KR101092621B1 - Wood preservative composition - Google Patents

Abstract

PURPOSE: A wood preservative composition is provided to restrain copper elution thereby having excellent antiseptic ability. CONSTITUTION: A wood preservative composition comprises 01-50wt% copper base inorganic preserver particles, 1-70wt% quaternary ammonium salt compound, 3-50wt% polyoxyethylene sorbitan fatty acid ester, and 5-95wt% water. The average particle size of the copper base inorganic particles is 0.40-0.65μm.

Description

Wood preservative composition

The present invention relates to wood preservation compositions.

To prevent biological degradation of wood, wood should be treated with preservatives, including one or more preservatives, preservatives and insect repellents. Such treatment may include, for example, treating wood in a closed pressurized or vacuum system, heating or impregnating system, and the like, or impregnating or dipping wood into a medicament containing a preservative for wood or spraying the medicament. And the like.

Conventional representative pressurized wood preservatives used in the wood treatment are soluble chromated copper arsenate (CCA). The CCA has been widely used because of its advantage in that it can be used for treatment in a pressure gauge, which is a short treatment time and an efficient treatment method, but has been banned in Korea since 2007 due to a hazard problem.

As another water-soluble compound to replace CCA, U. S. Patent No. 4,622, 248 discloses a method for preparing a copper amine complex by dissolving a mixture of copper carbonate and copper hydroxide in a mixture of ethanolamine and water. However, although the copper amine-based preservative has excellent weather resistance, there is a problem of causing environmental pollution due to copper dissolution. Therefore, copper dissolution can be suppressed, and a wood preservative excellent in antiseptic property is required.

US Patent Publication No. 2004/0258767 discloses wood preservative compositions comprising inorganic components such as metals and organic fungicides, wherein at least one of the inorganic components and organic fungicides is in particulate form.

US Patent Publication 2005/0256026 discloses an aqueous fungicide slurry comprising copper particles, zinc particles or mixtures thereof, quaternary ammonium salt compounds and one or more dispersants.

US 2006/0062926 discloses a wood preservation method for injecting wood into a slurry comprising a metal, a dispersant, and a solvent in particulate form.

However, despite these prior arts, there is still a need for wood preservation compositions that are high in stability and that provide improved anti-settling and metal preservation.

One aspect of the present invention is to provide a wood preservation composition that is stable for a long time, the copper dissolution is suppressed, and excellent antiseptic.

Another aspect of the present invention is to provide an antiseptic wood produced using the wood preservation composition.

According to one aspect of the invention

Copper-based inorganic preservative particles; Quaternary ammonium salt compounds; Polyoxyethylene sorbitan fatty acid esters; And water, wherein the copper-based inorganic preservative particles have a volume average particle diameter (d50) of 0.40 to 0.65 μm.

The polyoxyethylene sorbitan fatty acid ester is used as a dispersant in the wood preservation composition according to an aspect of the present invention, and it is stable for a long time by using copper-based inorganic preservative particles having a volume average particle size of 0.40 to 0.65 μm, and copper dissolution is suppressed. The wood preservation composition having excellent antiseptic power is obtained, and the wood treated with the wood preservation composition is suppressed from copper dissolution and has excellent antiseptic power.

1A to 1C are particle size distribution diagrams of copper fine particles dispersed in wood preservation compositions prepared in Comparative Examples 1 and 2 and Example 1, respectively.

Hereinafter will be described in more detail with respect to wood preservation composition according to an exemplary embodiment of the present invention.

Wood preservative composition according to one embodiment is a copper-based inorganic preservative particles; Quaternary ammonium salt compounds; Polyoxyethylene sorbitan fatty acid esters; And it includes water, the volume average particle diameter (d50) of the copper-based inorganic preservative particles is 0.40 to 0.65 ㎛.

The wood preservative composition is excellent in dispersion stability of the inorganic inorganic preservative particles and the penetration into wood by appropriate selection of polyoxyethylene sorbitan fatty acid ester and copper-based inorganic preservative particle size. In addition, the wood preservation composition can be solubilized in a high concentration of an organic preservative low solubility in water.

The wood preservation composition is a process for adjusting the size of the particles for a long time through the process of making microparticles of less than 1 ㎛ using a physical method such as a ball mill (ball mill) that requires a high cost and a long time work or a chemical method It can be prepared to disperse the fine secondary particles having a d50 value of less than 1 ㎛ using a commercially available copper-based inorganic preservative without passing through.

