JP4177719B2 - Anti-ant composition - Google Patents
Anti-ant composition Download PDFInfo
- Publication number
- JP4177719B2 JP4177719B2 JP2003179339A JP2003179339A JP4177719B2 JP 4177719 B2 JP4177719 B2 JP 4177719B2 JP 2003179339 A JP2003179339 A JP 2003179339A JP 2003179339 A JP2003179339 A JP 2003179339A JP 4177719 B2 JP4177719 B2 JP 4177719B2
- Authority
- JP
- Japan
- Prior art keywords
- ant
- polymer
- composition
- note
- charcoal
- 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.)
- Expired - Lifetime
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Description
【0001】
【発明の属する技術分野】
本発明はホウ酸系防蟻用組成物に関する。さらに詳しくは、白蟻の予防もしくは駆除効果に優れ、その効力の持続性に優れ、しかも、木材腐食性にも優れたホウ酸系防蟻用組成物に関する。
【0002】
【従来の技術】
従来、白蟻の予防もしくは駆除(以下、防蟻という。)を目的とした防蟻剤として、例えば、CCA系薬剤(クロム・銅・ヒ素の化合物)、クロルピリホス等の有機リン系薬剤等が知られている。しかしながら、CCA系薬剤は焼却の際の毒物発生による環境汚染の問題があり、有機リン系薬剤は毒性が強く、健康被害の発生も報告されており、(社)日本しろあり対策協会は2001年4月よりクロルピリホスの製造・使用を段階的に中止している。
【0003】
このような状況下、いまだに農薬系の薬剤を主成分とした防蟻用組成物が主に出回っており、シックハウス症候群等の原因となっている。消費者は、安全性の高い建材を要求するようになっており、工務店もその対応に苦慮している。
【0004】
天然の防蟻剤として、ヒバ精油、月桃等があるが、防蟻効果の持続性が弱く、また高価である。木酢液も白蟻に忌避行動を起こさせる点で有用であるが、独特のにおいが強く、床下材への使用は不向きである。また、クレオソート油も防腐・防蟻剤として使われているが、強い刺激性の臭いがあり、住宅用には向いていないばかりでなく、クレオソートが給排水に使用する塩化ビニル樹脂管を侵すということが最近分かってきた。
【0005】
このように、最近、木造家屋や他の建物、構築物等における木材を加害する白蟻に対し、その予防もしくは駆除対策(防除対策)が高まりつつある中で、安全性の高い、効力の強い防蟻用組成物の開発が望まれている。
【0006】
毒性が低く安全である薬剤としてホウ酸またはその塩(以下、ホウ酸類ともいう。)があるが、安定に配合できる濃度が低く高い効力が得られない上に、これらを配合した防蟻用組成物は水に容易に溶け、例えば長時間雨等にさらされるとホウ酸類が流出してしまい、効力がなくなってしまうという欠点がある。日本では、ホウ酸類は処理木材から溶脱する危険性があるため、木材保存剤として現在認められていない。
【0007】
また、従来の防蟻用組成物は、白蟻以外を原因とする木材の腐食からの防御という点では必ずしも充分に配慮されたものではない。
【0008】
【発明が解決しようとする課題】
本発明は上記事情に鑑みてなされたもので、その目的は、安全性の高いホウ酸類を配合した防蟻用組成物の上記欠点を改善して、防蟻効果に優れ、しかもその効果が長期にわたって持続し、さらに木材の菌等蟻以外による腐食耐久性にも優れたホウ酸類配合の防蟻用組成物を提供することにある。
【0009】
【課題を解決するための手段】
本発明者らは上記課題を解決するために鋭意研究を行った結果、ホウ酸類を含有した防蟻用組成物の中に、炭粉末と特定の高分子化合物を配合することにより上記課題が解決されることを見出し、本発明を完成するに至った。
【0010】
すなわち、本発明は、植物由来の炭粉末と、被膜形成性ポリマーエマルジョン、水溶性多糖類及びポリアミド樹脂からなる群から選ばれた1種又は2種以上と、ホウ酸類とを含有することを特徴とする防蟻用組成物である。
【0011】
本発明において、前記炭は、白炭又は白炭と黒炭の混合物であることが好ましい。
【0012】
また、前記被膜形成性ポリマーは、アクリル系ポリマー又は酢酸ビニル系ポリマーが、水溶性多糖類は、でんぷん又はセルロースエーテルが、ポリアミド樹脂は、非晶性でエタノール可溶性のポリアミドがそれぞれ好ましい。なお、前記セルロースエーテルは、メチルセルロース又はヒドロキシプロピルメチルセルロースが好ましい。
【0013】
本発明においては、前記防蟻用組成物に、さらに、シリカを配合すると防蟻効果の持続性をさらに向上させることができる。
【0014】
本発明においては、植物由来の炭粉末を主成分とした被膜形成性ポリマー、水溶性多糖類及びポリアミド樹脂含有組成物がホウ酸類を保持して木材等の表面に塗膜を形成する。そして、本発明防蟻用組成物の実使用下においては、該塗膜が白蟻の木材への侵入を防ぐとともに、白蟻は塗膜中の食毒性防蟻剤であるホウ酸類を食べ、木材等を食害する前に死んでしまう。したがって、木材等を食害されることがなく防蟻効果が有効に発揮される。
【0015】
前記塗膜は、木材上において炭粉末及び各種ポリマーの相乗的機能によって、例えば、ホウ酸類を強固に吸着保持し、さらに、木材等の塗布対象物への優れた付着性を発揮し、優れた撥水性と接着性により木材から流出されることなく、長期にわたってホウ酸類の防蟻効果を持続させることができる。
【0016】
また、前記塗膜の優れた耐水性により木材への水の侵入を阻止し、塗膜の防菌性、通気性とあいまって木材は長期に渡って腐食することがない。
【0017】
なお、本発明における防蟻用組成物の防蟻とは、白蟻の予防もしくは駆除を含む概念である。また、防蟻効果を有する薬剤、すなわち防蟻用薬剤を防蟻剤といい、この防蟻剤を含んだ組成物を防蟻用組成物という。したがって、本発明における防蟻用組成物は、現在防蟻用薬剤を配合して防蟻剤として販売されている商品を含む概念である。
【0018】
また、本発明における被膜形成性ポリマーとは、水に不溶性のポリマーであって、該ポリマーが水に分散されたポリマーエマルジョンを基材に塗布した後、乾燥して分散媒である水を揮散させたときに、基材上に被膜を形成する性質をもったポリマーである。
【0019】
なお、ポリマーエマルジョンとは、水に不溶性のポリマーが水に分散されたものであり、このようなポリマーの水分散系を一般にポリマーエマルジョンと称しているので、本発明においても、ポリマーエマルジョンという用語を用いる。したがって、被膜形成性ポリマーエマルジョンとは、水に不溶性の被膜形成性ポリマーが水に分散されている分散系である。
【0020】
【発明の実施の形態】
以下、本発明の実施形態について詳述する。
【0021】
本発明の防蟻用組成物は、植物由来の炭粉末を含有する。
【0022】
本発明において用いられる植物由来の炭(以下、単に炭ともいう。)としては、特に限定されず、例えば植物を空気を遮断して、加熱・乾留する一般の方法で得られる炭を用いることができる。炭の原料となる植物としては、カシ、ナラ、クヌギ、赤松、ゴムの木、マングローブ等の木、ヤシ、椿油のしぼり粕(殻)等の実、竹、わら等が挙げられるが、これらに限定されるものではない。入手のし易さからは前記木が好ましい。
【0023】
炭は製造方法(焼成温度)の相違により白炭及び黒炭等に大別される。白炭は、1000℃以上の高温で焼き、窯から掻き出した炭に適量の水に灰と土を混合した「スバイ」をかけて急冷することにより製造したものである。白炭の代表としてウバメガシ(姥目樫)や竹等から得られる備長炭がある。一方、黒炭はナラ、クヌギ、赤松、竹等を400〜700℃で焼き、自然に冷却して窯から取り出したものである。
【0024】
本発明においては、白炭、黒炭等いずれをも用いることができるが、特に、効果の点から白炭単独か、又は白炭と黒炭を混合して用いることが好ましい。白炭と黒炭の配合比は目的に応じて任意に設定することができる。本発明では、炭の中から1種又は2種以上が任意に選択されて用いることができる。
【0025】
炭粉末は、炭を粉砕等により粉末化することにより得られる。炭粉末の粒子径は使用形態によって異なり限定しにくいが、メディアン径で2〜300μmのものが好ましい。特に、防蟻用組成物が水分散液の形態である場合には、メディアン径で2〜200μmのものが好ましく、さらに好ましくは5〜100μmである。また、使用形態がエアゾールのような噴霧タイプの場合は、メディアン径で2〜11μmであることが好ましい。なお、以下において、粒子径は特に断りのない限り全てメディアン径である。
【0026】
炭粉末の含有量は、防蟻用組成物全量中1〜40質量%が好ましい。含有量が1質量%未満では塗膜の炭の機能が充分でなくなってくる傾向にあり、また、40質量%を越えて配合すると、塗布対象物への付着性が充分でなくなってくる傾向がある。特に好ましい含有量は10〜30質量%である。
