CN100518517C - Antisepticize and mildew preventive of bamboo wood material - Google Patents
Antisepticize and mildew preventive of bamboo wood material Download PDFInfo
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- CN100518517C CN100518517C CNB2008100595647A CN200810059564A CN100518517C CN 100518517 C CN100518517 C CN 100518517C CN B2008100595647 A CNB2008100595647 A CN B2008100595647A CN 200810059564 A CN200810059564 A CN 200810059564A CN 100518517 C CN100518517 C CN 100518517C
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Abstract
The invention provides an anti-septic and anti-mildew agent for bamboo and wood, which is obtained by adding zinc compounds, copper compounds and cationic surfactant to substrates. The invention adopts bamboo vinegar, wood vinegar and grass vinegar as main ingredients and is composed by water-insoluble inorganic compounds to prepare biological (of a chemical type) wood preservative and can also be added with ammonia, ammonium salt or nitrogen compounds of the ammonia to increase the solubility. The invention has the advantages of strong resistance of leachability (wastage rate is less than 2 percent), low moisture absorption, no frosting, low toxicity and good effect of anti-sepsis and anti-mildew, and can also be applied to discoloration of timber or bamboo.
Description
(1) technical field
The present invention relates to a kind of antisepticize and mildew preventive of bamboo wood material.
(2) background technology
Bamboo and timber material contains the needed nutrient of microorganism, under the environment when, microorganism is ruined the degraded bamboo and timber material easily, light downgrading is little to bamboo and timber material influence itself, serious then can make it lose use value, cause the wasting of resources, handle so general bamboo and timber material need carry out anticorrosion mildew-resistant before using.
The bamboo wood preservative comprises that mainly oils preservative, oil carry preservative and water ballast preservative 3 classes both at home and abroad at present, and the most widely used is the water ballast preservative.The oils preservative is except toxicity and the influence to environment to people and animals, and its another major defect is to handle the back product surface to pollute, and has pungent taste simultaneously, these drawbacks limit the range of application of oils preservative.Oil carries preservative because energy crisis, makes its processing cost costliness, and the organic solvent volatilization easily causes environmental pollution and causes fire in processing procedure, thereby is replaced by the water ballast preservative gradually at many application scenarios oil year preservative.CCA (chromatize copper arsenate) is the water ballast preservative that is most widely used in recent years, low price, and it is functional to handle back antiseptic property, mechanical property and top finishing, and resistance leachability is strong.But because its toxicity, Europe, the U.S., Japan forbid that gradually it uses in civilian occasion.Except CCA, other preservatives that contain arsenic or chromium also are faced with same problem.U.S. Koppers Arch, CSI, Osmose, companies such as German Dr Wolman, Belgian Janssen have carried out the research and development of green lumber preservative, wherein quaternary ammonium copper series (ACQ-C and ACQ-B), CuHDO, triazole etc. allegedly are expected to most replace CCA, and have entered practicality.But according to correlative study, this type of preservative is effective not as copper chromium arsenic class to the target effect, and cost is higher relatively, and smell is heavier, the influence operation.Inorganic boron class wood preservative uses the history that also has about 50 years, its advantage is hypotoxicity and broad spectrum antibacterial, but resistance leachability is very poor, present domestic use is more, effect preferably Antisepticize and mildew preventive mainly be copper chromate (ACC), ammonical copper arsenite (ACA) and copper chromium arsenic (CCA) and penta sodium pentachlorophenate and pentachlorophenol.Chromium arsenical copper series is owing to use back heavy metal pollution and arsenic to environmental influence; produce bioxin pollution etc. in pentachlorophenol or the penta sodium pentachlorophenate manufacture process; environment is had negative interaction, to the attention of environmental protection, more and more cause researcher's attention along with in the world.The Japan and the U.S. have forbidden the use of chromium arsenical copper series, and relevant policies are also prepared to put into effect by European countries.At present, also do not have relevant policies in China, the Antisepticize and mildew preventive of use is still based on this series, and large usage quantity, and it is imperative with the consumption that reduces chromium arsenical copper series to seek a kind of new environmental friendly, anti-corrosive mould inhibitor.
(3) summary of the invention
The object of the invention provides a kind of novel environment friendly and the good antisepticize and mildew preventive of bamboo wood material of anticorrosion anti-mold effect.
