JP2008144072A - Coating composition for coating wood and coating - Google Patents
Coating composition for coating wood and coating Download PDFInfo
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Abstract
Description
本発明は、木材の表面に塗布して、木材に防虫、防腐の機能を長期間にわたって付与することを可能とする木材塗装用塗料組成物及び該組成物を用いた木材塗装用塗料に関するものである。 The present invention relates to a coating composition for wood coating that can be applied to the surface of wood to give insects an antiseptic and antiseptic function over a long period of time, and a coating material for wood coating using the composition. is there.
例えば、建築物の防虫・防腐を考えた場合、家屋には「イエヒメアリ」をはじめとする家屋害虫が生息し、家屋内外の木材に食害を与えたり、また、高湿度の材木には腐敗菌が繁殖して木材を腐食させる。
従来、このような木材の防虫・防腐を目的とした木材用塗料としては、木酢液採取の際に副生する木タール木炭微粉を混合して、木タールの防虫・防腐効果を発揮させる塗料（特許文献１）や、木タールに粉状の活性炭を混合させた塗料を、船底、岸壁などに塗布して海洋生物の付着を防止する技術（特許文献２）などが開示されている。
Conventionally, as a wood paint for the purpose of such insect control / preservation of wood, a paint that demonstrates the anti-preservation / preservation effect of wood tar by mixing wood tar charcoal fine powder by-produced during the extraction of wood vinegar liquid ( Patent Document 1) and a technique (Patent Document 2) that prevents the adhesion of marine organisms by applying a paint obtained by mixing powdered activated carbon to wood tar to a ship bottom, a quay, or the like are disclosed.
しかしながら、上記した特許文献１、２の技術は、いずれも木タールを原料とするため、木タール中に存在するピッチなどの重質成分のため凝固し易く、かつ、人体に悪影響を及ぼす縮合環状化合物が存在し、更に、煤、灰などの夾雑物が大量に混入するため形成される塗布面が粗雑である。また、木タール特有の強い臭気（悪臭）のため、木材用塗料としては不適であるという問題点があった。
木タールは、木材を乾留して得られる凝縮液体を静置したときに分離する２層のうちの下層側の黒褐色の粘調な液体であって、有機酸類、ラクトン類、エステル類、フェノール類、アルデヒド類、ケトン類、塩基類、フラン類等の多種類の化合物を含み、特に、フェノール類、アルデヒド類は防虫、防腐性を有することから、海洋生物の付着が問題となる船底塗料には適しているといえる。しかし、木タールには常温でも固化するピッチ様の固まりや、塗膜表面の平滑さを阻害する遊離炭素の固まりが混在し、しかも、甚だしい臭気を発するため、一般的な塗料としては適していないとされていた。
特に、家屋の内外の柱、壁、床、屋根裏に使用する塗料は、ＪＩＳ Ｋ ５９６０「家庭用屋内塗料」に規定する規格に適合しなければならないが、現状の木タールを使用した塗料は、低温安定性（−１０℃に冷やしても変質しない）、乾燥時間（１時間以内）、低温造膜性（５℃で塗膜形成に異常がない）の規格値を満足するものではない。従って、優れた防虫・防腐効果を発揮する木タールを汎用性のある塗料として使用しようとする場合には、臭気が少ないとともに、低温安定性、乾燥時間及び低温造膜性が規格値を満足することが要求される。
本発明は、このような点に鑑みてなされたもので、防虫・防腐効果が高く、しかもその効果を長期間にわたって維持し、かつ、家庭用屋内塗料として全ての条件が規格に適合するとともに、臭気の面でも問題のない、きわめて実用性の高い木材用塗料組成物とこれを用いた木材塗装用塗料を提供することを課題とする。
However, since the techniques of Patent Documents 1 and 2 described above use wood tar as a raw material, they are easy to solidify due to heavy components such as pitch existing in wood tar, and have a negative influence on the human body. A compound is present, and furthermore, a large amount of foreign substances such as soot and ash are mixed therein, so that the formed coated surface is rough. Moreover, due to the strong odor (bad odor) peculiar to wood tar, there is a problem that it is not suitable as a paint for wood.