【0027】
本発明の防蟻用組成物は、さらに被膜形成性ポリマーエマルジョン、水溶性多糖類及びポリアミド樹脂からなる群から選ばれた1種又は2種以上を含有する。
【0028】
本発明における被膜形成性ポリマーエマルジョンについて詳述する。本発明におけるポリマーエマルジョンは、水に不溶性のポリマーが水に分散されているものであれば特に制限されないが、重合性モノマーを乳化重合して得られるポリマーエマルジョンが好ましいが、これに限定されるものではない。なお、乳化重合は一般的な公知の方法で行われる。
【0029】
本発明における被膜形成性ポリマーエマルジョンに分散されているポリマーは被膜形成性のポリマーであり、例えばアクリル酸エステル、メタクリル酸エステル等のアクリル酸エステル系モノマー、酢酸ビニル等のモノマーを少なくとも含む重合物(ポリマー)が好適な例として挙げられる。なお、前記アクリル酸エステル系モノマー中のアクリル酸エステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸ヘキシル、アクリル酸オクチル、アクリル酸2−エチルヘキシル等が挙げられ、メタクリル酸エステルとしては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタクリル酸オクチル、メタクリル酸2−エチルヘキシル等が挙げられる。
【0030】
例えば、アクリル酸エステル系モノマーを少なくとも含む重合物、すなわちアクリル系ポリマーとしては、前記アクリル酸エステル系モノマーからなるポリマーでも、他モノマーとのコポリマーでも構わない。前記他モノマーとしては、共重合できるモノマーであれば特に限定されないが、アクリル酸、メタクリル酸、酢酸ビニル、スチレン、エチレン、プロピレン等のオレフィン等が挙げられる。前記アクリル系ポリマーの中では、アクリル酸エステル及び/又はメタクリル酸エステルを主成分とするポリマーが好ましい。特に、アクリル酸エチル及び/又はメタクリル酸エチルを主成分とするポリマーが好ましい。なお、前記アクリル系ポリマーは、いずれも水不溶性のものから選ばれる。
【0031】
また、酢酸ビニルを少なくとも含む重合物、すなわち酢酸ビニル系ポリマーとしては、酢酸ビニルのホモポリマーでも、他モノマーとのコポリマーでも構わない。前記他モノマーとしては、共重合できるモノマーであれば特に限定されないが、前記アクリル酸エステル系モノマー、アクリル酸、メタクリル酸、スチレン、エチレン、プロピレン等のオレフィン等が挙げられる。酢酸ビニル系ポリマーの中では、特に酢酸ビニルホモポリマーが好ましい。なお、前記酢酸ビニル系ポリマーは、いずれも水不溶性のものから選ばれる。
【0032】
また、本発明の被膜形成性ポリマーエマルジョンには、ポリマーエマルジョンに一般的に配合されている塗膜を形成したときのポリマーの被膜を改善するための可塑剤や造膜助剤が配合されても構わない。
【0033】
本発明の被膜形成性ポリマーエマルジョンは、市販品を用いることが可能であり、市販品の例としては、例えばアクリル系ポリマーエマルジョンである、ダイトゾール5000AD、同5000SJ(以上、大東化成工業社製)、酢酸ビニル系ポリマーエマルジョンである、アイカNEWアイボンA−1410シリーズ(アイカ工業社製)等が挙げられる。なお、酢酸ビニル系ポリマーエマルジョンには、乳化重合の際のポリマーの分散安定化のためにポリビニルアルコールが含まれるケースがある。
【0034】
市販品をはじめとするポリマーエマルジョンは、一般に保存安定性、使いやすさ等からポリマー濃度が30〜60質量%にされているが、本発明の防蟻用組成物への配合に当たっては、これらのポリマーエマルジョンをそのまま配合しても、任意に希釈した後に配合しても構わない。いずれにしても、防蟻用組成物中にポリマー分散物が存在すればよい。
【0035】
次に、水溶性多糖類について詳述する。
【0036】
本発明に用いられる水溶性多糖類としては、特に制限されないが、例えば、でんぷん、水溶性セルロース系ポリマー等が好ましい例として挙げられる。このうち、水溶性セルロース系ポリマーとしては、セルロースエーテルが好ましく、例えば、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、カルボキシメチルセルロース等の他、セルロースのメチル及びヒドロキシプロピルの混合エーテル(以下、ヒドロキシプロピルメチルセルロースともいう。以下混合エーテルは全てこの形で表す。)、ヒドロキシエチルメチルセルロース等のように複数の置換基がついたセルロース等が挙げられる。水溶性セルロース系ポリマーの中では、メチルセルロース、ヒドロキシプロピルメチルセルロースが好ましい。
【0037】
水溶性セルロース系ポリマーは、市販品を用いることが可能であり、市販品の例としては、例えばメチルセルロースであるメトローズSM−15、同−25、同−100、同−400、同−1500、同−4000、同−8000(以上、信越化学工業社製)、ヒドロキシプロピルメチルセルロースであるメトローズ60SH−50、同−4000、同−10000、同65SH−50、同−400、同−1500、同−4000、同−15000、同90SH−04、同−100、同−400、同−4000、同−15000(以上、信越化学工業社製)等が挙げられる。
【0038】
次に、ポリアミド樹脂について詳述する。
【0039】
本発明におけるポリアミド樹脂は、二塩基酸とジアミンの重縮合物、ω−アミノ酸の重縮合物、カプロラクタムの重合物のいずれでも構わない。具体的には、6,6−ナイロン、6,10−ナイロン、6−ナイロン、12−ナイロン等が挙げられる。本発明にいてはポリアミド樹脂が、結晶性を弱めた非晶性でアルコールに溶解するものが好ましく、エタノールに可溶性のものが特に好ましい。ポリアミド樹脂は共重合体、特に分子構造の大きなモノマーを組み入れることによって結晶性を弱めることができる。したがって、本発明では上記共ポリアミド(あるいは共重合ナイロンともいう。)を用いることが好ましい。好ましい共ポリアミドの例としては、ε−カプロラクタムとヘキサメチレンジアミンとアジピン酸とセバシン酸との共ポリアミド(6−ナイロン、6,6−ナイロン、6,10−ナイロン共ポリアミド)、ε−カプロラクタムとヘキサメチレンジアミンとアジピン酸とセバシン酸とε−ラウロラクタムとω−アミノドデカン酸との共ポリアミド(6−ナイロン、6,6−ナイロン、6,10−ナイロン、12−ナイロン共ポリアミド)、ε−カプロラクタムとヘキサメチレンジアミンとアジピン酸とε−ラウロラクタムとω−アミノドデカン酸との共ポリアミド(6−ナイロン、6,6−ナイロン、12−ナイロン共ポリアミド)等が挙げられる。
【0040】
また、ポリアミド樹脂のアミド基の水素をメトキシメチル基で置換したN−メトキシメチル化ポリアミド樹脂も結晶性が弱められたポリアミド樹脂であり、本発明においては好ましく用いることができる。
【0041】
ポリアミド樹脂は、単独で使用してもよいが、ポリアクリル酸エステル、ポリ酢酸ビニル等と混合することにより基材への付着性を向上させることができる。また、ポリアクリル酸、ポリメタクリル酸等の配合により水溶性にすることもできる。水溶性のポリアミド樹脂は、アーテック工房株式会社製の水溶性ポリアミド樹脂を用いることもできる。
【0042】
さらに、市販品としては、例えば、CM−8000(東レ株式会社製の共ポリアミド;低融点型、6−ナイロン、12−ナイロン、6,6−ナイロン、6,10−ナイロンとを含有)、CM−4000(東レ株式会社製の共ポリアミド;高融点型、6−ナイロン、6,6−ナイロン、6,10−ナイロンとを含有)、EF−30T(帝国化学産業株式会社製のN−メトキシメチル化ポリアミド樹脂)、F−30K(帝国化学産業株式会社製のN−メトキシメチル化ポリアミド樹脂)が挙げられ、これらを用いることもできる。
【0043】
被膜形成性ポリマーエマルジョン、水溶性多糖類及びポリアミド樹脂の含有量は、これらからなる群から選ばれた1種又は2種以上の含有量として、防蟻用組成物全量中0.5〜30質量%が好ましい。さらに好ましくは5〜20質量%である。なお、被膜形成性ポリマーエマルジョンの場合は、ポリマー分としての含有量である。
【0044】
また、ポリマーエマルジョンとして存在する被膜形成性ポリマー、水溶性多糖類及びポリアミド樹脂からなる群から選ばれた1種又は2種以上は、防蟻用組成物中に炭粉末に対して1質量%〜4質量倍の範囲で配合することが好ましい。さらに好ましくは10質量%〜2質量倍である。特に、25〜100質量%が好ましい。
【0045】
次に、本発明に配合されるホウ酸類は、前記のとおりホウ酸又はホウ酸塩であり、防蟻効果のある水溶性のものであれば特に限定されない。ホウ酸塩としては、ホウ酸アルカリ金属塩、特にホウ酸ナトリウムが好ましい。ホウ酸類の含有量は防蟻用組成物中1〜40質量%が好ましく、さらに好ましくは3〜30質量%である。
【0046】
ホウ酸類の配合に際しては、ホウ酸類の溶媒として水が配合されるが、水とともに多価アルコールを配合することが好ましい。多価アルコールとしては、ソルビット、エリスリトール、キシリット、マルチトール、グリセリン、1,3−ブチレングリコール、プロピレングリコール、ジプロピレングリコール、ジグリセリン等が挙げられる。
【0047】
