JP2008207552A - 電子受容性物質を含有する木材保存剤組成物及び染料を指示薬として用いる該木材保存剤組成物の木質材料への浸潤度測定方法 - Google Patents
電子受容性物質を含有する木材保存剤組成物及び染料を指示薬として用いる該木材保存剤組成物の木質材料への浸潤度測定方法 Download PDFInfo
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- JP2008207552A JP2008207552A JP2008019090A JP2008019090A JP2008207552A JP 2008207552 A JP2008207552 A JP 2008207552A JP 2008019090 A JP2008019090 A JP 2008019090A JP 2008019090 A JP2008019090 A JP 2008019090A JP 2008207552 A JP2008207552 A JP 2008207552A
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
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Landscapes
- Chemical And Physical Treatments For Wood And The Like (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
【解決手段】処理薬剤に含有される電子受容性物質によって発色するロイコ染料を指示薬とすることで、浸潤度を測定できるようにした。
【選択図】なし
Description
以下に、この発明に係る木材保存剤組成物及びその製剤法について述べる。
電子受容性物質(呈色剤)としては、例えば、次のような感熱記録材料などで公知の酸性物質、例えばフェノール誘導体、酸性ポリマーまたはその金属変性物、有機カルボン酸またはその金属塩などの顕色剤が挙げられる。これらは、単独でまたは2種以上を組み合わせて用いることができる。
1)フェノール誘導体:4−tert−ブチルフェノール、4−オクチルフェノール、4−フェニルフェノール、1−ナフトール、2−ナフトール、ハイドロキノン、レゾルシノール、4−tert−オクチルカテコール、2,2’−ジヒドロキシビフェニル、4,4’−ジヒドロキシジフェニルエーテル、2,2−ビス(4−ヒドロキシフェニル)プロパン[一般名ビスフェノールA]。
フェノール樹脂、アルキルフェノール樹脂、マレイン酸樹脂、フェノール−アセチレン樹脂、フェノール−ホルムアルデヒド樹脂、少なくとも1個のヒドロキシ基を有するカルボン酸とホルムアルデヒドとの縮合物、およびこれらの亜鉛、ニッケル等の多価金属変性物等。
サリチル酸、3−イソプロピルサリチル酸、3−tert−ブチルサリチル酸、3−ベンジルサリチル酸、3−クロル−5−(α−メチルベンジル)サリチル酸、3−フェニル−5−(α,α−ジメチルベンジル)サリチル酸、3,5−ジ−(α−メチルベンジル)サリチル酸、4−(3−p−トリルスルホニルプロピルオキシ)サリチル酸、5−{p−[2−(p−メトキシフェノキシ)エトキシ]クミル}サリチル酸、3−シクロヘキシルサリチル酸、3,5−ジ−tert−ブチルサリチル酸、3−メチル−5−α−メチルベンジルサリチル酸、4−[2−(4−メトキシフェノキシ)エトキシ]サリチル酸、2−ヒドロキシ−3−ナフトエ酸、2−ヒドロキシ−6−ナフトエ酸、フタル酸モノベンジルエステル、フタル酸モノフェニルエステル、4−ニトロ安息香酸、3−ニトロ安息香酸、2−ニトロ安息香酸、4−クロロ安息香酸等の有機酸、あるいはこれらの金属塩(たとえば、ニッケル、亜鉛、アルミニウム、カルシウム等の金属塩)、チオシアン酸亜鉛アンチピリン錯体、モリブデン酸アセチルアセトン錯体等の錯体。
また、電子受容性物質としては、ノニオン系又はアニオン系界面活性剤もまた用いることができる。
ポリオキシエチレンヒマシ油エーテル、ポリオキシエチレンオレイン酸エステルなどが挙げられる。