Wood tar is a dark brown viscous liquid on the lower side of the two layers that separates when the condensate obtained by dry distillation of wood is allowed to stand, and includes organic acids, lactones, esters, phenols It contains many kinds of compounds such as aldehydes, ketones, bases, furans, etc. Especially, phenols and aldehydes have insect and antiseptic properties, so marine organisms have a problem of adhesion to marine organisms. It can be said that it is suitable. However, wood tar is not suitable as a general paint because it contains pitch-like clumps that solidify even at room temperature and free carbon clumps that hinder the smoothness of the coating surface, and emits a strong odor. It was said.
In particular, paint used on pillars, walls, floors, and attics inside and outside the house must conform to the standards specified in JIS K 5960 “Indoor paint for home use”. It does not satisfy the standard values of low temperature stability (no deterioration even when cooled to −10 ° C.), drying time (within 1 hour), and low temperature film forming property (no abnormality in coating film formation at 5 ° C.). Therefore, when trying to use wood tar that exhibits an excellent insecticidal and antiseptic effect as a general-purpose paint, it has low odor and low-temperature stability, drying time and low-temperature film-forming properties satisfy standard values. Is required.
The present invention has been made in view of such points, and has a high insecticidal and antiseptic effect, and the effect is maintained over a long period of time. It is an object of the present invention to provide a highly practical wood coating composition having no problem in terms of odor and a wood coating material using the same.
上記課題を解決するための本発明に係る塗料組成物は、木タール、竹タールもしくは籾タールに極性有機溶剤を接触させることにより、タール中の防虫・防腐に有効な成分を溶出して得られたタール抽出液と多孔質粉末を混合したことを特徴とする。
また、上記塗料組成物は、タール抽出液１００重量部に、多孔質粉末を５〜１２０重量部を混合すること、多孔質粉末の比表面積が１０ｍ２／ｇ以上であること、極性有機溶剤は、融点が０℃以上、沸点が５０℃以上の、ヒドロキシル基、カルボキシル基、カルボニル基もしくはエーテル基を有するものであることが好ましい。
更に、本発明に係る木材塗装用塗料は、上述したいずれかの塗料組成物に、結合剤を配合したことを特徴とする。
A coating composition according to the present invention for solving the above-mentioned problems is obtained by eluting components effective in insect and antiseptic in tar by bringing a polar organic solvent into contact with wood tar, bamboo tar or straw tar. The tar extract and the porous powder are mixed.
The coating composition is prepared by mixing 5 to 120 parts by weight of a porous powder with 100 parts by weight of a tar extract, that the specific surface area of the porous powder is 10 m 2 / g or more, It preferably has a hydroxyl group, carboxyl group, carbonyl group or ether group having a melting point of 0 ° C. or higher and a boiling point of 50 ° C. or higher.
Furthermore, the coating material for wood coating according to the present invention is characterized in that a binder is blended in any of the coating compositions described above.
本発明の塗料組成物によれば、木タールを原料とするが、その優れた防虫・防腐作用を損なうことなく、臭気などの問題点を解消したものであり、かつ、適量の多孔質物質の配合により木タールが該多孔質物質の細孔に吸着されることから、防虫・防腐効果が長く保持される。従って、本発明は木材用塗料用として最良な塗料組成物であるといえる。特に、家屋に有害な「イエヒメアリ」をはじめとする家屋害虫に対し有効である。 According to the coating composition of the present invention, wood tar is used as a raw material, but it eliminates problems such as odor without impairing its excellent insect-proofing and antiseptic action, and an appropriate amount of porous material. Since wood tar is adsorbed to the pores of the porous material by blending, the insect and antiseptic effects are maintained for a long time. Therefore, it can be said that the present invention is the best coating composition for wood coating. In particular, it is effective against house pests such as “Yehimeari” that are harmful to houses.
以下、本発明を完成するに至った経緯と本発明の実施形態について説明する。
本発明者は、木タールの優れた防虫・防腐効果は、含有する成分中のクレゾール、ジメチルフェノール、カテコール、ピロガロール、グアヤコール等のフェノール類、及びバレルアルデヒド、プロピオンアルデヒド等のアルデヒド類であることに着目し、これら有効税分のみを木タールから分離して木材用塗料の原料として使用することを検討した結果、以下の事実を見出した。
すなわち、木タールを特定の溶媒で処理することにより、上述の有効成分を溶媒中に抽出することが可能であること、この抽出液を木材用塗料の原料として用いたところ、無処理の木タールを原料とした木材用塗料よりも優れた防虫・防腐効果を発揮するとともに、臭気は格段に少なくなり、「家庭用屋内塗料」として要求される、低温安定性、乾燥時間及び低温造膜性が規格値をすべて満足する木材用塗料が得られることを知見した。
なお、木タール中の防虫・防腐効果を有する有効物質を蒸留により分離する方法も考えられるが、フェノール類の沸点は高く、例えばクレゾールは２００℃、2,3-ジメチルフェノールは２１８℃、カテコールは２４０℃であるため、大気圧下では蒸留により溜出させることはできない。一方、減圧蒸留法によれば溜出は可能であるが、膨大なエネルギーコストを要する問題があり、また、水蒸気蒸留で有効成分を取出すことも可能であるが、希薄な水溶液となるため、塗料成分として使用するには適さない問題がある。
Hereinafter, the background to the completion of the present invention and embodiments of the present invention will be described.