本発明の防蟻用組成物には、必要に応じて、本発明の効果を損なわない範囲で上記した成分以外の他の成分を適宜配合することができる。適宜配合成分としては、例えば、粉末、顔料、上記以外の水溶性高分子、増粘剤、ホウ酸類以外の他の防蟻剤、有機溶剤、界面活性剤、金属イオン封鎖剤、酸化防止剤、香料、分散剤、粘度調整剤、消泡剤等が挙げられる。
【0048】
粉末としては、例えば、シリカ、ケイ酸ナトリウム、酸化亜鉛、ベントナイト、アルミナ、酸化チタン、酸化マグネシウム等が挙げられる。
【0049】
これらの中で、シリカを配合すると、防蟻効果の持続性をさらに向上させることができる。シリカの中でも多孔質のシリカであると、ホウ酸類の対象物への吸着性や、塗膜の通気性が優れたものとなるので、特に好ましい。配合する場合の。シリカの配合量は防蟻用組成物中1〜30質量%が効果的であり、さらに好ましくは5〜15質量%である。
【0050】
有機溶剤としては、メタノール、エタノール、n−プロパノール、i−プロパノール、n−ブタノール、i−ブタノール、ベンジルアルコール、アセトン等が挙げられる。これらの中、メタノール、エタノール、プロパノール等の炭素数1〜3の脂肪族1価アルコールが好ましく、特にエタノールが好ましい。有機溶剤の配合により、対象物への付着性を向上させることができる。
【0051】
また、塗膜の乾燥速度を調節する助有機溶剤として一分子中に1〜2個のエーテル結合を有する一価アルコールであって、適度な揮発性を有するもの、例えばメチルセロソルブ、エチルセロソルブ、プロピルセロソルブ(ノルマル、イソ、第二又は三級)、ブチルセロソルブ、メチルカルビトール、エチルカルビトール、ジエチレングリコールモノメチルエーテル等を用いることができる。
【0052】
水溶性高分子としては、カラギーナン、アラビアガム、キサンタンガム、カードラン、サクシノグルカン、キチン、キトサン、寒天、ポリビニルアルコール、ポリビニルピロリドン、カルボキシビニルポリマー、ポリアクリル酸ナトリウム、ポリエチレングリコール等が挙げられる。
【0053】
界面活性剤としては、例えば、脂肪酸セッケン(ラウリン酸ナトリウム、パルミチン酸ナトリウム等)、ラウリル硫酸カリウム、アルキル硫酸トリエタノールアミンエーテル、アシルメチルタウリン塩等のアニオン界面活性剤;塩化ステアリルトリメチルアンモニウム、塩化ベンザルコニウム、ラウリルアミンオキサイド等のカチオン界面活性剤;イミダゾリン系両性界面活性剤(2−ココイル−2−イミダゾリニウムヒドロキサイド−1−カルボキシエチロキシ2ナトリウム塩等)、ベタイン系界面活性剤(アルキルベタイン、アミドベタイン、スルホベタイン等)等の両性界面活性剤;
【0054】
ソルビタン脂肪酸エステル類(ソルビタンモノステアレート、セスキオレイン酸ソルビタン等)、グリセリン脂肪酸類(モノステアリン酸グリセリン等)、プロピレングリコール脂肪酸エステル類(モノステアリン酸プロピレングリコール等)、硬化ヒマシ油誘導体、グリセリンアルキルエーテル、POEソルビタン脂肪酸エステル類(POEソルビタンモノオレエート、モノステアリン酸ポリオキエチレンソルビタン等)、POEソルビット脂肪酸エステル類(POE−ソルビットモノラウレート等)、POEグリセリン脂肪酸エステル類(POE−グリセリンモノイソステアレート等)、POE脂肪酸エステル類(ポリエチレングリコールモノオレート、POEジステアレート等)、POEアルキルエーテル類(POE2−オクチルドデシルエーテル等)、POEアルキルフェニルエーテル類(POEノニルフェニルエーテル等)、プルロニック型類、POE・POPアルキルエーテル類(POE・POP2−デシルテトラデシルエーテル等)、テトロニック類、POEヒマシ油・硬化ヒマシ油誘導体(POEヒマシ油、POE硬化ヒマシ油等)等の非イオン界面活性剤等が挙げられる。
【0055】
防蟻用組成物の形態としては、炭粉末、被膜形成性ポリマー等が水その他の溶媒に分散された水分散系である。また、本発明の防蟻用組成物はエアゾールの原液として使用され、噴霧タイプの使用形態が可能である。したがって、本発明の防蟻用組成物を使用するに当たっては、一般に塗布または噴霧される。例えば、木材面に塗布し(噴霧、刷毛塗り、ローラー塗り等による)、次いで自然条件下で乾燥することにより、所望の防蟻効力を有する塗膜状の防蟻用組成物が木材上に形成される。
【0056】
【実施例】
以下実施例を挙げて本発明を具体的に説明する。配合量は特に断りのない限り質量%である。実施例の説明に先立ち本発明で用いた効果試験方法について説明する。
【0057】
[防蟻効果]
(社)日本木材保存協会規格 第11号 1992 「塗布・吹付け・浸せき処理用木材防蟻剤の防蟻効力試験方法」(1)室内試験方法 4.3総合試験に準じて行った。以下、上記試験法のポイントを具体的に記載する。
【0058】
(試験方法)
(1)供試木材片
(イ)試験に供する木材片は、アカマツの辺材(20(L)×10(R)×10(T)mm)の直方体とする。
(ロ)木材片は温度60℃の恒温器中で24時間乾燥する。
【0059】
(2)試験体
(イ)試験体は木材片を試料で処理した処理試験体と、試料処理をしない無処理試験体の2種類とする。さらに処理試験体は試料処理をした後(2)・(ニ)に規定する耐候操作を行ったものと、行わないものとに分ける。
(ロ)試験体の数は耐候操作を行った処理試験体、耐候操作を行わない処理試験体および無処理試験体についてそれぞれ5個とする。
(ハ)木材片に刷毛を用いて試料を110g/m2の割合で塗布した後、室温で20日間以上放置した後、耐候操作を行うもの5個と行わないもの5個の2グループに分ける。
(ニ)耐候操作は湿潤操作と揮散操作を交互に10回繰り返す。
湿潤操作:耐候操作を行う試料処理木材片をまとめて室温で静水に30秒浸せきした後、底部に水をはったデシケータ中に入れ、温度26℃の恒温室に4時間放置する。
揮散操作:湿潤操作を終わった試料処理木材片は、ただちに温度40℃の循環式熱風恒温器中に20時間放置する。
(ホ)耐候操作を行った試料処理木材片、耐候操作を行わない試料処理木材片および無処理木材片は、温度60℃で48時間乾燥し、約30分間デシケータ中に放置した後、その質量(W1)を0.01gまではかり、試験体とする。
【0060】
(3)飼育容器
飼育容器としては直径8cm、長さ6cmのアクリル樹脂製円筒の一部に硬石こうを厚さ約5mmに固めたものを用い、これをあらかじめ約2cmの厚さに湿潤綿を敷きつめた蓋付き容器中に10〜15個置く。湿潤綿は、湿潤綿100gに水130〜150mlを加える。蓋には通気のため小孔をあけておく。
【0061】
(4)飼育
(イ)前項で調製された飼育容器中の硬石こうの上に、試験体のマサ目面を上下にして、処理試験体あるいは無処理試験体を1個づつ水平におき、無作為に巣から取り出した職蟻150頭と兵蟻15頭を投入する。
(ロ)蓋付き容器は、温度28℃の暗所に21日間静置して飼育する。
【0062】
(試験結果)
(1)21日間経過したら試験体を飼育容器より取り出し、試験体表面の付着物をていねいに取り除き、温度60℃で48時間乾燥し、約30分間デシケータ中に放置した後0.01gまで秤量して質量(W2)を求める。
(2)シロアリの職蟻の死亡頭数を記録する。
【0063】
(結果の表示)
(1)次式により試験体の質量減少率を算出し、無処理試験体については5個の平均質量減少率を求める。
質量減少率(%)=[(W1−W2)/W1]×100
(2)次式により死虫率を算出し、平均死虫率を求める。
死虫率(%)=[死虫数/150]×100
【0064】
[付着性]
試料を刷毛で木材にほぼ一定量塗布し、乾燥後、手で擦り、擦りに対しての評価を、下記評価基準に基づいて行った。
(評価基準)
○:木材の塗膜が剥がれ落ちなかった。
△:木材の塗膜がやや剥がれ落ちた。
×:木材の塗膜が剥がれ落ちた。
【0065】
[木材腐食耐久性]
(社)日本木材保存協会規格 第1号 1992 「塗布・吹付け・浸せき処理用木材防腐剤の防腐効力試験方法」に準じて行った。以下、上記試験法のポイントを具体的に記載する。
【0066】
(1)木材片
木材片は、スギ、ブナの辺材よりとる(厚さ5mm、幅20mm、長さ40mmで、40×20mmの面がまさ目面のものとする。)。木口面は常温硬化型のエポキシ樹脂でシールする。
【0067】
(2)樹種と供試菌の組み合わせ
樹種別に菌種をきめて抗菌操作を行う。その組合せは次のとおりとする。
スギ…オオウズラタケ
ブナ…カワラタケ
【0068】
(3)試験体
試験体は、処理試験体と無処理試験体の2種類とする。
(イ)処理試験体
処理試験体は、木材片を試料を用いて、塗布・吹付けまたは浸せき処理したもので、試料の吸収量は110g/m2とする。なお、浸せき処理にあっては、処理後木材片の表面をろ紙で軽くぬぐう。
【0069】
(ロ)試料吸収量
木材片の個々の試料吸収量は、次の式によって算出する。
試料吸収量(g/m2)=(W1−W2)/A
W1:試料吸収後の木材片の質量(g)
W2:試料吸収前の木材片の質量(g)
A:木材片の面木口面を除いた表面積(m2)
【0070】
(ハ)試験体の所要個数
試験に用いる試験体の所要個数は、表1のとおりとする。
【0071】
【表1】
【0072】
(4)試験
試験は前記(3)(イ)において調製された試験体を20日間風乾した後耐候操作を行い、耐候操作を終わった後抗菌操作を行う。
(イ)耐候操作
耐候操作は、溶脱と揮散の操作を交互に30回繰り返す。