本発明の木材保存剤組成物に使用される殺虫剤としては、例えば、プロペタンホスなどの有機リン系化合物類;ペルメトリンなどのピレスロイド系化合物類;シラフルオフェン、エントフェンプロックスなどのピレスロイド様化合物類;フェノブカルブなどのカーバメート系化合物類;トリプロピルイソシアヌレートなどのトリアジン系化合物類;モノクロルナフタリンなどのナフタリン系化合物類;オクタクロロジプロピルエーテルなどの塩素化ジアルキルエーテル添加系化合物類;イミダクロプリドなどのネコニコチノイド系化合物類などが挙げられる。その他の殺虫剤を系統別に挙げると下記のとおりである。
フェニルピラゾール系:アセトプロール、エチプロール、フィプロニル、バニリプロール、ピリプロール、ピラフルプロール、TI−809。
ジベンゾイルヒドラジン系化合物類:クロマフェノジド、ハロフェノジド、メトキシフェノジド、テブフェノジド。
アルキルアミンアセテート:炭素数8〜18の混合または単一アルキルアミンアセテート。
フタル酸ジアミド系化合物類:フルベンジアミド。
アンスラニルアミド系化合物類:リナキシピル。
オキサジアジン系化合物類:インドキサカルブ。
フェニルピロール系化合物類:クロルフェナピル。
マクロライド系化合物類:アバメクチン、エマメクチン、ミルベメクチン、ミルベマイシンオキシム、モキシデクチン、スピノサド。
キチン合成阻害系化合物類:ビストリフルロン、ブプロフェジン、クロルフルアズロン、ジフルベンズロン、ヘキサフルムロン、ルフェヌノン、ノビフルムロン、トリフルムロン。
幼若ホルモン系化合物類:フェノキシカルブ、メトプレン、ピリプロキシフェン。
本発明の木材保存剤組成物に使用される木材防腐剤としては、例えば、下記の
とおりである。
3−ブロモ−2,3−ジヨード−2−プロペニルエチルカルボナートなどの有機ヨード系化合物類。
ナフテン酸銅、ナフテン酸亜鉛などの金属塩類。
N−ニトロソ−シクロヘキシルヒドロキシルアミンアルミニウムなどのヒドロキシルアミン系化合物類。
モノクロルナフタリンなどのナフタリン系化合物類。
N,N−ジメチル−N’−フェニル−N’(ジクロフルオロメチルチオ)スルファミドなどのハロアルキルチオ系化合物類。
テトラクロルイソフタロニトリルなどのニトリル系化合物類。
クレオソート油などのタール系化合物類。
ジニトロフェノールなどのフェノール系化合物類。
ジデシルジメチルアンモニウムクロライドなどの第4級アンモニウム塩。
ホルマリンなどのアルデヒド類。
桂皮酸などの芳香族カルボン酸。
トリブチルスズフタレートなどの有機スズ誘導体。
エタノールなどのアルコール類。
2−メルカプトベンゾチアゾールなどのベンゾチアゾール系化合物類。
銅化合物、ホウ酸などの無機化合物などが挙げられる。本発明において利用可能なその他の防腐剤を下記に列挙する。
本発明で指示薬として使用される染料としては、下記のロイコ染料が好ましく、これらを単独で又は2種以上を混合して使用することが出来る。本発明で使用可能なロイコ染料を下記に列挙する。
水溶性製剤とする場合には、通常、有効成分をアルコール系などの水溶性有機溶媒に溶解し、これに界面活性剤および水を加えて製剤化する。また、水溶性製剤を木材に塗布処理した場合の被膜形成のために、必要に応じて水溶性製剤に樹脂エマルションを添加してもよい。
1)脂肪族炭化水素系:n−ヘキサン、シクロヘキサン、ヘプタン、オクタンなど。
2)芳香族炭化水素系:キシレン、トルエン、エチルベンゼン、クメン、モノイソプロピルナフタレン、ジイソプロピルナフタレン、モノイソプロピルビフェニルなど。
3)エステル系:酢酸エチル、酢酸メチル、酢酸n−ブチル、酢酸アミルなど。
5)ケトン系:アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノンなど。
6)カーボネート系:プロピレンカーボネートなど。
7)含窒素化合物系:N−メチル−2−ピロリドンなど。
乳剤とする場合には、通常、有効成分を有機溶媒に溶解し、これを界面活性剤(乳化剤)に加え、水を適宜添加して製剤化する。また、乳剤を木材に塗布処理した場合の被膜形成のために、必要に応じて乳剤に樹脂エマルションを添加してもよい。有機溶媒、界面活性剤および樹脂エマルションは、水溶性製剤について例示したものを使用することができる。乳剤では、疎水性有機溶媒が好適に用いられる。