In addition, the wood preservation composition is easy to transport, storage, etc. by including a high concentration of the inorganic preservatives and copper-based inorganic preservatives and optionally organic preservatives for the implementation of preservative wood, can be prepared in a large amount of diluent in a small amount It is economical. In addition, since the composition does not contain anionic surfactants, there is no problem of dissolution of fine copper particles, and there is no problem of iron (Fe) corrosion since the foam is small during the preservative treatment and the pH of the diluent obtained by dilution with water is neutral. .

If the volume average particle diameter (d50) of the copper-based inorganic preservative particles is too small, the aggregation phenomenon between the particles becomes remarkable, causing precipitation, and once the aggregated particles may be difficult to disperse again, the copper-based inorganic If the volume average particle diameter (d50) of the preservative particles is too large, there may be a problem that is not only easy to precipitate but also difficult to disperse in water.

In addition, the d98 of the copper-based inorganic preservative particles in the wood preservation composition may be 1.0 to 5.0 ㎛. If the d98 is too small may have a problem that the aggregation phenomenon is more remarkable, if the d98 is too large may have a problem that the precipitation phenomenon is remarkable.

When the polyoxyethylene sorbitan fatty acid ester is used in combination with a quaternary ammonium compound, the average particle diameter of the copper-based inorganic preservative dispersed in the wood preservation composition may be greatly reduced, thereby contributing to long-term stability of the composition. In addition, the polyoxyethylene sorbitan fatty acid ester may solubilize organic preservatives that are not soluble in water at high concentration.

The number of polyoxyethylene repeating units in the polyoxyethylene sorbitan fatty acid ester in the wood preservation composition may be 0 to 25. If the number of the polyoxyethylene repeating unit is too small, there is a problem that the dispersibility to water is lowered to precipitate a copper-based inorganic preservative, if the number of the polyoxyethylene repeating unit is too large solubility in water too As a result, the dispersion affinity for the copper-based inorganic preservative in the form of hydrophobic particles may be lowered, thereby causing a problem of precipitation.

The polyoxyethylene sorbitan fatty acid ester is polyoxyethylene [20] sorbitan monolaurate, polyoxyethylene [20] sorbitan monopalmitate, polyoxyethylene [20] Polyoxyethylene sorbitan monooleate, polyoxyethylene [20] sorbitan monostearate, polyoxyethylene [20] sorbitan tristearate, polyoxyethylene [20] Polyoxyethylene sorbitan triisostearate, polyoxyethylene [20] polyoxyethylene sorbitan trioleate or mixtures thereof are preferred, but are not necessarily limited to these and may be used in the art. Any oxyethylene sorbitan fatty acid ester can be used.

The content of the polyoxyethylene sorbitan fatty acid ester may include 0.5 to 80% by weight of the total weight of the composition. For example, it may include 10 to 50% by weight. When the content of the polyoxyethylene sorbitan fatty acid ester is too low, the secondary particle size of the copper-based inorganic preservative particles is increased by 1 μm or more, so that it is not easy to penetrate into the interior of the wood, resulting in an increase in copper dissolution. Antiseptic force may be lowered. When the content of the polyoxyethylene sorbitan fatty acid ester is too high, the content of the copper-based inorganic preservative and the quaternary ammonium salt compound is lowered, thereby reducing the active ingredient exhibiting the preservative performance of the wood, and increasing the viscosity of the wood preservation composition Mixing can be difficult.

In the wood preservation composition, the copper-based inorganic preservative is preferably a salt containing copper or a complex containing copper or a mixture thereof. Specifically, the copper-based inorganic preservatives include copper carbonate, copper hydroxide, copper oxide, copper oxychloride, copper sulfate, copper nitrate, and copper nitrate. Copper chloride, or a mixture thereof.

The copper-based inorganic preservative may be a micronized powder having a particle size range of 0.001 to 100 ㎛. For example, a high content of a copper-based inorganic preservative may be penetrated into wood by using a wood-preserving composition comprising a copper-based inorganic preservative particle powder having a particle size range of 1 μm or less. In addition, the wood treated with the wood preservative composition can suppress the leaching of the copper-based inorganic preservative and can have improved antiseptic performance.