The present inventor said that the excellent insecticidal and antiseptic effects of wood tar are phenols such as cresol, dimethylphenol, catechol, pyrogallol and guaiacol, and aldehydes such as valeraldehyde and propionaldehyde in the contained components. As a result of studying the use of only these effective taxes as a raw material for wood paints by separating them from wood tar, the following facts were found.
That is, it is possible to extract the above-mentioned active ingredient into a solvent by treating wood tar with a specific solvent, and using this extract as a raw material for wood paint, In addition to exhibiting superior insecticidal and antiseptic effects than wood-based paints made from wood, the odor is remarkably reduced, and the low-temperature stability, drying time, and low-temperature film-forming properties required as “household indoor paints” It was found that a paint for wood that satisfies all the standard values can be obtained.
A method of separating effective substances having an insecticidal and antiseptic effect in wood tar by distillation is also conceivable, but the boiling points of phenols are high, for example, cresol is 200 ° C., 2,3-dimethylphenol is 218 ° C., catechol is Since it is 240 ° C., it cannot be distilled by distillation under atmospheric pressure. On the other hand, although distillation is possible by the vacuum distillation method, there is a problem that enormous energy cost is required, and it is possible to take out the active ingredient by steam distillation. There is a problem that is not suitable for use as an ingredient.
以上の点を考慮して本発明においては、木タールを特定溶媒で処理することにより、木タール中の防虫、防腐に有効な成分である、クレゾール、ジメチルフェノール、カテコール、ピロガロール、グアヤコール等のフェノール類、及びバレルアルデヒド、プロピオンアルデヒド等のアルデヒド類を抽出し、低温度で固化するピッチ性状の固まりや、塗膜表面の平滑さを阻害する遊離炭素の固まりを分離・除去する。そして、抽出液を木材用塗料の原料として用いることにより、臭気が少なく、低温安定性、乾燥時間及び低温造膜性が規格値を満足させる木材用塗料を得ることが可能となった。
なお、特定溶剤は、木タール中に微量ながら含まれている人体に有害なアントラセン、ベンゾピレン等の縮合環状化合物を溶解せずに、抽出液中にこれらの有害物質が混入しないものが要求される。
In view of the above points, in the present invention, by treating wood tar with a specific solvent, phenol, such as cresol, dimethylphenol, catechol, pyrogallol, guaiacol, which is an effective ingredient for insect repellent and antiseptic in wood tar And aldehydes such as valeraldehyde, propionaldehyde, etc. are extracted to separate and remove pitch-like masses that solidify at low temperatures and free carbon masses that hinder the smoothness of the coating surface. By using the extract as a raw material for wood paints, it is possible to obtain wood paints with less odor and low temperature stability, drying time and low temperature film-forming properties satisfying standard values.
In addition, specific solvents are required that do not dissolve these harmful substances in the extract without dissolving condensed cyclic compounds such as anthracene and benzopyrene that are harmful to the human body even though they are contained in trace amounts in wood tar. .
また、木タールを処理するための特定溶剤としては、木タール中の有効成分が確実に溶解、抽出する極性有機溶剤を用いることが必要である。この極性有機溶剤としては、融点が０℃以上、沸点が５０℃以上の、ヒドロキシル基を有するメタノール、エタノール等、カルボキシル基を有する酢酸、プロピオン酸等、カルボニル基を有するアセトン、メチルエチルケトン等、エーテル基を有するジ−ｎ−プロピルエーテル、エチル−ｎ−ブチルエーテル等を挙げることができる。なお、木タールに極性有機溶剤を接触させることにより木タール中の特定成分（防虫・防腐に有効な成分）を溶出して得られる抽出液を、以下単に「木タール抽出液」と称する。 Moreover, as a specific solvent for treating wood tar, it is necessary to use a polar organic solvent that reliably dissolves and extracts an active ingredient in wood tar. Examples of the polar organic solvent include methanol having a melting point of 0 ° C. or higher and a boiling point of 50 ° C. or higher, ethanol having a carboxyl group, acetic acid having a carboxyl group, propionic acid, etc., acetone having a carbonyl group, methyl ethyl ketone, etc. And di-n-propyl ether, ethyl-n-butyl ether and the like. In addition, the extract obtained by eluting a specific component (a component effective for insecticide / preservation) in the wood tar by contacting the wood tar with a polar organic solvent is hereinafter simply referred to as a “wood tar extract”.