(a)溶脱操作は、同一処理のものをまとめ、相互に接触しないようにして、25℃の静水に5時間浸せきして溶脱分を溶脱させる。水と試験体の容積比は10:1とし、操作の繰り返しごとに新しい水にとりかえる。
(b)揮散操作は、溶脱操作を終わった試験体を、軽く水切りをした後、ただちに温度40℃の循環式乾燥器中に19時間放置して、揮散させる。
(c)耐候操作を終わった試験体は、60℃で48時間循環式乾燥器で乾燥した後、約30分間デシケータ中に放置してその質量(W3)を0.01gまで量る。
【0073】
(ロ)抗菌操作
耐候操作を終わった試験体について抗菌操作を行う。
(a)処理試験体及び無処理試験体は、別々に1培養びんごとに3個ずつテフロン(登録商標)板枠にはめ、殺菌したのち、40×5mmの面が下になるように供試菌の菌そうにのせ、温度26℃、関係湿度70%以上のところに8週間おく。
(b)8週間を経過したのち試験体をとり出し、表面の菌糸その他の付着物をていねいに取り除き、約24時間風乾した後、温度60℃で48時間循環式乾燥器で乾燥し、約30分間デシケータ中に放置した後その質量(W4)を0.01gまで量る。
【0074】
(5)試験結果
試験結果は、抗菌操作を行った処理試験体の抗菌操作による平均質量減少率で表す。
(イ)質量減少率
個々の試験体の質量減少率は次の式によって算出し、その平均値を求める。
質量減少率(%)=[(W3−W4)/W3]×100
【0075】
(実施例1〜5)
表2に示す処方の防蟻用組成物を以下の方法で調製した。A容器にアクリル系ポリマーエマルジョン、酢酸ビニル系ポリマーエマルジョン、でんぷん、メチルセルロース、ポリアミド樹脂のいずれかと、界面活性剤と、エタノールと、酸化亜鉛と、多孔質シリカとを混入して撹拌し、静置した(A容器)。また、B容器にホウ酸ナトリウム、ソルビット、水を混入して撹拌し、静置した(B容器)。翌日前記A容器に木炭粉末を静かに入れ、ゆっくりと木炭粉末を沈殿させておき、すべて沈殿した後撹拌した。次いで、A容器とB容器とを混ぜ、さらにヒノキチオールを入れ、よく撹拌した。
【0076】
【表2】
【0077】
表2中、
(注1)白炭(ウバメガシ;備長炭)、粒子径;24μm
(注2)ダイトゾール5000AD(50質量%ポリマー濃度)
(注3)40質量%ポリマー濃度
(注4)メトローズSM−8000
(注5)CM8000
(注6)イオネットRAP−400(三洋化成工業株式会社製)
【0078】
上記実施例1〜5の防蟻効果評価結果を表3に示す。
【0079】
【表3】
【0080】
(注)表3中、実施例1〜5の上段は耐候操作ありの場合、また下段は耐候操作なしの場合のデータを示す。なお、無処理試験体は耐候操作なしの場合のデータである。
【0081】
表3から明らかなように、木炭粉末と、アクリル系ポリマーエマルジョン、酢酸ビニル系ポリマーエマルジョン、でんぷん、メチルセルロースまたはポリアミド樹脂とを配合した実施例1〜5のホウ酸系防蟻用組成物は、いずれも優れた防蟻効果を発揮し、その持続性も優れていることが分かる。
【0082】
上記実施例1〜5の付着性評価結果を表4に示す。
【0083】
【表4】
【0084】
表4から分かるように、木炭粉末と、アクリル系ポリマーエマルジョン、酢酸ビニル系ポリマーエマルジョン、でんぷん、メチルセルロースまたはポリアミド樹脂とを配合した実施例1〜5のホウ酸系防蟻用組成物は、いずれも炭粉末を含有しているにも係わらず剥がれ落ちることがなく、優れた付着性を示した。
【0085】
上記実施例1〜5の木材腐食耐久性評価結果(質量減少率)を表5に示す。
【0086】
【表5】
【0087】
表5から明らかなように、木炭粉末と、アクリル系ポリマーエマルジョン、酢酸ビニル系ポリマーエマルジョン、でんぷん、メチルセルロースまたはポリアミド樹脂とを配合した実施例1〜5のホウ酸系防蟻用組成物は、いずれも優れた木材腐食耐久効果を発揮することが分かる。
【0088】
以下、さらに本発明防蟻用組成物の実施例を示す。なお、製造は実施例1〜5の方法に準じて行った。また、上記の効果試験をこれらにおいて行ったところ、いずれも優れた効果が得られた。
【0089】
【0090】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)メトローズ60SH−10000(信越化学工業株式会社製)
(注3)イオネットRAP−400(三洋化成工業株式会社製)
【0091】
【0092】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)ダイトゾール5000SJ(50質量%ポリマー濃度)
(注3)メトローズ60SH−10000(信越化学工業株式会社製)
(注4)メトローズSM−8000(信越化学工業株式会社製)
(注5)イオネットLEC(三洋化成工業株式会社製)
【0093】
【0094】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)メトローズ60SH−10000(信越化学工業株式会社製)
(注3)メトローズ65SH−15000(信越化学工業株式会社製)
(注4)メトローズ90SH−4000(信越化学工業株式会社製)
(注5)イオネットRAP−400(三洋化成工業株式会社製)
【0095】
【0096】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)メトローズ60SH−10000(信越化学工業株式会社製)
【0097】
【0098】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)40質量%ポリマー濃度
(注3)メトローズ60SH−10000(信越化学工業株式会社製)
【0099】
【0100】
(エアゾール)
原液 40.0(容量%)
噴射剤(ジメチルエーテル) 60.0(容量%)
【0101】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)メトローズ60SH−10000(信越化学工業株式会社製)
(注3)イオネットRAP−400(三洋化成工業株式会社製)
【0102】
【0103】
(エアゾール)
原液 50.0(容量%)
噴射剤(ジメチルエーテル) 50.0(容量%)
【0104】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)メトローズ60SH−10000(信越化学工業株式会社製)
【0105】
【0106】
(エアゾール)
原液 40.0(容量%)
噴射剤(ジメチルエーテル) 60.0(容量%)
【0107】
(注1)ダイトゾール5000SJ(50質量%ポリマー濃度)
(注2)メトローズ60SH−10000(信越化学工業株式会社製)
【0108】
【0109】
(注1)メトローズ60SH−10000(信越化学工業株式会社製)
(注2)イオネットRAP−400(三洋化成工業株式会社製)
【0110】
【0111】
(注1)メトローズ60SH−10000(信越化学工業株式会社製)
(注2)メトローズSM−8000(信越化学工業株式会社製)
(注3)イオネットLEC(三洋化成工業株式会社製)
【0112】
【0113】
(注1)メトローズ60SH−10000(信越化学工業株式会社製)
(注2)メトローズ65SH−15000(信越化学工業株式会社製)
(注3)メトローズ90SH−4000(信越化学工業株式会社製)
(注4)メトローズSM−4000(信越化学工業株式会社製)
(注5)イオネットRAP−400(三洋化成工業株式会社製)
【0114】
【0115】
(注1)メトローズSM−8000(信越化学工業株式会社製)
(注2)イオネットLEC(三洋化成工業株式会社製)
【0116】
【0117】
(注1)イオネットRAP−400(三洋化成工業株式会社製)
【0118】
【0119】
(注1)CM−8000
(注2)F30K
【0120】
【0121】
(注1)CM−4000
【0122】
【0123】
(注1)CM−8000
【0124】
【0125】
(注1)ダイトゾール5000AD(50質量%ポリマー濃度)
(注2)イオネットRAP−400(三洋化成工業株式会社製)
【0126】
【発明の効果】
以上、詳述したように本発明によれば、安全性の高いホウ酸類を植物由来の炭粉末と被膜形成性ポリマーエマルジョン、水溶性多糖類及びポリアミド樹脂からなる群から選ばれた1種又は2種以上とともに配合して防蟻用組成物を調製したので、従来ホウ酸類配合の防蟻用組成物有していた欠点を改善して、白蟻の予防もしくは駆除効果に優れ、しかもその効果が長期にわたって持続し、さらに蟻以外の菌等に対しても耐久性に優れた、安全な防蟻用組成物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a boric acid type ant composition. More specifically, the present invention relates to a boric acid type ant preventive composition that is excellent in preventing or extermination of white ants, has excellent durability, and is also excellent in wood corrosiveness.