The content of the copper-based inorganic preservative may be 0.1 to 50% by weight of the total weight of the composition. For example, it may be 1 to 40% by weight. If the copper-based inorganic preservative content is less than 0.1% by weight, the antiseptic performance may be lowered. If the content is 50% by weight or more, the stability of the composition may be lowered.

In the wood preservation composition, the quaternary ammonium salt compound plays a secondary role in dispersing the copper-based inorganic preservative, and acts as a water-soluble organic preservative and solubilizes an organic preservative that is insoluble in water at a high concentration.

The cation of the quaternary ammonium salt compound in the wood preservation composition may be at least one selected from the group consisting of N-dimethylbenzylalkylammonium and didecyldimethylammonium. In addition, the anion of the quaternary ammonium salt compound is hydroxide (hydroxide), chloride (carbonate), carbonate (carbonate), bicarbonate (bicarbonate), fluoride (fluoride), sulfate (sulfate), nitrate (nitrate), It may be at least one selected from the group consisting of phosphate, and acetate.

The content of the quaternary ammonium salt compound is preferably 1 to 70% by weight of the total weight of the composition. If the quaternary ammonium compound is less than 1% by weight, the synergistic effect of the antiseptic performance is not exhibited together with the copper-based inorganic preservative, and it is difficult to implement a secondary role as a dispersion stabilizer. If the content is more than 70% by weight, the copper-based inorganic preservative In addition to lowering the amount of polyoxyethylene sorbitan fatty acid esters that play a major role in the long-term stability of the cause of the precipitation of copper-based inorganic preservatives in storage and preservative performance of the preservative wood may be lowered.

The wood preservative composition is 0.1 to 50% by weight of a copper-based inorganic preservative; 1 to 70 wt% of quaternary ammonium salt compound, 3 to 50 wt% of polyoxyethylene sorbitan fatty acid ester; And 5 to 95% by weight of water; may include. Wood preservation composition in the composition range can provide properties such as improved phase stability. In the composition, the sum of the quaternary ammonium salt compound and the polyoxyethylene sorbitan fatty acid ester may be 10% by weight or more. If the content is less than 10% by weight, the stability of the wood preservation composition may be lowered and precipitation may occur.

The wood preservative composition may further comprise an organic preservative. The organic preservative may be an organic iodine compound, a triazole compound, another fungicide or a mixture thereof. The triazole-based compound, organic iodine compound and other fungicides may be used as preservatives and / or preservatives.

The preservative and / or preservative content may be 0.1 to 20% by weight to provide a synergistic effect on the preservative performance of the wood preservative composition. If the amount of the preservative and / or the preservative is less than 0.1% by weight, the preservative may not be exhibited. If the content is more than 20% by weight, precipitation may occur.

The organoiodine compound is 3-iodo-2-propynylbutyl carbamate (IPBC), 3-iodo-2-propynylbutyl carbamate pyridyl phosphorothioate (3 -iodo-2-propynylbutyl carbamate phylidyl phospholothiolate (IPBCP), 3-iodo-3-propynyl succinate, p-chlorophenyl-3-iodopropynyl formal (p chlorophenyl-3-iodopropynyl formal, triiodoallyl alcohols, or mixtures thereof.

The triazole-based compound may include tebuconazole, propiconazole, azaconazole, cyproconazole, phenbuconazole, myclobutanil, and tribuconazole. It may be triadimenol or a mixture thereof.

The other fungicides may be pyrimidine compounds, sulfonamide compounds, nitrile compounds, benzothiazole compounds, isothiazoline compounds, benzoisothiazoline compounds, pyridine compounds, or mixtures thereof.

For example, the other fungicides include nuarimol, phenarimol, tolylfluanide, dichlorofluanide, chlorothalonil, hexaconazole, Benzothiazole, octhilinone, or mixtures thereof.

The wood preservation composition may further include other pesticides. For example, the other insecticides include bifenthrin, siraflofen, tralomethrin, cyphenothrin, acrinathrin, cypermethrin, Permethrin, deltamethrin, diazinon, chlorofenvinphos, phoxim, chloropyriphos, smithion, or mixtures thereof.

For example, the insecticide may be deltamethrin, cypermethrin, or permethrin, which is low toxicity and has excellent drug sustainability.

For example, the organic preservative may be ciproconazole, tebuconazole, propicoazole, benzothiazole, iodopropylbutylcarbamate (IPBC), methylisothiazolidone, bifenthrin, deltamethrin, permethrin And at least one selected from the group consisting of cypermethrin.

