies |
| CN111516080A (en) * | 2020-04-29 | 2020-08-11 | 三裕化工(深圳)有限公司 | Wood preservative and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07118970B2 (en) | 1995-12-20 |
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