次に、本発明においては、上記の木タール抽出液を吸着して塗料を木材に塗装後、長期にわたって木タール抽出液の含有成分が保持する防虫・防腐の効果を発揮させるために、多孔質粉末を配合することが必要である。
本発明において使用しうる多孔質粉末の例としては、下記に示すとおりであり、併せてその比表面積（ｍ２／ｇ）を示す。これらの多孔質粉末を単独もしくは２種以上適宜混合して用いることができる。
・ＳＡＦブラック（super abrasion furnace black） ９０〜１６３（ｍ２／ｇ）
・ＩＳＡＦブラック（intermediate super abrasion furnace black）
１１８〜１２８
・ＨＡＦブラック（high abrasion furnace black） ８０〜１００
・ＭＡＦブラック（medium abrasion furnace black） ７５
・ＧＰＦブラック（general purpose furnace black） ２８〜４６
・ＳＲＦブラック（semi-reinforcing furnace black） ２５〜３０
・ＦＴブラック（fine thermal black） １３〜１９
・乾式ホワイトカーボン １３０〜３８０
・湿式ホワイトカーボン １５０〜２５０
・クレー（珪酸アルミニウム） ４０〜１３０
・珪藻土 １０〜４０
・天然ゼオライト ２５〜３５
・合成ゼオライト ４００
・活性炭 ５００〜１０００
・活性炭素繊維裁断粉末 １５００〜２５００
Next, in the present invention, in order to exhibit the insecticidal and antiseptic effects retained by the components contained in the wood tar extract over a long period of time after adsorbing the wood tar extract and applying the paint to wood, It is necessary to blend the powder.
Examples of the porous powder that can be used in the present invention are as follows, and the specific surface area (m 2 / g) is also shown. These porous powders can be used alone or in admixture of two or more.
-SAF black (super abrasion furnace black) 90-163 (m 2 / g)
・ ISAF black (intermediate super abrasion furnace black)
118-128
・ HAF black (high abrasion furnace black) 80-100
・ MAF black (medium abrasion furnace black) 75
・ GPF black (general purpose furnace black) 28-46
・ SRF black (semi-reinforcing furnace black) 25-30
・ FT black (fine thermal black) 13-19
・ Dry-type white carbon 130-380
・ Wet white carbon 150-250
・ Clay (aluminum silicate) 40-130
・ Diatomaceous earth 10-40
・ Natural zeolite 25-35
・ Synthetic zeolite 400
・ Activated carbon 500-1000
-Activated carbon fiber cutting powder 1500-2500
上述した多孔質粉末は、その機能をより効果的に発揮させるためには、木タール抽出液との配合割合と比表面積の特定が必要である。すなわち、木タール抽出液１００重量部に対し多孔質粉末を５〜１２０重量部配合することが好ましく、また、多孔質粉末の比表面積は１０ｍ２／ｇ以上であることが望ましい。
多孔質粉末が木タール抽出液１００重量部に対し５重量部未満であると、多孔質粉末が少なすぎて木タール抽出液を十分に吸着することができず、また、１２０重量部を超えて配合してもその効果が飽和するとともに他の成分の配合量にも影響を与えるため、多孔質粉末は５〜１２０重量部とした。特に、好適な配合量は、３０〜８０重量部の範囲である。
また、多孔質粉末の比表面積を１０ｍ２／ｇ以上と規定したのは、１０ｍ２／ｇ未満であると、粉末の粒度が大きく表面積が小さいため木タール抽出液の吸着性が低くなって好ましくないことから、１０ｍ２／ｇ以上とした。比表面積の上限は特に規定しないが、１０ｍ２／ｇ以上の比表面積で使用可能なものであればいかなるものでもよく、コストや実用性を考慮して適宜選択すればよい。
In order for the porous powder described above to exhibit its functions more effectively, it is necessary to specify the blending ratio with the wood tar extract and the specific surface area. That is, it is preferable to mix 5 to 120 parts by weight of the porous powder with respect to 100 parts by weight of the wood tar extract, and the specific surface area of the porous powder is preferably 10 m 2 / g or more.