The organic preservative compounds are easily decomposed in alkali, but the wood preservative composition is neutral between pH 5 and 7 so that the compounds are not decomposed and can maintain antiseptic, antiseptic, and insect repellent properties.

The wood preservative composition is 0.1 to 50% by weight of a copper-based inorganic preservative; 1 to 70 wt% of quaternary ammonium salt compound, 3 to 50 wt% of polyoxyethylene sorbitan fatty acid ester; It may include 0.1 to 20% by weight of the organic preservative and 5 to 95% by weight of water. Wood preservation composition in the composition range can provide properties such as improved antiseptic force. In the composition, the sum of the quaternary ammonium salt compound and the polyoxyethylene sorbitan fatty acid ester may be 10% by weight or more. If the content is less than 10% by weight, the stability of the wood preservation composition may be lowered and precipitation may occur.

According to another embodiment of the present invention, there is provided an antiseptic wood produced using the wood preservation composition described above. The method of preserving the wood may be mass production of antiseptic wood using a general vacuum pressurized anticorrosive production equipment as well as a method of immersion, spraying, etc. Vacuum pressurized methods can be used.

The present invention is described in more detail through the following examples and comparative examples. However, the examples are provided to illustrate the present invention, and the scope of the present invention is not limited only to these examples.

(Preparation of wood preservation composition)

Wood preservation compositions of the following examples and comparative examples were prepared by sufficiently mixing so that components such as copper carbonate powder can be stably dispersed and / or solubilized in water. The micronized copper carbonate powder used in the following examples and comparative examples was obtained from Philbro-Tech.

Example 1

30% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

40 wt% of water

The volume average particle diameter (d50) of the micronized copper carbonate powder measured using a laser diffraction size analyzer (Sympatec GmbH) in the composition was 0.62 μm, and d98 was 1.80 μm.

Example 2

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 3.33 wt%

6.67 weight% of polyoxyethylene (20) sorbitan monooleate (Tween 80)

80% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.89 μm.

Example 3

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 5% by weight

Polyoxyethylene (20) sorbitan monooleate (Tween 80) 10% by weight

75% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.63 μm.

Example 4

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 6.66 wt%

Polyoxyethylene (20) sorbitan monooleate (Tween 80) 13.34 wt%

70% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.62 μm.

Example 5

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

60% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.62 μm.

Example 6

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 15% by weight

Polyoxyethylene (20) sorbitan monooleate (Tween 80) 30% by weight

45 wt% of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.62 μm.

Example 7

10% by weight of micronized copper carbonate powder

20% by weight of didecyldimethylammonium carbonate (DDAC)

40 weight% of polyoxyethylene (20) sorbitan monooleate (Tween 80)

30% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.62 μm.

Example 8

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 25% by weight

50% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

15% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.62 μm.

Example 9

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

IPBC 5%

55% by weight of water

Example 10

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

Ciproconazole 5%

55% by weight of water

Example 11

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

Tebuconazole 5%

55% by weight of water

Example 12

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

Propicosol 5%

55% by weight of water

Example 13

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

Benzothiazole 5%

55% by weight of water

Comparative Example 1

30% by weight of micronized copper carbonate powder

70% by weight of water

The volume average particle diameter (d50) of the micronized copper carbonate powder measured using a laser diffraction size analyzer (Sympatec GmbH) in the composition was 14.6 μm, and d98 was 24.6 μm.

Comparative Example 2

30% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

40 wt% of water

The volume average particle diameter (d50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 4.2 μm, and d98 was 14.6 μm.

Comparative Example 3

10% by weight of micronized copper carbonate powder

90 wt% of water

Comparative Example 4

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

80% by weight of water

Comparative Example 5

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 0.33 wt%

Polyoxyethylene (20) sorbitan monooleate (Tween 80) 0.67 wt%

89% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 12 μm.

Comparative Example 6

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 0.66 wt%

Polyoxyethylene (20) sorbitan monooleate (Tween 80) 1.34 wt%

88% by weight of water

The volume average particle diameter (d50) of the micronized copper carbonate powder measured using a laser diffraction size analyzer (Sympatec GmbH) in the composition was 7 μm.

Comparative Example 7

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 1.33 wt%

Polyoxyethylene (20) sorbitan monooleate (Tween 80) 2.67% by weight

86% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 5 μm.