The technical solution used in the present invention is:
A kind of antisepticize and mildew preventive of bamboo wood material mainly adds zinc compound, copper-containing compound and cationic surfactant by matrix and obtains;
Described matrix is one or more in Bamboo vinegar solution, pyroligneous liquor, the careless vinegar liquid;
Described zinc compound is one of following or wherein multiple mixture: Firebrake ZB, zinc oxide, zinc hydroxide, and addition is: per 1 liter of matrix is added the described zinc compound of 1～200g;
Described copper-containing compound is one of following or wherein multiple mixture: copper borate, copper oxide, Kocide SD, basic copper carbonate, and addition is: per 1 liter of matrix is added the described copper-containing compound of 1～300g;
Described cationic surfactant is one of following or wherein multiple mixture: Dodecyl trimethyl ammonium chloride, DTAB, hexadecyltrimethylammonium chloride, softex kw, OTAC, octadecyl trimethylammonium bromide, myristyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, two dodecyl dimethyl ammonium chloride, Sa Paming, multi-quaternary ammonium salt, Tego amphoteric surfactant, addition is: per 1 liter of matrix is added the described cationic surfactant of 1～300g.
Bamboo vinegar solution, pyroligneous liquor and careless vinegar liquid composition dewater exceptionally, mainly are more than 200 kind of materials such as organic acid, ketone, aldehydes, phenols.These materials itself just have expelling parasite sterilization antibacterial action, add the compound action of each complicated component, so expelling parasite and sterilization antibacterial action are obvious.In addition, Bamboo vinegar solution, pyroligneous liquor and careless vinegar liquid itself also are the good solvents of a kind ofization, and the solubilizer that letones that the inside comprises and being of alcohols material are good is again good bleeding agent.Active component can well be dissolved in the Bamboo vinegar solution and also effectively permeate, is diffused in the bamboo and timber material and goes in the Antisepticize and mildew preventive, thereby better brings into play drug effect, reduces dosing, has played the effect of good raising drug effect.Bamboo vinegar solution, pyroligneous liquor and careless vinegar liquid itself is nontoxic, belongs to the recyclability resource.
With Bamboo vinegar solution, pyroligneous liquor and careless vinegar liquid is main component, and composite water-insoluble inorganic compound makes biology (chemical type) wood preservative, has following advantage: at first, this wood preservative resistance leachability is strong; Secondly, the wood materials of handling with this kind wood preservative is in follow-up use, and hygroscopicity is low, to the problem of the moisture absorption deliquescence that present most of preservative had or handle the material surface and the bloom phenomenon occurs and reduce greatly; The 3rd, because Bamboo vinegar solution, pyroligneous liquor and careless vinegar liquid itself have the effect of anticorrosion mildew-resistant, add the anticorrosion mildew-proof function of zinc compound, can regulate being incorporated in not of control copper-containing compound according to the abominable degree of environment for use.Reaching on the identical antiseptic effect, can reduce toxicity greatly; The 4th, this protectant is except being used for the anticorrosion mildew-resistant of timber bamboo wood, and the variable color that can also be used for timber, bamboo wood is handled.
Also can contain nitrogen-containing compounds such as ammonia, ammonium salt or amine during described antisepticize and mildew preventive of bamboo wood material is formed to increase its dissolubility, its addition is that every 1L matrix is added the 1-200g nitrogen-containing compound.
Concrete, described antisepticize and mildew preventive of bamboo wood material consists of: per 1 liter of matrix is added the described zinc compound of 1～200g, the described copper-containing compound of 1～300g and the described cationic surfactant of 1～300g.
Perhaps, described antisepticize and mildew preventive of bamboo wood material consists of: per 1 liter of matrix is added the described zinc compound of 1～200g, the described copper-containing compound of 1～300g, the described cationic surfactant of 1～300g and the described nitrogen-containing compound of 1-200g.
Preferably, described antisepticize and mildew preventive of bamboo wood material is prepared by following method: in matrix, add zinc compound, after the stirring and dissolving, add the nitrogen-containing compound that is selected from ammonia, ammonium salt or amine and form complex compound, add copper-containing compound again, or add copper-containing compound and cationic surfactant successively, obtain described antisepticize and mildew preventive of bamboo wood material.Described nitrogen-containing compound can increase solvability, can be one of following: ammoniacal liquor, MEA, diethanol amine, triethanolamine, double focusing cyanamide, melamine and ethylenediamine.
Preferably, described antisepticize and mildew preventive of bamboo wood material consists of: per 1 liter of matrix is added 10～50g zinc oxide, 10～50g copper oxide, 20～60g myristyl dimethyl benzyl ammonium chloride.