When the porous powder is less than 5 parts by weight based on 100 parts by weight of the wood tar extract, the porous powder is too small to sufficiently adsorb the wood tar extract, and more than 120 parts by weight. Even if it mix | blends, since the effect will be saturated and it will also affect the compounding quantity of another component, the porous powder was 5-120 weight part. In particular, the preferred blending amount is in the range of 30 to 80 parts by weight.
Also, the specific surface area of the porous powder is defined as 10 m 2 / g or more, preferably less than 10 m 2 / g, because the powder has a large particle size and a small surface area, so that the adsorptivity of the wood tar extract is reduced. Therefore, it was set to 10 m 2 / g or more. Although the upper limit of the specific surface area is not particularly defined, any upper limit can be used as long as it can be used with a specific surface area of 10 m 2 / g or more, and it may be appropriately selected in consideration of cost and practicality.
なお、実際の木材用塗料として用いる場合には、塗料を固化させる機能を果たすために、結合剤を配合することが必要である。結合剤としては通常広く用いられている所謂「水性接着剤」が適しており、例えば、酢酸ビニル樹脂系エマルジョン、エチレン・酢酸ビニル共重合樹脂系エマルジョン、アクリル酸樹脂系エマルジョン、水性高分子、イソシアネート、合成ゴム系ラテックス等が使用可能である。なお、本発明においてはこれらのものを総称して「水性接着剤」という。
水性接着剤の配合量は、特に規定しないが、塗料としての適度の粘性や塗装作業性を維持させるためには、前記木タール抽出液１００重量部に対し、３０〜８０重量部の範囲で配合することが望ましい。
When used as an actual wood paint, it is necessary to add a binder in order to fulfill the function of solidifying the paint. As the binder, a so-called “water-based adhesive” that is usually widely used is suitable, for example, vinyl acetate resin emulsion, ethylene / vinyl acetate copolymer resin emulsion, acrylic resin emulsion, aqueous polymer, isocyanate. Synthetic rubber latex can be used. In the present invention, these are collectively referred to as “water-based adhesive”.
The blending amount of the water-based adhesive is not particularly specified, but in order to maintain an appropriate viscosity as a paint and coating workability, it is blended in a range of 30 to 80 parts by weight with respect to 100 parts by weight of the wood tar extract. It is desirable to do.
以上説明した本発明では抽出液として木タール抽出液を代表例にしたが、本発明はこれに限定するものではなく、孟宗竹から竹酢液を製造する際に副生する竹タールや、籾殻から籾酢液を製造する際に副生する籾タールを、木タールと同様に処理することで得られる竹タール抽出液や、籾タール抽出液についても、木タール抽出液と何ら変わることなく、防虫・防腐効果を長期にわたって維持することが可能な塗料組成物材料であることが確認されている。 In the present invention described above, a wood tar extract is used as a representative example of the extract. However, the present invention is not limited to this. From the bamboo tar produced as a by-product when producing bamboo vinegar from Sosetsu bamboo or rice husks. Bamboo tar extract obtained by treating cocoon tar produced as a by-product when producing vinegar vinegar in the same manner as wood tar and potato tar extract, insecticide is not different from wood tar extract. -It has been confirmed that it is a coating composition material capable of maintaining the antiseptic effect over a long period of time.
以下、本発明の実施例を説明するが、合わせて本発明において用いる木タール抽出液及び多孔質粉末の有効性を検証するための実験例を示す。なお、実験例及び実施例において用いる木タール及びその抽出液の詳細は次の通りである。
（１）木タール
ナラを主体とする木材を燃焼炉中で送風空気量不足状態で燃焼させ、排出したガスを冷却して凝縮した液を３ヶ月間静置することで、上下２層に分離したうちの、上層の褐色透明な「木酢液」を取り除いた残りの下層の黒色液が木タールである。比重約１．２、粘調な黒色液体で、甚だしい臭気を発する。
（２）木タール抽出液
ガラス製２リットルビーカーを使用し、上記の木タール５００ｇにエタノール２５０ｇを混合し、プロペラ回転式攪拌機にて３０分攪拌後、２４時間静置したところ、混合液は茶褐色の上層と黒色の下層の２層に分離した。上層部は、臭気の少ない粘性の低い液体で、木タール中のエタノール可溶成分の抽出液（「木タール抽出液」）であり、下層部は悪臭の強い粘調な抽出残渣液である。ビーカーを傾けて抽出液を別の容器に移し、重量を算出したところ、木タール抽出液は４００ｇ、抽出残渣は２５０ｇであった。
Examples of the present invention will be described below, but experimental examples for verifying the effectiveness of the wood tar extract and the porous powder used in the present invention are also shown below. The details of the wood tar and its extract used in the experimental examples and examples are as follows.