[0002]
[Prior art]
Conventionally, for example, CCA chemicals (chromium / copper / arsenic compounds), organophosphorus chemicals such as chlorpyrifos, etc. are known as ant control agents for the purpose of prevention or extermination of white ants (hereinafter referred to as anti-ants). ing. However, CCA drugs have environmental pollution problems due to the generation of toxic substances during incineration. Organophosphorus drugs are highly toxic and have been reported to cause health damage. The production and use of chlorpyrifos has been phased out since the month.
[0003]
Under such circumstances, ant-proofing compositions mainly composed of agricultural chemicals are still on the market, causing sick house syndrome and the like. Consumers are demanding highly safe building materials, and construction companies are struggling to deal with it.
[0004]
Natural ant repellents include Hiba essential oil, moon peach, etc., but their ant preventive effect is weak and expensive. Wood vinegar is also useful in causing white ants to avoid repelling, but it has a unique smell and is unsuitable for use under flooring. Creosote oil is also used as an antiseptic and ant repellant, but it has a strong irritating odor and is not suitable for residential use. Creosote also attacks the polyvinyl chloride resin pipe used for water supply and drainage. It has recently been understood.
[0005]
In this way, the prevention and extermination measures (control measures) against white ants that injure timber in wooden houses and other buildings and structures have been increasing recently. Development of compositions for use is desired.
[0006]
Boric acid or a salt thereof (hereinafter also referred to as boric acid) is a safe and low toxic agent, but the concentration that can be stably added is low and high efficacy cannot be obtained. Things are easily dissolved in water, for example, when exposed to rain for a long time, boric acids will flow out and have the disadvantage of not being effective. In Japan, boric acids are not currently accepted as wood preservatives because of the risk of leaching from treated wood.
[0007]
Further, conventional ant protection compositions are not always sufficiently considered in terms of protection from corrosion of wood caused by other than white ants.
[0008]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and its purpose is to improve the above-mentioned drawbacks of the composition for ant protection containing boric acids with high safety, and to have an excellent ant protection effect, and the effect is long-lasting. It is another object of the present invention to provide a composition for preventing ants containing boric acids that lasts for a long time and has excellent corrosion resistance due to other than ants such as fungi on wood.
[0009]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors solved the above problems by blending charcoal powder and a specific polymer compound in a composition for preventing ant containing boric acids. As a result, the present invention has been completed.
[0010]
That is, the present invention comprises plant-derived charcoal powder, one or more selected from the group consisting of a film-forming polymer emulsion, a water-soluble polysaccharide and a polyamide resin, and boric acids. An anti-ant composition.
[0011]
In the present invention, the charcoal is preferably white charcoal or a mixture of white charcoal and black charcoal.
[0012]
The film-forming polymer is preferably an acrylic polymer or vinyl acetate polymer, the water-soluble polysaccharide is preferably starch or cellulose ether, and the polyamide resin is preferably an amorphous and ethanol-soluble polyamide. The cellulose ether is preferably methyl cellulose or hydroxypropyl methyl cellulose.
[0013]
In the present invention, the sustainability of the ant-repellent effect can be further improved by adding silica to the ant-proof composition.
[0014]
In the present invention, a film-forming polymer composed mainly of plant-derived charcoal powder, a water-soluble polysaccharide and a polyamide resin-containing composition holds boric acids and forms a coating film on the surface of wood or the like. And under actual use of the composition for ant protection of the present invention, the coating prevents the white ants from entering the wood, and the white ants eat boric acids which are edible anticides in the coating, You die before eating damage. Therefore, the ant-proof effect is exhibited effectively without being damaged by wood.
[0015]
The coating film, for example, strongly adsorbs and retains boric acids by virtue of the synergistic function of charcoal powder and various polymers on wood, and further exhibits excellent adhesion to coated objects such as wood. Due to water repellency and adhesiveness, the ant-proof effect of boric acids can be maintained for a long time without flowing out of the wood.
[0016]
In addition, the water resistance of the coating film prevents water from entering the wood, and the wood does not corrode for a long time, combined with the antibacterial and breathable properties of the coating film.
[0017]
In addition, the termite prevention of the composition for termites in this invention is a concept including prevention or extermination of a white ant. Moreover, the chemical | medical agent which has an ant preventive effect, ie, the ant preventive agent, is called an ant preventive agent, and the composition containing this ant preventive agent is called an ant preventive composition. Therefore, the composition for ant protection in this invention is a concept including the goods currently mix | blended with the medicine for ant protection and marketed as an ant protection agent.
[0018]
In addition, the film-forming polymer in the present invention is a water-insoluble polymer, and after the polymer emulsion in which the polymer is dispersed in water is applied to a substrate, it is dried to volatilize water as a dispersion medium. The polymer has the property of forming a film on the substrate.
[0019]
The polymer emulsion is a polymer in which a water-insoluble polymer is dispersed in water, and such an aqueous dispersion system of a polymer is generally called a polymer emulsion. Therefore, in the present invention, the term polymer emulsion is also used. Use. Therefore, the film-forming polymer emulsion is a dispersion system in which a water-insoluble film-forming polymer is dispersed in water.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0021]
The composition for ant protection of the present invention contains plant-derived charcoal powder.
[0022]
The plant-derived charcoal (hereinafter also simply referred to as charcoal) used in the present invention is not particularly limited, and for example, charcoal obtained by a general method of heating and dry-distilling the plant while blocking air is used. it can. Plants that can be used as raw materials for charcoal include oak, oak, cucumber, red pine, rubber trees, mangrove trees, coconut, coconut oil squeezed husks (shells), bamboo, straw, etc. It is not limited. The tree is preferable from the viewpoint of availability.
[0023]
Charcoal is roughly classified into white charcoal and black charcoal depending on the production method (firing temperature). White charcoal is manufactured by baking at a high temperature of 1000 ° C. or higher and quenching the charcoal scraped from the kiln by applying “sube” in which ash and earth are mixed in an appropriate amount of water. Representative of white coal is Bincho charcoal obtained from Umegamegashi and bamboo. On the other hand, black charcoal is obtained by baking oak, kunugi, red pine, bamboo, etc. at 400 to 700 ° C., naturally cooling and taking out from the kiln.
[0024]
In the present invention, any of white charcoal, black charcoal, and the like can be used. In particular, it is preferable to use white charcoal alone or a mixture of white charcoal and black charcoal in terms of effects. The blending ratio of white coal and black coal can be arbitrarily set according to the purpose. In the present invention, one or more kinds of charcoal can be arbitrarily selected and used.
[0025]
The charcoal powder is obtained by pulverizing charcoal by pulverization or the like. The particle diameter of the charcoal powder varies depending on the use form and is difficult to limit, but a median diameter of 2 to 300 μm is preferable. In particular, when the ant-proofing composition is in the form of an aqueous dispersion, the median diameter is preferably 2 to 200 μm, more preferably 5 to 100 μm. Moreover, when a usage form is a spray type like aerosol, it is preferable that it is 2-11 micrometers in median diameter. In the following, all particle diameters are median diameters unless otherwise specified.