Preferably, described antisepticize and mildew preventive of bamboo wood material is obtained by following method: per 1 liter of matrix is added 80～120g zinc oxide, the adding volume is that the mass concentration of matrix volume 1～5% is 10～20% ammoniacal liquor formation complex compound, add 5～20g basic copper carbonate, 5～20g stearyl dimethyl benzyl ammonium chloride more successively, obtain described antisepticize and mildew preventive of bamboo wood material.
The beneficial effect of antisepticize and mildew preventive of bamboo wood material of the present invention is mainly reflected in: resistance leachability strong (turnover rate is less than 2%), hygroscopicity are low, no frosting phenomenon, and low, the anticorrosion anti-mold effect of toxicity is good, can also be used for the variable color processing of timber, bamboo wood.
(4) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Toward 1L pyroligneous liquor (Zhejiang Forest Zhongzhu Technology Co., Ltd.'s product, down together), add 40g zinc oxide, stirring adds the dissolving of 10g copper oxide again up to dissolving, then adds 30g myristyl dimethyl benzyl ammonium chloride (technical grade, intelligent extra large (group) the development in science and technology Co., Ltd in Guangzhou product) obtain preservative, soak bamboo wood after 3 hours, placed in the open 1 month, observe anticorrosion anti-mold effect.
Embodiment 2:
Toward 1L Bamboo vinegar solution (the refreshing bamboo charcoal industry in Suichang, Zhejiang Co., Ltd product, down together), add 100g zinc oxide, after the complexing of adding 30ml20% ammoniacal liquor, stir up to dissolving, add 10g basic carbonate copper dissolution again, then add 10g stearyl dimethyl benzyl ammonium chloride (technical grade, intelligent extra large (group) the development in science and technology Co., Ltd in Guangzhou product) obtain preservative, soak bamboo wood after 1 hour, the open-air placement 1 month observed anticorrosion anti-mold effect.
Embodiment 3:
In the 1L Bamboo vinegar solution, add the 100g zinc hydroxide, after adding the 10% diethanol amine aqueous solution complexing of 50ml, stir, add the dissolving of 30g copper oxide again up to dissolving, add the two dodecyl dimethyl ammonium chloride (technical grades of 20g at last, intelligent extra large (group) the development in science and technology Co., Ltd in Guangzhou product), obtain preservative soaked bamboo wood after 2 hours, the open-air placement 1 month observed anticorrosion anti-mold effect.
Embodiment 4:
In the 1L pyroligneous liquor, add the 150g zinc hydroxide, after adding the 15% ethylenediamine solution complexing of 40ml, stir, add 100g basic carbonate copper dissolution again up to dissolving, add 50g octadecyl trimethylammonium bromide (technical grade at last, intelligent extra large (group) the development in science and technology Co., Ltd in Guangzhou product), obtain preservative soaked masson pine timber after 3 hours, the open-air placement 1 month observed anticorrosion anti-mold effect.
Embodiment 5:
Toward 1L grass vinegar liquid (Zhejiang Forest Zhongzhu Technology Co., Ltd.'s product, down together), add the 50g Firebrake ZB, after the 20% double focusing cyanamide aqueous solution complexing of adding 30ml, stirring is up to dissolving, add the dissolving of 150g copper borate again, add 150g Sa Paming (technical grade, Nanjing WeiEr chemical engineering Co., Ltd's product) at last, obtain preservative, soak bamboo wood after 2 hours, placed in the open 1 month, observe anticorrosion anti-mold effect.
Embodiment 6:
In the 1L Bamboo vinegar solution, add 20g zinc oxide, after adding the 25% triethanolamine aqueous solution complexing of 20ml, stir, add the dissolving of 100g copper borate and 100g copper oxide again up to dissolving, add 50gTego amphoteric surfactant (technical grade at last, Nanjing WeiEr chemical engineering Co., Ltd's product), obtain preservative soaked masson pine timber after 4 hours, the open-air placement 1 month observed anticorrosion anti-mold effect.
Embodiment 7:
In the 1L Bamboo vinegar solution, add 20g zinc oxide and 20g zinc hydroxide, stir up to dissolving, add the 10g copper oxide again, stirring and dissolving adds 20g dodecyl methyl ammonium bromide obtain preservative at last, soak bamboo wood after 1 hour, placed in the open 1 month, observe anticorrosion anti-mold effect.