(1) Wood tar Wood mainly made of oak is burned in a combustion furnace with insufficient air flow, and the condensed gas is cooled and condensed for 3 months. The remaining black liquid in the lower layer, from which the upper brown transparent “wood vinegar” is removed, is wood tar. It has a specific gravity of about 1.2 and a viscous black liquid that emits a strong odor.
(2) Wood tar extract Using a glass 2-liter beaker, 250 g of ethanol was mixed with 500 g of the above wood tar, stirred for 30 minutes with a propeller rotary stirrer, and allowed to stand for 24 hours. The upper layer and the black lower layer were separated into two layers. The upper layer is a liquid with low odor and low viscosity, which is an extract of ethanol-soluble components in wood tar (“wood tar extract”), and the lower part is a viscous extract residue liquid with strong malodor. When the beaker was tilted and the extract was transferred to another container and the weight was calculated, the wood tar extract was 400 g and the extraction residue was 250 g.
［実験例１］
上記の木タール１００ｇと酢酸ビニル樹脂系エマルジョン接着剤５０ｇを秤取し、高速攪拌機によって混合した後（この混合液を混合液Ａとする）、容量５００ｍｌの蓋付ポリエチレン容器に移して蓋をし、２３℃の恒温室に静置した。２４時間後ガラス棒でかき混ぜて容器の中での液体の状態を観察した。また、ベニヤ板に刷毛で塗装して作業性と塗装面の外観を観察した。
一方、上記の木タール抽出液１００ｇと酢酸ビニル樹脂系エマルジョン接着剤５０ｇを秤り取り、前記混合液Ａと同様の方法にて別の混合液（混合液Ｂとする）を調製するとともに、液体の状態観察と塗装作業性及び塗装面の外観を観察した。
その結果、混合液Ａでは、容器中の状態が「固まりが沈積」、塗装作業性が「塗装し難い」、塗装面の外観が「小突起が多い」ことが認められた。これに対し、混合液Ｂでは、それぞれ「固まりが無く一様」、「塗装に支障無し」、「平滑である」ことが認められた。従って、木タールは塗料の原料としては適切ではないが、木タール抽出液は容器中の状態、塗装作業性、塗装面の外観の点で優れており、塗料の原料として適していることが確認された。
[Experimental Example 1]
100 g of the above wood tar and 50 g of vinyl acetate resin emulsion adhesive are weighed and mixed with a high-speed stirrer (this mixture is referred to as mixture A), then transferred to a 500 ml lidded polyethylene container and capped. And kept in a constant temperature room at 23 ° C. After 24 hours, the mixture was stirred with a glass rod and the liquid state in the container was observed. The veneer board was painted with a brush and the workability and the appearance of the painted surface were observed.
On the other hand, 100 g of the above wood tar extract and 50 g of vinyl acetate resin emulsion adhesive are weighed out to prepare another mixed liquid (mixed liquid B) in the same manner as the mixed liquid A, and liquid The state observation and painting workability and appearance of the painted surface were observed.
As a result, it was recognized that in the mixed liquid A, the state in the container was “deposited in the mass”, the painting workability was “difficult to paint”, and the appearance of the painted surface was “many small protrusions”. On the other hand, in the mixed solution B, it was recognized that “there was no solidity and was uniform”, “no problem in coating”, and “smooth”. Therefore, wood tar is not suitable as a raw material for paint, but wood tar extract is excellent in terms of the condition in the container, painting workability, and appearance of the painted surface, confirming that it is suitable as a raw material for paint. It was done.