[0026]
The content of the charcoal powder is preferably 1 to 40% by mass in the total amount of the composition for ant protection. If the content is less than 1% by mass, the charcoal function of the coating tends to be insufficient, and if it exceeds 40% by mass, the adhesion to the coating object tends to be insufficient. is there. A particularly preferable content is 10 to 30% by mass.
[0027]
The composition for ant protection of the present invention further contains one or more selected from the group consisting of a film-forming polymer emulsion, a water-soluble polysaccharide and a polyamide resin.
[0028]
The film-forming polymer emulsion in the present invention will be described in detail. The polymer emulsion in the present invention is not particularly limited as long as a water-insoluble polymer is dispersed in water, but a polymer emulsion obtained by emulsion polymerization of a polymerizable monomer is preferable, but is not limited thereto. is not. The emulsion polymerization is performed by a general known method.
[0029]
The polymer dispersed in the film-forming polymer emulsion in the present invention is a film-forming polymer, for example, a polymer containing at least a monomer such as an acrylic acid ester monomer such as acrylic acid ester or methacrylic acid ester or vinyl acetate ( Polymer) is a suitable example. Examples of the acrylate ester in the acrylate monomer include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, and the like. Examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate and the like.
[0030]
For example, a polymer containing at least an acrylate ester monomer, that is, an acryl polymer may be a polymer composed of the acrylate ester monomer or a copolymer with another monomer. The other monomer is not particularly limited as long as it is a copolymerizable monomer, and examples thereof include olefins such as acrylic acid, methacrylic acid, vinyl acetate, styrene, ethylene, and propylene. Among the acrylic polymers, polymers having an acrylic ester and / or methacrylic ester as a main component are preferable. In particular, a polymer mainly composed of ethyl acrylate and / or ethyl methacrylate is preferable. The acrylic polymer is selected from water-insoluble ones.
[0031]
The polymer containing at least vinyl acetate, that is, the vinyl acetate-based polymer may be a homopolymer of vinyl acetate or a copolymer with other monomers. The other monomer is not particularly limited as long as it is a copolymerizable monomer, and examples thereof include acrylate monomers, olefins such as acrylic acid, methacrylic acid, styrene, ethylene, and propylene. Among vinyl acetate polymers, vinyl acetate homopolymer is particularly preferable. The vinyl acetate polymer is selected from water-insoluble polymers.
[0032]
Further, the film-forming polymer emulsion of the present invention may contain a plasticizer or a film-forming aid for improving the polymer film when a coating film generally blended in the polymer emulsion is formed. I do not care.
[0033]
Commercially available products can be used for the film-forming polymer emulsion of the present invention. Examples of commercially available products include, for example, acrylic polymer emulsions such as Daitozol 5000AD and 5000SJ (manufactured by Daito Kasei Kogyo Co., Ltd.), Examples thereof include Aika NEW Ivon A-1410 series (manufactured by Aika Industries Co., Ltd.), which is a vinyl acetate polymer emulsion. In some cases, the vinyl acetate polymer emulsion contains polyvinyl alcohol to stabilize the dispersion of the polymer during emulsion polymerization.
[0034]
Polymer emulsions including commercially available products generally have a polymer concentration of 30 to 60% by mass from the viewpoint of storage stability, ease of use, and the like. You may mix | blend a polymer emulsion as it is, or you may mix | blend after diluting arbitrarily. In any case, it is sufficient that a polymer dispersion is present in the composition for preventing ants.
[0035]
Next, the water-soluble polysaccharide will be described in detail.
[0036]
Although it does not restrict | limit especially as a water-soluble polysaccharide used for this invention, For example, a starch, a water-soluble cellulose polymer, etc. are mentioned as a preferable example. Among these, as the water-soluble cellulose polymer, cellulose ether is preferable. For example, in addition to methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and the like, a mixed ether of methyl methyl and hydroxypropyl (hereinafter, hydroxypropyl methylcellulose). Hereinafter, all mixed ethers are represented in this form.), Cellulose having a plurality of substituents such as hydroxyethylmethylcellulose, and the like. Among the water-soluble cellulose polymers, methyl cellulose and hydroxypropyl methyl cellulose are preferable.
[0037]
Commercially available products can be used as the water-soluble cellulose polymer. Examples of commercially available products include, for example, methyl cellulose Metroses SM-15, -25, -100, -4400, -1500, -1 -4000, -8000 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), Metrolose 60SH-50, -4000, -10000, 65SH-50, which is hydroxypropyl methylcellulose, -400, -1,500, -4000 -15000, 90SH-04, -100, -400, -44000, -15000 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
[0038]
Next, the polyamide resin will be described in detail.
[0039]
The polyamide resin in the present invention may be a polycondensate of dibasic acid and diamine, a polycondensate of ω-amino acid, or a polymer of caprolactam. Specific examples include 6,6-nylon, 6,10-nylon, 6-nylon, 12-nylon and the like. In the present invention, the polyamide resin is preferably amorphous with weak crystallinity and soluble in alcohol, particularly preferably soluble in ethanol. Polyamide resin can weaken crystallinity by incorporating a copolymer, particularly a monomer having a large molecular structure. Therefore, in the present invention, it is preferable to use the above-mentioned copolyamide (also referred to as copolymer nylon). Examples of preferred copolyamides include copolyamides of ε-caprolactam, hexamethylenediamine, adipic acid and sebacic acid (6-nylon, 6,6-nylon, 6,10-nylon copolyamide), ε-caprolactam and hexa Copolyamides of methylenediamine, adipic acid, sebacic acid, ε-laurolactam and ω-aminododecanoic acid (6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon copolyamide), ε-caprolactam And a copolyamide (6-nylon, 6,6-nylon, 12-nylon copolyamide) of hexamethylenediamine, adipic acid, ε-laurolactam, and ω-aminododecanoic acid.
[0040]
An N-methoxymethylated polyamide resin in which hydrogen of the amide group of the polyamide resin is substituted with a methoxymethyl group is also a polyamide resin with reduced crystallinity, and can be preferably used in the present invention.
[0041]
The polyamide resin may be used alone, but the adhesion to the substrate can be improved by mixing with a polyacrylate ester, polyvinyl acetate or the like. Moreover, it can also be made water-soluble by blending polyacrylic acid, polymethacrylic acid or the like. As the water-soluble polyamide resin, a water-soluble polyamide resin manufactured by Artec Kobo Co., Ltd. can also be used.
[0042]
Further, commercially available products include, for example, CM-8000 (copolyamide manufactured by Toray Industries, Inc .; low melting point type, 6-nylon, 12-nylon, 6,6-nylon, 6,10-nylon), CM -4000 (co-polyamide manufactured by Toray Industries, Inc .; high melting point type, containing 6-nylon, 6,6-nylon, 6,10-nylon), EF-30T (N-methoxymethyl manufactured by Teikoku Chemical Industry Co., Ltd.) Polyamide resin) and F-30K (N-methoxymethylated polyamide resin manufactured by Teikoku Chemical Industry Co., Ltd.), and these can also be used.
[0043]
The content of the film-forming polymer emulsion, the water-soluble polysaccharide, and the polyamide resin is 0.5 to 30 mass in the total amount of the composition for ant protection, as the content of one or more selected from the group consisting of these. % Is preferred. More preferably, it is 5-20 mass%. In the case of a film-forming polymer emulsion, the content is a polymer content.
[0044]
Moreover, 1 type (s) or 2 or more types selected from the group consisting of a film-forming polymer, a water-soluble polysaccharide and a polyamide resin present as a polymer emulsion are 1% by mass to It is preferable to mix in the range of 4 times by mass. More preferably, it is 10 mass%-2 mass times. In particular, 25-100 mass% is preferable.
[0045]
Next, the boric acid compounded in the present invention is boric acid or a borate as described above, and is not particularly limited as long as it is water-soluble with an ant-proof effect. As the borate, an alkali metal borate, particularly sodium borate is preferable. The content of boric acids is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, in the composition for ant protection.
[0046]
In blending boric acids, water is blended as a boric acid solvent, but it is preferable to blend a polyhydric alcohol with water. Examples of the polyhydric alcohol include sorbitol, erythritol, xylit, maltitol, glycerin, 1,3-butylene glycol, propylene glycol, dipropylene glycol, diglycerin and the like.
[0047]
In the composition for ant protection of the present invention, if necessary, other components than the above-described components can be appropriately blended within a range not impairing the effects of the present invention. As appropriate blending components, for example, powders, pigments, water-soluble polymers other than those described above, thickeners, other anti-anticides other than boric acids, organic solvents, surfactants, sequestering agents, antioxidants, A fragrance | flavor, a dispersing agent, a viscosity modifier, an antifoamer, etc. are mentioned.