Embodiment 14:
In the 1L Bamboo vinegar solution, add 40g zinc oxide, stir up to dissolving, add the 10g copper oxide again, stirring and dissolving adds 30g dodecyl methyl ammonium chloride obtain preservative at last, soaks bamboo wood after 1 hour, places in the open 1 month, observes anticorrosion anti-mold effect.
Embodiment 15:
In the 1L Bamboo vinegar solution, add the 60g zinc hydroxide, stir up to dissolving, add the 40g basic copper carbonate again, stirring and dissolving adds 20g myristyl methyl-benzyl ammonium chloride obtain preservative at last, soak masson pine timber after 2 hours, placed in the open 1 month, observe anticorrosion anti-mold effect.
Embodiment 16:
In the 1L pyroligneous liquor, add 50g zinc oxide and 30g Firebrake ZB, stirring is up to dissolving, add 10g copper oxide, 10g Kocide SD and 30g basic carbonate copper dissolution again, add 40g stearyl dimethyl benzyl ammonium chloride and 40g myristyl methyl-benzyl ammonium chloride obtain preservative at last, soak bamboo wood after 2 hours, placed in the open 1 month, observe anticorrosion anti-mold effect.
Embodiment 17:
In the 1L pyroligneous liquor, add 10g Firebrake ZB and 40g zinc oxide, stir up to dissolving, add the dissolving of 20g copper borate again, add 20g dodecyl bromination ammonium obtain preservative at last, soak bamboo wood after 4 hours, placed in the open 1 month, observe anticorrosion anti-mold effect.
Embodiment 18:
In 1L grass vinegar liquid, add the 30g zinc hydroxide, stir up to dissolving, add the dissolving of 10g copper oxide and 40g Kocide SD again, add 50g tetradecyl dimethyl benzyl ammonium obtain preservative then, soak bamboo wood after 5 hours, the open-air placement 1 month observed anticorrosion anti-mold effect.
Embodiment 19:
In 1L grass vinegar liquid, add 20g Firebrake ZB, 20g zinc oxide and 20g zinc hydroxide, stir up to dissolving, add the dissolving of 20g copper borate again, add 50g hexadecyltrimethylammonium chloride obtain preservative at last, soak bamboo wood after 1 hour, the open-air placement 1 month observed anticorrosion anti-mold effect.
Embodiment 20:
In the 1L pyroligneous liquor, add 50g zinc oxide, stir up to dissolving, add the dissolving of 20g copper borate again, then add 20g stearyl dimethyl benzyl ammonium chloride obtain preservative, soak bamboo wood after 3 hours, placed in the open 1 month, observe anticorrosion anti-mold effect.
Comparative Examples 1:
In 1L water, add the 50g zinc chloride, stir up to dissolving, add the dissolving of 50g copper chloride again, then add 30g hexadecyltrimethylammonium chloride obtain preservative, soak bamboo wood after 5 hours, placed in the open 1 month, observe anticorrosion anti-mold effect.
Comparative Examples 2:
In the 1L Bamboo vinegar solution, add 50g copper sulphate, stir up to dissolving, obtain preservative soaked bamboo wood after 3 hours, placed in the open 1 month, observed anticorrosion anti-mold effect.
Comparative Examples 3:
In the 1L Bamboo vinegar solution, add 50g copper sulphate and 50g triazole copper, stir up to dissolving, obtain preservative soaked masson pine timber after 3 hours, placed in the open 1 month, observed anticorrosion anti-mold effect.
Comparative Examples 4:
In the 1L Bamboo vinegar solution, add 50g copper sulphate, 50g penta sodium pentachlorophenate and 50g pentachlorophenol, stir up to dissolving, obtain preservative soaked bamboo wood after 3 hours, placed in the open 1 month, observed anticorrosion anti-mold effect.