［本発明の実施例１〜５及び比較例１〜４］
以下、本発明において規定した条件を満足する実施例１〜５と本発明で規定した条件のいずれかが範囲外の比較例１〜４を表１に示す。
表１において、防虫効果は、次のように判定した。まず、各塗料をベニヤ板（３×３０×５０ｍｍ）２枚の表裏と縁端部に万遍なく塗布し、温度２３℃、相対湿度５０％の恒温室に２４時間放置して、塗布面を固化させた。塗布後２４時間経過したところで、１枚の試験片を所定時間経過毎に、「イエヒメアリ」５匹を入れた５００ｍｌのビーカーに装入し、「イエヒメアリ」の忌避の有無を観察した。５匹全てが近づかない場合を「忌避あり」、１匹でも近づいた場合は「忌避なし」とした。また、防腐効果は、次のように判定した。同一の試験片を３０℃の水蒸気飽和雰囲気の環境の下に曝したことにより行った。試験片にカビの発生が認められた場合に「腐食あり」、全く何らの変化が見られない場合を「変化なし」とした。
[Examples 1 to 5 and Comparative Examples 1 to 4 of the present invention]
Table 1 shows Examples 1 to 5 that satisfy the conditions defined in the present invention and Comparative Examples 1 to 4 in which any of the conditions defined in the present invention is out of the range.
In Table 1, the insect repellent effect was determined as follows. First, each paint is applied evenly on the front and back and edges of two veneer plates (3 x 30 x 50 mm) and left in a temperature-controlled room at 23 ° C and 50% relative humidity for 24 hours to solidify the coated surface. I let you. After 24 hours from the application, each test piece was loaded into a 500 ml beaker containing 5 “Yhimehime” every predetermined time, and the presence or absence of “Yeshimeari” was observed. The case where all five animals were not approached was “repelled”, and the case where one animal was approached was “not repelled”. Further, the antiseptic effect was determined as follows. The same test piece was exposed to an environment of a steam saturated atmosphere at 30 ° C. When the occurrence of mold on the test piece was observed, “corrosion” was indicated, and when no change was observed at all, “no change” was indicated.
表１の比較例１、２から木タール抽出液のみを配合した場合、また、比表面積が１０ｍ２／ｇ未満の場合には、いずれも防虫・防腐効果が短期間で失われてしまい、実用的でないことが分かった。これに対し本発明の実施例１、２では防虫・防腐効果が長期間持続することが認められた。
また、比較例３では、多孔質粉末の配合量が５重量部未満であるため、防虫・防腐効果が長続きせず、比較例４では防虫・防腐効果は満足するが、多孔質粉末の配合量が多すぎることから、塗装作業性や塗装外観が劣り、塗料としての特性が低下することが判明した。
When only the wood tar extract is blended from Comparative Examples 1 and 2 in Table 1, and when the specific surface area is less than 10 m 2 / g, the insect-proofing and antiseptic effects are lost in a short period of time. I knew it was n’t right. On the other hand, in Examples 1 and 2 of the present invention, it was confirmed that the insect repellent and antiseptic effects last for a long time.
In Comparative Example 3, the amount of the porous powder is less than 5 parts by weight, so that the insect repellent / preservative effect does not last long. In Comparative Example 4, the insect repellent / preservative effect is satisfied, but the amount of the porous powder combined Therefore, it was found that the coating workability and the coating appearance were inferior, and the properties as a coating were lowered.
［本発明の実施例６］
表１に示す本発明の実施例のうち実施例５と同一の塗料について、その性能をＪＩＳ Ｋ ５９６０「家庭用屋内塗料」に基づいて評価した。その結果は下記の通りであり、全ての点で問題がなかった。
（塗料性能評価結果）
・容器の中での状態 かき混ぜたとき、堅い固まりが発生せずに一様である。
・塗装作業性 刷毛及びローラーブラシ塗りで塗装作業に支障なし。
・低温安定性 １０℃に冷却しても変質しない。
・加温貯蔵安定性 ５０℃で７日間貯蔵しても安定である。
・乾燥時間 １時間以内
・塗装の外観 塗膜の外観が正常である。
・低温造膜性 ５℃の塗膜形成に異常がない。
・塗り面積 ２回の塗りで１リットル当たり４ｍ２以上塗れる。
[Embodiment 6 of the present invention]
Among the examples of the present invention shown in Table 1, the performance of the same paint as in Example 5 was evaluated based on JIS K 5960 “household indoor paint”. The results were as follows and there were no problems in all respects.
(Paint performance evaluation results)
-State in the container When stirred, it is uniform without producing a hard mass.