Comparative Example 8

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 2% by weight

4% by weight of polyoxyethylene (20) sorbitan monooleate (Tween 80)

84% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 3 μm.

Comparative Example 9

10% by weight of micronized copper carbonate powder

Didesyldimethylammonium carbonate (DDAC) 2.66 wt%

5.34 weight% of polyoxyethylene (20) sorbitan monooleate (Tween 80)

82% by weight of water

The volume average particle diameter (d50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 1.5 μm.

Comparative Example 10

10% by weight of micronized copper carbonate powder

10% by weight of cetyl trimethylammonium bromide

0.1 wt% sodium polyacrylate

79.9% by weight of water

The volume average particle diameter (d 50) of the micronized copper carbonate powder measured using a laser diffraction particle size analyzer (Sympatec GmbH) in the composition was 0.20 μm.

Comparative Example 11

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene nonylphenyl ether

60% by weight of water

Comparative Example 12

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene octylphenyl ether

60% by weight of water

Comparative Example 13

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene lauryl ether

60% by weight of water

Comparative Example 14

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene stearyl ether

60% by weight of water

Comparative Example 15

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene tridecyl ether

60% by weight of water

Comparative Example 16

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene lauryl ether

60% by weight of water

Comparative Example 17

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene lauryl amine

60% by weight of water

Comparative Example 18

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene stearyl amine

60% by weight of water

Comparative Example 19

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene tallow amine

60% by weight of water

Comparative Example 20

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight sodium dodecyl benzene sulfonate

60% by weight of water

Comparative Example 21

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of sodium polyoxyethylene nonylphenyl sulfate

60% by weight of water

Comparative Example 22

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of ammonium polyoxyethylene stearyl sulfate

60% by weight of water

Comparative Example 23

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene phenyl ether phosphate

60% by weight of water

Comparative Example 24

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene lauryl ether phosphate

60% by weight of water

Comparative Example 25

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of stearyl ether phosphate

60% by weight of water

Comparative Example 26

10% by weight of micronized copper carbonate powder

10% by weight of didecyldimethylammonium carbonate (DDAC)

20% by weight of polyoxyethylene monotridecyl ether phosphate

60% by weight of water

Evaluation Example 1: Stability Evaluation

It was visually observed whether precipitation occurred after leaving the wood preservation compositions of Examples 1 to 13 and Comparative Examples 1 to 26 at room temperature for 3 months.

Wood preservation composition of Examples 1 to 13 was maintained stability without precipitation even after 3 months at room temperature. In contrast, the wood preservative composition of Comparative Examples 1 to 26 was precipitated within 2 to 3 days at room temperature.

In addition, the stock preservation composition and the 100-fold dilution (dilution with water) of Examples 9 to 13, which additionally include an organic preservative, were left for 3 months at -4 ° C and 25 ° C, respectively, and then visually observed for precipitation.

The composition stock solutions and the 100-fold dilutions of Examples 9 to 13 did not generate precipitation at -4 ° C and 25 ° C after 3 months. Thus, the compositions of Examples 9 to 13, which contain an organic preservative with low solubility in water, maintain the stability of the dispersion when diluted to produce the preservative wood.

Evaluation Example 2 Copper Elution Test According to Dispersed Copper Particle Size

Wood specimens used to measure copper dissolution were prepared by the following method. First, the wood preservation composition prepared in Examples 2 to 8 and Comparative Examples 5 to 10 was treated with a pressurized method by diluting the wood preservation composition prepared in Examples 2 to 8 and Comparative Examples 5 to 10 with lumber having a size of 10.5 × 10.5 × 400 cm ³ , which is a pine pine (670-720 kg / m ³ ). . Specifically, the pressurization process was performed in order of full exhaust stage (600 mmHg, 30 minutes), pressurization (15 kg / m ³ , 3 hours), rear exhaust stage (600 mmHg, 30 minutes), and stop (30 minutes). The injection volume of the diluted wood preservative composition was 120-200 kg / m ^{3 of US} pine. The injection amount is a value obtained by the difference between the weight of wood after treatment and the weight of wood before treatment, and means the absorption of pure chemical liquid.

The copper content contained in the specimens treated with the wood preservation compositions of Examples 2 to 8 and Comparative Examples 5 to 10 was measured by the Atomic Absorption Spectroscopy (ABS) method of measuring the infiltration and absorption of preservative and insect repellent wood of National Forest Research Institute Notification No. 2004-7. It measured according to.