Observed result sees Table 1:
Table 1
| Embodiment | Antiseptic effect | Anti-mold effect |
| 1 | II | 0 |
| 2 | II | 1 |
| 3 | I | 1 |
| 4 | I | 0 |
| 5 | I | 0 |
| 6 | I | 0 |
| 7 | I | 0 |
| 8 | II | 0 |
| 9 | I | 0 |
| 10 | I | 1 |
| 11 | I | 0 |
| 12 | II | 0 |
| 13 | I | 1 |
| 14 | I | 0 |
| 15 | I | 0 |
| 16 | II | 0 |
| 17 | I | 1 |
| 18 | I | 0 |
| 19 | I | 1 |
| 20 | I | 1 |
| Comparative Examples 1 | III | 3 |
| Comparative Examples 2 | II | 2 |
| Comparative Examples 3 | III | 1 |
| Comparative Examples 4 | II | 2 |
| Blank bamboo wood | IV | 4 |
| Blank masson pine | IV | 4 |
The mildew-resistant experiment effect is estimated:
0: specimen surface does not have mycelia
1: specimen surface infection hypha area＜1/4
2: specimen surface infection hypha area is 1/4～1/2
3: specimen surface infection hypha area 1/2～3/4
4: specimen surface infection hypha area〉3/4
Corrosion resistant grade and weight loss percentage see Table 2:
Table 2
| The rotten grade of corrosion resistant | Weight loss percentage |
| The strong corrosion resistant of I | 0～10％ |
| The II corrosion resistant | 11～24％ |
| III corrosion resistant slightly is rotten | 25～44％ |
| IV is corrosion resistant not | >45％ |
Claims (7)
1. an antisepticize and mildew preventive of bamboo wood material mainly adds zinc compound, copper-containing compound and cationic surfactant by matrix and obtains;
Described matrix is one or more in Bamboo vinegar solution, pyroligneous liquor, the careless vinegar liquid;
Described zinc compound is one of following or wherein multiple mixture: Firebrake ZB, zinc oxide, zinc hydroxide, and addition is: per 1 liter of matrix is added the described zinc compound of 1～200g;
Described copper-containing compound is one of following or wherein multiple mixture: copper borate, copper oxide, Kocide SD, basic copper carbonate, and addition is: per 1 liter of matrix is added the described copper-containing compound of 1～300g;
Described cationic surfactant is one of following or wherein multiple mixture: Dodecyl trimethyl ammonium chloride, DTAB, hexadecyltrimethylammonium chloride, softex kw, OTAC, octadecyl trimethylammonium bromide, myristyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, two dodecyl dimethyl ammonium chloride, Sa Paming, multi-quaternary ammonium salt, Tego amphoteric surfactant, addition is: per 1 liter of matrix is added the described cationic surfactant of 1～300g.
2. antisepticize and mildew preventive of bamboo wood material as claimed in claim 1 is characterized in that: described antisepticize and mildew preventive of bamboo wood material also contains nitrogen-containing compound in forming, and addition is that every 1L matrix is added 1～200g nitrogen-containing compound;
Described nitrogen-containing compound is one of following: ammoniacal liquor, MEA, diethanol amine, triethanolamine, double focusing cyanamide, melamine and ethylenediamine.
3. antisepticize and mildew preventive of bamboo wood material as claimed in claim 1 is characterized in that: described antisepticize and mildew preventive of bamboo wood material consists of: per 1 liter of matrix is added the described zinc compound of 1～200g, the described copper-containing compound of 1～300g and the described cationic surfactant of 1～300g.
4. antisepticize and mildew preventive of bamboo wood material as claimed in claim 2 is characterized in that: described antisepticize and mildew preventive of bamboo wood material consists of: per 1 liter of matrix is added the described zinc compound of 1～200g, the described copper-containing compound of 1～300g, the described cationic surfactant of 1～300g and the described nitrogen-containing compound of 1～200g.
5. antisepticize and mildew preventive of bamboo wood material as claimed in claim 2, it is characterized in that: described antisepticize and mildew preventive of bamboo wood material is prepared by following method: in matrix, add zinc compound, after the stirring and dissolving, add described nitrogen-containing compound and form complex compound, add copper-containing compound and cationic surfactant more successively, obtain described antisepticize and mildew preventive of bamboo wood material.
6. antisepticize and mildew preventive of bamboo wood material as claimed in claim 1 is characterized in that: described antisepticize and mildew preventive of bamboo wood material consists of: per 1 liter of matrix is added 10～50g zinc oxide, 10～50g copper oxide, 20～60g myristyl dimethyl benzyl ammonium chloride.
7. antisepticize and mildew preventive of bamboo wood material as claimed in claim 3, it is characterized in that: described antisepticize and mildew preventive of bamboo wood material is obtained by following method: per 1 liter of matrix is added 80～120g zinc oxide, the adding volume is that the concentration of matrix 1～5% is 10～20% ammoniacal liquor formation complex compound, add 5～20g basic copper carbonate, 5～20g stearyl dimethyl benzyl ammonium chloride more successively, obtain described antisepticize and mildew preventive of bamboo wood material.
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2008
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