・ Coating workability Brush and roller brush painting do not interfere with painting work.
-Low temperature stability Does not change even when cooled to 10 ° C.
-Warm storage stability It is stable even when stored at 50 ° C for 7 days.
・ Drying time Within 1 hour ・ Appearance of coating The appearance of the coating film is normal.
・ Low-temperature film-forming properties No abnormalities in coating film formation at 5 ° C.
・ Coating area 4m 2 or more per liter can be applied by applying twice.
［本発明の実施例７、８及び比較例５、６］
極性有機溶剤の処理効果を検証するために、木タール処理溶媒を種々変更させてそれぞれの防虫・防腐効果を調査した。前掲の実施例１〜５及び比較例１〜４において用いたエタノール処理の木タール抽出液を、溶媒としてｎ-プロパノール（実施例７）、アセトン（実施例８）、蒸留水（比較例５）、トルエン（比較例６）をそれぞれ使用し、これに所定量の湿式ホワイトカーボン、酢酸ビニル樹脂系エマルジョン接着剤を添加し、高速攪拌機で混合した。試験片の調製及び防虫・防腐試験は前掲の場合と同一である。結果を表２として示す。
[Examples 7 and 8 and Comparative Examples 5 and 6 of the present invention]
In order to verify the treatment effect of the polar organic solvent, various insecticide and antiseptic effects were investigated by changing the wood tar treatment solvent. The ethanol-treated wood tar extract used in Examples 1 to 5 and Comparative Examples 1 to 4 described above was used as a solvent with n-propanol (Example 7), acetone (Example 8), distilled water (Comparative Example 5). Toluene (Comparative Example 6) was used, and a predetermined amount of wet white carbon and vinyl acetate resin emulsion adhesive were added thereto and mixed with a high-speed stirrer. The preparation of the test piece and the insect and antiseptic tests are the same as described above. The results are shown in Table 2.
比較例５の極性を有するが無機の溶媒である蒸留水で処理した「水処理木タール抽出液」及び比較例６の無極性の有機溶媒であるトルエンで処理した「トルエン処理木タール抽出液」は、木タール中の防虫・防腐効果の高いフェノール類、アルデヒド類の十分な量を抽出することができず、防虫・防腐効果の持続時間が短かった。これに対し、実施例７の極性有機溶媒であるｎ-プロパノールで処理した「ｎ-プロパノール処理木タール抽出液」及び実施例８の極性有機溶媒であるアセトンで処理した「アセトン処理木タール抽出液」では、十分な量のフェノール類、アルデヒド類が抽出できるので、長期にわたる防虫・防腐効果を維持し得ることが確認された。 "Water-treated wood tar extract" treated with distilled water, which is a polar but inorganic solvent of Comparative Example 5, and "Toluene-treated wood tar extract" treated with toluene, a nonpolar organic solvent, of Comparative Example 6 Was unable to extract sufficient amounts of phenols and aldehydes having high insecticidal and antiseptic effects in wood tar, and the duration of the insecticidal and antiseptic effects was short. In contrast, “n-propanol-treated wood tar extract” treated with n-propanol, which is the polar organic solvent of Example 7, and “acetone-treated wood tar extract, treated with acetone, the polar organic solvent of Example 8,” It was confirmed that a sufficient amount of phenols and aldehydes can be extracted, so that the insecticidal and antiseptic effects can be maintained over a long period of time.
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| KR100994890B1 (en) * | 2010-06-22 | 2010-11-16 | 김의연 | Anti-fouling paint composition for anti-dirtiness of attached marine organism using wood-tar and method of anti-fouling painting for vessel and marine iron construction using thereof |
| KR100994883B1 (en) * | 2010-06-24 | 2010-11-16 | 김의연 | Aqueous anti-fouling paint composition of pro-environment using wood-tar and method of anti-fouling painting for inside the ship and the building using thereof |
| KR101224062B1 (en) | 2010-10-11 | 2013-01-24 | 대한민국 | Preparation method of high calory material from wood-tar |
| CN115179383A (en) * | 2022-07-19 | 2022-10-14 | 常州市瑞悦车业有限公司 | Boxcar bottom plate material and preparation process thereof |
| CN117140670A (en) * | 2023-09-07 | 2023-12-01 | 安徽亮发家居有限公司 | Production method of softened and anti-corrosion wicker branches |
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| LAPS | Cancellation because of no payment of annual fees |