[0048]
Examples of the powder include silica, sodium silicate, zinc oxide, bentonite, alumina, titanium oxide, magnesium oxide and the like.
[0049]
Among these, when silica is blended, the sustainability of the ant-repellent effect can be further improved. Among silicas, porous silica is particularly preferable because it is excellent in adsorbability of boric acids to an object and air permeability of a coating film. When blending. The effective amount of silica is 1 to 30% by mass, more preferably 5 to 15% by mass in the composition for ant protection.
[0050]
Examples of the organic solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, benzyl alcohol, acetone and the like. Among these, C1-C3 aliphatic monohydric alcohols such as methanol, ethanol, and propanol are preferable, and ethanol is particularly preferable. Adhesion to the object can be improved by blending the organic solvent.
[0051]
In addition, a monohydric alcohol having 1 to 2 ether bonds in one molecule as an auxiliary organic solvent for adjusting the drying speed of the coating film, and having appropriate volatility, such as methyl cellosolve, ethyl cellosolve, propyl Cellosolve (normal, iso, secondary or tertiary), butyl cellosolve, methyl carbitol, ethyl carbitol, diethylene glycol monomethyl ether and the like can be used.
[0052]
Examples of the water-soluble polymer include carrageenan, gum arabic, xanthan gum, curdlan, succinoglucan, chitin, chitosan, agar, polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, sodium polyacrylate, polyethylene glycol and the like.
[0053]
Examples of surfactants include anionic surfactants such as fatty acid soap (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, alkyl sulfate triethanolamine ether, acylmethyl taurate; stearyltrimethylammonium chloride, benzaza chloride Cationic surfactants such as luconium and laurylamine oxide; imidazoline-based amphoteric surfactants (such as 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt), betaine-based surfactants (alkyl) Amphoteric surfactants such as betaine, amide betaine, sulfobetaine);
[0054]
Sorbitan fatty acid esters (such as sorbitan monostearate and sorbitan sesquioleate), glycerin fatty acids (such as glyceryl monostearate), propylene glycol fatty acid esters (such as propylene glycol monostearate), hydrogenated castor oil derivatives, glycerin alkyl ether POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbite fatty acid esters (POE-sorbite monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisosteare) Rate), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyldede) Ethers), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE / POP alkyl ethers (POE / POP2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hardened castor oil Nonionic surfactants such as derivatives (POE castor oil, POE hydrogenated castor oil, etc.) and the like can be mentioned.
[0055]
The form of the ant-proof composition is an aqueous dispersion system in which charcoal powder, a film-forming polymer, etc. are dispersed in water or other solvent. Moreover, the composition for ant protection of the present invention is used as an aerosol stock solution, and can be used in a spray type. Therefore, when using the composition for ant protection of the present invention, it is generally applied or sprayed. For example, by applying to a wood surface (by spraying, brushing, roller coating, etc.) and then drying under natural conditions, a film-like composition for ant protection having a desired ant protection effect is formed on wood. Is done.
[0056]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples. The blending amount is mass% unless otherwise specified. Prior to the description of the examples, the effect test method used in the present invention will be described.
[0057]
[Anti-ant effect]
(Company) Japan Wood Preservation Association Standard No. 11 1992 “Method for testing ant proofing effect of wood ant protection agent for coating, spraying and dipping treatment” (1) Laboratory test method 4.3 It was performed according to the comprehensive test. Hereinafter, the points of the test method will be specifically described.
[0058]
(Test method)
(1) Wood specimen
(A) The wood piece to be used for the test is a pine sapwood (20 (L) × 10 (R) × 10 (T) mm) rectangular parallelepiped.
(B) Wood pieces are dried for 24 hours in a thermostat at a temperature of 60 ° C.
[0059]
(2) Specimen
(B) Two types of specimens are used: a treated specimen obtained by treating a piece of wood with a sample and an untreated specimen that is not treated with a sample. Furthermore, after processing the sample, the test specimen is divided into those subjected to the weathering operation specified in (2) and (d) and those not.
(B) The number of test specimens shall be five for each of the treated specimen subjected to weathering operation, the treated specimen not subjected to weathering operation, and the untreated specimen.
(C) Using a brush on a piece of wood, a sample of 110 g / m 2 After being applied at a rate of 20%, it is allowed to stand at room temperature for 20 days or more, and then divided into 2 groups of 5 which are subjected to weathering operation and 5 which are not.
(D) The weathering operation repeats the wetting operation and the volatilization operation 10 times alternately.
Wetting operation: Sample-treated wood pieces subjected to weathering operation are put together and soaked in still water at room temperature for 30 seconds, then placed in a desiccator with water at the bottom and left in a constant temperature room at 26 ° C. for 4 hours.
Volatilization operation: The sample-treated wood piece that has been subjected to the wetting operation is immediately left in a circulating hot air incubator at a temperature of 40 ° C. for 20 hours.
(E) Sample treated wood pieces subjected to weathering operation, sample treated wood pieces not subjected to weathering operation, and untreated wood pieces were dried at a temperature of 60 ° C. for 48 hours, left in a desiccator for about 30 minutes, and then their mass (W 1 ) To 0.01 g to obtain a test specimen.
[0060]
(3) Breeding container
As a rearing container, a container with a lid of 8 cm in diameter and 6 cm in length made of hardened gypsum hardened to a thickness of about 5 mm on a part of a cylinder made of acrylic resin, which is preliminarily covered with wet cotton to a thickness of about 2 cm. Place 10-15 pieces inside. For wet cotton, 130-150 ml of water is added to 100 g of wet cotton. Make a small hole in the lid for ventilation.
[0061]
(4) Rearing
(B) Place the treated specimens or untreated specimens one by one horizontally on the hard stone plaster in the breeding container prepared in the previous section, and place them randomly from the nest. Throw out 150 craft ants and 15 soldier ants.
(B) The lidded container is kept in a dark place at a temperature of 28 ° C. for 21 days.
[0062]
(Test results)
(1) After 21 days, remove the specimen from the breeding container, carefully remove the deposits on the specimen surface, dry at a temperature of 60 ° C. for 48 hours, leave it in a desiccator for about 30 minutes, and weigh to 0.01 g. Mass (W 2 )
(2) Record the number of dead termite ants.
[0063]
(Display results)
(1) The mass reduction rate of the test specimen is calculated according to the following formula, and the average mass reduction ratio of five is determined for the untreated test specimen.
Mass reduction rate (%) = [(W 1 -W 2 ) / W 1 ] × 100
(2) Calculate the mortality rate according to the following formula and obtain the average mortality rate.
Death rate (%) = [Number of dead insects / 150] × 100
[0064]
[Adhesiveness]
The sample was applied to the wood with a brush with a substantially constant amount, dried, rubbed by hand, and evaluated for rubbing based on the following evaluation criteria.
(Evaluation criteria)
○: The wood coating was not peeled off.
(Triangle | delta): The coating film of wood peeled off a little.
X: The coating film of wood peeled off.
[0065]
[Wood corrosion durability]
This was carried out in accordance with Japan Wood Preservation Association Standard No. 1 1992 “Preservation efficacy test method for wood preservatives for coating, spraying and dipping treatment”. Hereinafter, the points of the test method will be specifically described.
[0066]
(1) Wood pieces
A piece of wood is taken from sapwood and beech sapwood (thickness is 5 mm, width is 20 mm, length is 40 mm, and a surface of 40 × 20 mm is a square surface). The mouth end is sealed with a room temperature curing epoxy resin.
[0067]
(2) Combination of tree species and test bacteria
Antibacterial operation is performed by selecting the fungus species for each tree type. The combinations are as follows.
Sugi ...
Beech ... Kawaratake
[0068]
(3) Specimen
There are two types of test specimens: a treated specimen and an untreated specimen.
(B) Processed specimen
The treated specimen is a piece of wood that has been coated, sprayed or dipped using a sample, and the sample absorbs 110 g / m. 2 And In the dipping treatment, the surface of the wood piece after treatment is lightly wiped with filter paper.
[0069]
(B) Sample absorption
The individual sample absorption of wood pieces is calculated by the following formula.
Sample absorption (g / m 2 ) = (W 1 -W 2 ) / A
W 1 : Mass of wood piece after sample absorption (g)
W 2 : Mass of wood piece before sample absorption (g)
A: Surface area of the piece of wood excluding the facet (m 2 )
[0070]
(C) Required number of specimens
The required number of specimens used in the test is as shown in Table 1.
[0071]
[Table 1]
[0072]
(4) Test
In the test, the test specimen prepared in (3) (A) is air-dried for 20 days and then subjected to weathering, and after the weathering is finished, antibacterial operation is performed.
(I) Weatherproof operation
In the weathering operation, leaching and volatilization operations are repeated 30 times alternately.