The untreated wood specimen used in the measuring method was taken to a thickness of 5 mm from the inner side of 30 cm from the fiber direction cut surface, and cut the section cut to a width of 10 mm from the center part of the collected test piece to 1/2 in the longitudinal direction again. One was used. It was immersed in distilled water for 5 months for copper leaching. In order to accurately quantify the accumulated amount of the eluted copper, it was measured using an atomic absorptivity meter.

The amount of copper leaching over time was calculated from the difference between the copper content in the wood specimens and the copper content in the wooden specimens over time before dipping into distilled water.

Elapsed time
[month] Copper Dissolution Rate [ppm] Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 One 8 5 2 0.7 0.5 4 2 22 13 5 7 2 11 3 37 26 13 13 5 24 4 40 38 25 18 9 32 5 51 45 33 24 15 48 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 One 0.3 0.2 0.1 0.2 0.1 0.1 2 1.2 1.9 2.1 2.3 1.8 1.2 3 3.4 2.8 2.5 2.8 2.4 2.0 4 5.6 3.2 3.2 3.2 3.2 2.8 5 8.0 3.2 3.2 3.2 3.2 3.2 Example 8 One 0.1 2 1.7 3 2. 4 3.0 5 3.2

As shown in Table 1, the wood treated with the wood preservative composition of Examples 2 to 8 was significantly inhibited copper dissolution compared to the wood treated with the wood preservative composition of Comparative Examples 5 to 10.

Evaluation Example 3 Copper Dissolution Test According to Dispersant Type

The copper content contained in the specimens treated with the wood preservative compositions of Examples 5, 9 to 13 and Comparative Examples 3 to 4, 11 to 26 was measured by the Korea Forest Research Institute, Notification No. 2004-7. It measured according to the atomic absorption spectroscopy item of a measuring method.

The specific measuring method is the same as that of the evaluation example 2.

Elapsed time
[month] Copper Desorption (ppm) Example 5 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 3 Comparative Example 4 One 0.2 0.2 0.5 0.1 0.5 0.3 73.7 52.1 2 2.3 1.5 1.2 0.9 1.7 0.8 79.4 60.6 3 2.8 2.7 1.9 1.4 2.2 1.2 92.6 75.9 4 3.2 3.5 2.4 2.0 2.6 2.0 104.1 89.2 5 3.2 3.8 3.0 2.9 3.7 2.5 135.0 107.2 Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 One 34 54 28 22 19 32 48 75 2 48 61 38 31 29 44 63 88 3 67 82 53 42 38 69 81 103 4 85 109 60 49 45 89 102 119 5 101 122 78 56 54 108 117 138 Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26 One 56 120 100 112 108 127 121 132 2 71 172 153 151 140 190 173 207 3 90 221 178 193 193 272 256 320 4 102 294 199 254 220 341 301 412 5 129 340 221 304 285 379 352 480

As shown in Table 2, the wood treated with the wood preservation composition of Examples 5, 9 to 13 was significantly inhibited copper leaching compared to the wood treated with the wood preservation composition of Comparative Examples 3 to 4, 11 to 26.

Evaluation example 4: antiseptic test

The preservation condition of the wood surface was evaluated after leaving it outdoors for 12 months for the preservative wood treated using the wood preservation composition of Examples 5, 9 to 13 and Comparative Examples 3 to 4, 11 to 26. The evaluation results are shown in Table 3 below.

Preservation status was evaluated according to the following criteria.

(Circle): When microbial contamination is not observed visually, ie, the microbial contamination of wood surface is substantially 0% of wood surface area.

(Triangle | delta): The microscopic contamination was observed locally visually, ie, the microscopic contamination was visually observed in the range in which the contamination of the wood surface by microorganisms is less than 10% of the wood surface area.

X: Wood surface contamination by microbial contamination was observed visually within 10-30% of the surface area of wood.

XX: Wood surface contamination to microbial contamination is visually observed within 30% or more of the wood surface area.