フロアブル製剤とする場合には、乳化剤及び/又は増粘剤を用いて製剤化する。
油剤とする場合には、水性溶媒で例示された有機溶媒の他、灯油、重油、スピンドル油などの炭化水素溶媒を用いて製剤化する。
粉剤や水和剤とする場合には、通常、有効成分を固体希釈剤(例えば、カオリン、クレー、ベントナイト、CMC、二酸化チタン、ホワイトカーボン、タルク、木粉、デンプン、デキストリン、シリカゲル粉末、水酸化カルシウムなどのカルシウム塩、無水石膏など)で希釈し、混合粉砕して製剤化する。粒剤とする場合には、粉剤を成形して製剤化する。
本発明の木材保存剤組成物の木材への処理方法は、塗布、吹付け、浸漬、減圧、加圧などの方法が挙げられるがこれらに限定されるものではない。また、減圧、加圧の方法については、油剤、あるいは水溶性剤を用いて処理する方法に加え、揮発性有機溶媒に不揮発性の木材保存剤および電子受容性物質を溶解した溶液を用いて、含浸タンクの中で木材の保存処理を行い、その後、揮発性有機溶媒を揮発させることにより、不揮発性の木材保存剤および電子受容性物質が木材に残留するようにする方法をとることもできる。
本発明の木材保存剤組成物の木材への湿潤度は、ロイコ染料を指示薬として用いて測定する。すなわち、木材保存剤組成物で処理した対象木材に対して、ロイコ染料を塗布又は噴霧して放置し、塗布又は噴霧面を目視観察し、所定の色に呈色した部分を浸潤部として、薬剤浸潤度を測定する。
また、本発明では、ロイコ染料の塗布又は噴霧面に、さらに水又は緩衝液、好ましくは緩衝液、より好ましくはpHを約5付近に調整した緩衝液を噴霧するのが、所定の色が濃く呈色する点で好ましい。
農林水産省告示第143号「針葉樹の構造用製材の日本農林規格」浸潤度試験の試験法−1に基づいた方法により浸潤度試験を行なう。すなわち、農林水産省告示第143号「針葉樹の構造用製材の日本農林規格」浸潤度試験の項に記載の「試験法−1」に準拠して、浸潤度を評価する。具体的には、処理した対象木材を長さの中央付近で切断し、試料片を得、指示薬を塗布または噴霧して放置し、塗布または噴霧面を目視観察し、所定の色に呈色した部分を浸潤部とする方法である。
浸潤度D1(%)=試験片の辺材部分の呈色面積/試験片の辺材部分の面積×100
浸潤度D2(%)=A/B×100
D1:処理木材の辺材部分の浸潤度(%)
D2:処理木材の表面から深さd(mm)までの心材部分の浸潤度(%)
A:処理木材の表面からの深さd(mm)までの心材部分の浸潤面積
B:処理木材の表面からの深さd(mm)までの心材部分の面積
なお、通常dは10mmである。また、浸潤度D1およびD2の良否の判定は、木材の種類や用途、形状などによって異なるが、通常、80%以上のとき合格とし、80%未満のとき不合格とする。
以下、本発明の具体化した木材防腐処理剤と呈色について、その効果を確認した実施例および試験例により詳細に説明するが、この製剤例および試験例によりこの発明が限定されるものではない。
表1、2のように木材防腐処理剤を調製した。
表1に示した処理剤を75倍希釈し、ベイマツ木片の一部に滴下した。乾燥後3−(4−ジエチルアミノ−2−エトキシフェニル)−3−(1−エチル−2−メチルインドール−3−イル)−4−アザフタリド(Blue−63)溶液(0.2% w/v 酢酸エチル溶液)を木片に滴下したところ、処理剤で処理された部分が発色したことを確認した。但し、境界線は識別可能であるものの非処理部分にも若干発色がみられた。
(試験例2)呈色確認試験2
Blue−63を6’−〔エチル(4−メチルフェニルアミノ)−3’−メチル−2’−(フェニルアミノ)〕−スピロ〔イソベンゾフラン−1(3H),9’−(9H)キサンテン〕−3−オン(S−205)溶液(3% w/v アセトン溶液)に置き換えた以外、試験例1と同様に試験したところ、処理剤で処理された部分が発色した。試験例1の結果と比較し、非処理部分の発色は非常に薄いものであった。また、発色は水を噴霧すると更に濃くなった。
(試験例3)呈色確認試験3