(A) In the leaching operation, the same treatments are put together, so as not to come into contact with each other, soaked in a still water at 25 ° C. for 5 hours to leaches out the leached portion. The volume ratio of water to the specimen is 10: 1 and is replaced with new water each time the operation is repeated.
(B) In the volatilization operation, the test specimen after the leaching operation is drained lightly, and immediately left in a circulation dryer at a temperature of 40 ° C. for 19 hours to volatilize.
(C) After the weathering operation was finished, the test specimen was dried in a circulation dryer at 60 ° C. for 48 hours, and then left in a desiccator for about 30 minutes to determine its mass (W Three ) To 0.01 g.
[0073]
(B) Antibacterial operation
Antibacterial operation is performed on the specimen after the weathering operation.
(A) Treated test specimens and untreated test specimens were separately placed in a Teflon (registered trademark) plate frame for each culture bottle, and sterilized. Place on the fungus soak for 8 weeks at a temperature of 26 ° C and a relative humidity of 70% or higher.
(B) After 8 weeks, remove the specimen, carefully remove the mycelium and other deposits on the surface, air dry for about 24 hours, and then dry in a circulation dryer at a temperature of 60 ° C. for 48 hours, about 30 Its mass (W Four ) To 0.01 g.
[0074]
(5) Test results
A test result is represented by the average mass reduction | decrease rate by the antibacterial operation of the process test body which performed antibacterial operation.
(I) Mass reduction rate
The mass reduction rate of each specimen is calculated by the following formula, and the average value is obtained.
Mass reduction rate (%) = [(W Three -W Four ) / W Three ] × 100
[0075]
(Examples 1-5)
The composition for ant prevention of the prescription shown in Table 2 was prepared by the following method. A container was mixed with acrylic polymer emulsion, vinyl acetate polymer emulsion, starch, methylcellulose, polyamide resin, surfactant, ethanol, zinc oxide, and porous silica, stirred and allowed to stand. (A container). Further, sodium borate, sorbite and water were mixed in the B container, stirred and allowed to stand (B container). The next day, the charcoal powder was gently put into the A container, and the charcoal powder was slowly precipitated, and after all precipitated, the mixture was stirred. Next, the A container and the B container were mixed, and further hinokitiol was added and stirred well.
[0076]
[Table 2]
[0077]
In Table 2,
(Note 1) White coal (Ubamegashi; Bincho charcoal), particle size: 24 μm
(Note 2) Daitozol 5000AD (50% polymer concentration)
(Note 3) 40% polymer concentration
(Note 4) Metrows SM-8000
(Note 5) CM8000
(Note 6) Ionette RAP-400 (manufactured by Sanyo Chemical Industries, Ltd.)
[0078]
Table 3 shows the results of evaluation of the ant-proof effect of Examples 1 to 5 described above.
[0079]
[Table 3]
[0080]
(Note) In Table 3, the upper row of Examples 1 to 5 shows data when weathering operation is performed, and the lower row shows data when weathering operation is not performed. The untreated specimen is data when there is no weathering operation.
[0081]
As is apparent from Table 3, the boric acid-based anti-ant composition of Examples 1 to 5 containing charcoal powder and an acrylic polymer emulsion, a vinyl acetate polymer emulsion, starch, methylcellulose, or a polyamide resin, It can be seen that it exhibits an excellent ant-repellent effect and has excellent sustainability.
[0082]
The adhesion evaluation results of Examples 1 to 5 are shown in Table 4.
[0083]
[Table 4]
[0084]
As can be seen from Table 4, the boric acid-based anti-ant composition of Examples 1 to 5 in which charcoal powder and an acrylic polymer emulsion, vinyl acetate polymer emulsion, starch, methylcellulose or polyamide resin were blended were used. Despite containing charcoal powder, it did not peel off and showed excellent adhesion.
[0085]
Table 5 shows the evaluation results (mass reduction rate) of the wood corrosion durability of Examples 1 to 5 described above.
[0086]
[Table 5]
[0087]
As is apparent from Table 5, the boric acid-based anti-ant composition of Examples 1 to 5 containing charcoal powder and an acrylic polymer emulsion, vinyl acetate polymer emulsion, starch, methylcellulose or polyamide resin It can also be seen that it exhibits an excellent wood corrosion durability effect.
[0088]
Hereinafter, examples of the composition for ant protection according to the present invention will be shown. In addition, manufacture was performed according to the method of Examples 1-5. Moreover, when the above effect tests were performed on these, excellent effects were obtained in all cases.
[0089]
[0090]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) Metrows 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Ionette RAP-400 (manufactured by Sanyo Chemical Industries, Ltd.)
[0091]
[0092]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) Daitozol 5000SJ (50% polymer concentration)
(Note 3) Metroz 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) Metrows SM-8000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 5) Ionette LEC (manufactured by Sanyo Chemical Industries)
[0093]
[0094]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) Metrows 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Metrows 65SH-15000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) Metroz 90SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 5) Ionette RAP-400 (manufactured by Sanyo Chemical Industries)
[0095]
[0096]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) Metrows 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
[0097]
[0098]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) 40% polymer concentration
(Note 3) Metroz 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
[0099]
[0100]
(aerosol)
Stock solution 40.0 (volume%)
Propellant (dimethyl ether) 60.0 (volume%)
[0101]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) Metrows 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Ionette RAP-400 (manufactured by Sanyo Chemical Industries, Ltd.)
[0102]
[0103]
(aerosol)
Stock solution 50.0 (volume%)
Propellant (dimethyl ether) 50.0 (volume%)
[0104]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) Metrows 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
[0105]
[0106]
(aerosol)
Stock solution 40.0 (volume%)
Propellant (dimethyl ether) 60.0 (volume%)
[0107]
(Note 1) Daitozol 5000SJ (50% polymer concentration)
(Note 2) Metrows 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
[0108]
[0109]
(Note 1) Metroz 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Ionette RAP-400 (manufactured by Sanyo Chemical Industries)
[0110]
[0111]
(Note 1) Metroz 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Metrows SM-8000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Ionette LEC (manufactured by Sanyo Chemical Industries, Ltd.)
[0112]
[0113]
(Note 1) Metroz 60SH-10000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Metrows 65SH-15000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 3) Metroz 90SH-4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 4) Metrows SM-4000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 5) Ionette RAP-400 (manufactured by Sanyo Chemical Industries)
[0114]
[0115]
(Note 1) Metrows SM-8000 (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Note 2) Ionette LEC (manufactured by Sanyo Chemical Industries)
[0116]
[0117]
(Note 1) Ionette RAP-400 (manufactured by Sanyo Chemical Industries)
[0118]
[0119]
(Note 1) CM-8000
(Note 2) F30K
[0120]
[0121]
(Note 1) CM-4000
[0122]
[0123]
(Note 1) CM-8000
[0124]
[0125]
(Note 1) Daitozol 5000AD (50% polymer concentration)
(Note 2) Ionette RAP-400 (manufactured by Sanyo Chemical Industries)
[0126]
【The invention's effect】
As described above in detail, according to the present invention, highly safe boric acids are selected from the group consisting of plant-derived charcoal powder, a film-forming polymer emulsion, a water-soluble polysaccharide, and a polyamide resin. Since an anti-ant composition was prepared by blending with more than seeds, it improved the disadvantages of the conventional anti-ant composition containing boric acids, and was excellent in preventing or extinguishing white ants, and the effect was long-lasting. In addition, a safe composition for preventing ants is obtained that lasts for a long time and has excellent durability against bacteria other than ants.
Claims (7)
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| JP2003179339A JP4177719B2 (en) | 2002-06-28 | 2003-06-24 | Anti-ant composition |
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| JP2003179339A JP4177719B2 (en) | 2002-06-28 | 2003-06-24 | Anti-ant composition |
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| JP2007051236A (en) * | 2005-08-19 | 2007-03-01 | Shin Etsu Chem Co Ltd | Silicone emulsion composition and method for treating wood |
| JP5537061B2 (en) * | 2009-04-03 | 2014-07-02 | 株式会社エプコ | Underfloor structure and ant protection method |
| WO2015037610A1 (en) * | 2013-09-13 | 2015-03-19 | 日本曹達株式会社 | Aqueous liquid composition for solid material treatment |
| WO2018229850A1 (en) * | 2017-06-13 | 2018-12-20 | アーテック株式会社 | Aqueous coating composition, air cleaning mechanism, and air cleaning method |
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| JP2517718B2 (en) * | 1987-02-07 | 1996-07-24 | 義之 大串 | A coating agent for combating termites and cockroaches using boric acid |
| JPH01318071A (en) * | 1988-06-17 | 1989-12-22 | Asahi Glass Co Ltd | Insecticidal and antibacterial coating material, its production and its product of application |
| JP3133962B2 (en) * | 1997-07-10 | 2001-02-13 | 道晴 吉松 | Paint composition |
| JP2002121497A (en) * | 2000-10-17 | 2002-04-23 | Keiichi Ogaki | Coating material and method for producing the same |
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