処理剤を表1の組成から、表2の組成のものに置き換えた以外、試験例2と同様に試験したところ、試験例2と同様の結果が得られた。
工程(1)下記の2溶液を調製した。
A.染料:S−205溶液(3% w/v アセトン溶液)
B.緩衝液(pH5):クエン酸0.5%、クエン酸ナトリウム1%水溶液
1)75倍に水希釈した表2の組成の処理剤に試料を浸漬して加圧処理し(室温で60分間減圧後、1.47MPa{15kgf/cm2}で120分間加圧)、切断した。
2)試験材を充分に乾燥した。(部分的に水分があったりするとムラになる)
3)染料(S−205)溶液(A)を切断面に霧吹きで均一に噴霧した。
4)アセトンを完全に揮発させた(2分放置)。
5)緩衝液(B)を噴霧した(2分放置)。
S−205を2−アニリノ−6−ジブチルアミノ−3−メチルフルオラン(ODB−2)に置き換えた以外、試験例2と同様の試験を実施し、処理剤が浸透した部分が発色したことを確認した。
(試験例6)呈色確認試験6
S−205を6−ジエチルアミノ−3−メチル−2−(3−トルイジノ)フルオラン(ODB−7)に置き換えた以外、試験例2と同様の試験を実施し、処理剤が浸透した部分が発色したことを確認した。
(試験例7)呈色試験確認試験7
S−205を6−ジエチルアミノ−3−メチル−2−(2,4−キシリジノ)−フルオラン(BK−15)に置き換えた以外、試験例2と同様の試験を実施し、処理剤が浸透した部分が発色したことを確認した。
ロイコ染料による注入処理材発色部分と、有効成分の分布状況が一致するかどうか調べた。
1)インサイジングされたベイマツ、ベイツガ、ベイモミのそれぞれの角材(10.5×10.5×40cm)に、表2の製剤の75倍希釈液を試験例4と同様に加圧注入した。
2)それぞれの樹種で、注入量が比較的多い材と、少ない材を選別した。
3)各注入材を約2cm分の厚さ(1cm厚×2枚)で切断し、S−205(3%アセトン溶液)を噴霧・乾燥後、pH5の緩衝液を噴霧し、発色部分を確認した。
4)材の中央部分から、両端の発色状況が似ている箇所を選び、約2cm幅で切り出し、さらに、切り出した材を端から0.5cm間隔で切断した(深さ1.5cm)。
5)切断した両端の同一深さの部分を混合粉砕し(それぞれ計1.4〜2.3g)、40mLのメタノールに1晩浸漬後、メタノール抽出液をエバポレーターで乾固して、2mLのメタノールに溶解し、有効成分検定液とした。
6)HPLCにより、検定液中の有効成分量を測定して、注入材端からの距離と、対理論値薬剤回収率(飽和部分の木材量に対する吸液量比を1.3として算出)との関係をみた。
(結果)
Claims (7)
- 電子受容性物質及び木材保存剤を含有することを特徴とする木材保存剤組成物。
- 上記電子受容性物質が、アニオン系界面活性剤、ノニオン系界面活性剤又は酸性物質の少なくとも一種を含有する、請求項1に記載の木材保存剤組成物。
- 上記木材保存剤が、殺虫剤、及び/又は防腐剤を含有することを特徴とする、請求項1又は2記載の木材保存剤組成物。
- 上記殺虫剤が、ネオニコチノイド系、フェニルピラゾール系、ジベンゾイルヒドラジン系、ピレスロイド系、ピレスロイド様、ネライストキシン系、有機リン系、カーバメート系、バチルス・チューリンゲンシス菌トキシン系、トリアジン系、ナフタリン系、塩素化ジアルキルエーテル添加系、トロポロン系、アルキルアミンアセテート、フタル酸ジアミド系、アンスラニルアミド系、フェニルピロール系、オキサジアジン系、マクロライド系、幼若ホルモン系、キチン合成阻害系、ピリダリル、及びヒドラメチルノンからなる化学物質の群より選択される、請求項3に記載の木材保存剤組成物。
- 上記防腐剤が、トリアゾール誘導体、スルホンアミド系、ベンゾイミダゾール系、チオシアネート系、第4級アンモニウム塩、モルホリン誘導体、フェノール系、有機ヨード系、有機ブロモ誘導体、イソチアゾリン系、ベンゾイソチアゾリン系、ピリジン系、金属塩類、有機スズ誘導体、ジアルキルジチオカルバメート系、ニトリル系、活性ハロゲン原子を含有する微生物剤、ベンゾチアゾール系、キノリン系、ホルムアルデヒドを放出する化合物、ヒドロキシルアミン系、ナフタリン系、アニリド系、ハロアルキルチオ系、ニトリル系、タール系、アルデヒド類、直鎖脂肪酸、芳香族カルボン酸、アルコール類、イソチアゾリン系、及び無機化合物からなる化学物質の群より選択される、請求項3に記載の木材保存剤組成物。
- 請求項1〜5に記載の木材保存剤組成物で処理された木材にロイコ染料を指示薬として用いることによる、処理した対象木材に対して、指示薬を塗布又は噴霧して放置し、塗布又は噴霧面を目視観察し、所定の色に呈色した部分を浸潤部とする、薬剤浸潤度測定方法。
- 上記ロイコ染料が、フタリド系、アザフタリド系、フルオラン系、ジアリールフタリド系、インドリルフタリド系、ビニローグフタリド系、ジアリールメタン系、ローダミンラクタム系、チアジン系、スピロピラン系、フルオレン系、フェノチアジン系、及びロイコオーラミン系からなる群より選択される、請求項6に記載の薬剤浸潤度測定方法。
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JPS63172604A (ja) * | 1987-01-09 | 1988-07-16 | 大日本木材防腐株式会社 | スプレ−用の木材保存剤 |
JPH08197509A (ja) * | 1995-01-23 | 1996-08-06 | Sds Biotech Kk | 木材保存剤組成物及び木材保存剤の浸透性改善方法 |
JPH08509437A (ja) * | 1993-06-21 | 1996-10-08 | バイエル・アクチエンゲゼルシヤフト | 殺菌・殺カビ活性化合物の組合せ |
JPH08291006A (ja) * | 1995-04-19 | 1996-11-05 | Sds Biotech Kk | 木材保存剤組成物及び木材保存剤処理時の木材変色防止方法 |
JP2002307406A (ja) * | 2001-04-11 | 2002-10-23 | Takeda Chem Ind Ltd | 木材保存剤 |
JP2004527451A (ja) * | 2000-04-18 | 2004-09-09 | バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト | フェニル置換4−ヒドロキシテトラヒドロピリドン |
JP2005120097A (ja) * | 2003-09-25 | 2005-05-12 | Syngenta Japan Kk | 乳化安定な殺虫組成物 |
JP2005263813A (ja) * | 2005-06-14 | 2005-09-29 | Japan Enviro Chemicals Ltd | 木材保存剤 |
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JPS63172604A (ja) * | 1987-01-09 | 1988-07-16 | 大日本木材防腐株式会社 | スプレ−用の木材保存剤 |
JPH08509437A (ja) * | 1993-06-21 | 1996-10-08 | バイエル・アクチエンゲゼルシヤフト | 殺菌・殺カビ活性化合物の組合せ |
JPH08197509A (ja) * | 1995-01-23 | 1996-08-06 | Sds Biotech Kk | 木材保存剤組成物及び木材保存剤の浸透性改善方法 |
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JP2002307406A (ja) * | 2001-04-11 | 2002-10-23 | Takeda Chem Ind Ltd | 木材保存剤 |
JP2005120097A (ja) * | 2003-09-25 | 2005-05-12 | Syngenta Japan Kk | 乳化安定な殺虫組成物 |
JP2005263813A (ja) * | 2005-06-14 | 2005-09-29 | Japan Enviro Chemicals Ltd | 木材保存剤 |
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