Elapsed time Example 5 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 3 Comparative Example 4 Right after manufacturing ○ ○ ○ ○ ○ ○ ○ ○ 1 month ○ ○ ○ ○ ○ ○ ○ ○ 2 months ○ ○ ○ ○ ○ ○ ○ ○ 4 months ○ ○ ○ ○ ○ ○ △ ○ 6 months ○ ○ ○ ○ ○ ○ △ △ 8 months ○ ○ ○ ○ ○ ○ X △ 10 months ○ ○ ○ ○ ○ ○ XX △ 12 months △ ○ ○ ○ ○ ○ XX X Elapsed time Comparative Example 11 Comparative Example 12 Comparative Example 13 Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Right after manufacturing ○ ○ ○ ○ ○ ○ ○ ○ 1 month ○ ○ ○ ○ ○ ○ ○ ○ 2 months ○ ○ ○ ○ ○ ○ ○ ○ 4 months △ △ △ ○ ○ △ △ △ 6 months △ X X △ △ △ △ X 8 months X X X △ △ X X X 10 months X XX XX X X X X XX 12 months XX XX XX XX XX XX XX XX Elapsed time Comparative Example 19 Comparative Example 20 Comparative Example 21 Comparative Example 224 Comparative Example 23 Comparative Example 24 Comparative Example 25 Comparative Example 26 Right after manufacturing ○ ○ ○ ○ ○ ○ ○ ○ 1 month ○ ○ ○ ○ ○ ○ ○ X 2 months ○ X X X X X X X 4 months △ X X X X X X XX 6 months △ XX XX XX XX XX XX XX 8 months X XX XX XX XX XX XX XX 10 months X XX XX XX XX XX XX XX 12 months XX XX XX XX XX XX XX XX

As shown in Table 3, the preservative wood prepared using the wood preservative composition of Examples 5, 9 to 13 showed excellent antiseptic force, and further improved antiseptic force when the organic preservative was contained.

On the other hand, the preservative timber prepared using the wood preservation composition of Comparative Examples 3 to 4, 11 to 26 was poor antiseptic force.

Evaluation Example 5: Iron Corrosion Test

Iron corrosion test was performed on the anticorrosive wood prepared using the wood preservation compositions of Examples 5, 9 to 13 and Comparative Examples 3 to 4 and 11 to 26. The iron corrosion test determined the weight loss rate due to corrosion after nailing the wooden specimen for 10 days.

Preservative wood prepared using the wood preservation compositions of Examples 5, 9-13 had no weight loss due to corrosion. In contrast, partial corrosion was observed in the preservative wood prepared using the wood preservative compositions of Comparative Examples 3 to 4 and 11 to 19, and remarkable in the preservative wood produced using the wood preservation compositions of Comparative Examples 20 to 26. Corrosion was observed.

Claims (10)

Copper-based inorganic preservative particles; Quaternary ammonium salt compounds; Polyoxyethylene sorbitan fatty acid esters; And water, wherein the volume average particle diameter (d 50) of the copper-based inorganic preservative particles is 0.40 to 0.65 μm,
0.1-50 wt% of copper-based inorganic preservative; 1 to 70% by weight of quaternary ammonium salt compound, 3 to 50% by weight of polyoxyethylene sorbitan fatty acid ester; And 5 to 95% by weight of water; wood preservation composition comprising. The wood preservation composition of claim 1, wherein the d98 of the copper-based inorganic preservative particles is 1.0 to 5.0 µm. The wood preservation composition of claim 1, wherein the number of polyoxyethylene repeating units in the polyoxyethylene sorbitan fatty acid ester is 15 to 25. The method of claim 1, wherein the polyoxyethylene sorbitan fatty acid ester is polyoxyethylene [20] sorbitan monolaurate, polyoxyethylene [20] sorbitan monopalmitate, poly Oxyethylene [20] sorbitan monooleate, polyoxyethylene [20] sorbitan monostearate, polyoxyethylene [20] sorbitan tristearate, Wood preservation composition of at least one compound selected from the group consisting of polyoxyethylene [20] sorbitan triisostearate, polyoxyethylene [20] sorbitan trioleate. The method of claim 1, wherein the copper-based inorganic preservative is copper carbonate, copper hydroxide, copper oxide (copper oxide), copper sulfate, copper nitrate (copper nitrate), copper chloride (copper) chloride), and copper oxychloride (copper oxychloride) wood preservation composition, characterized in that at least one selected from the group consisting of. The method according to claim 1, wherein the cation of the quaternary ammonium salt compound is at least one selected from the group consisting of N-dimethylbenzylalkylammonium and didecyldimethylammonium, and the anion of the quaternary ammonium salt compound is hydroxide, At least one selected from the group consisting of chloride, carbonate, bicarbonate, fluoride, sulfate, nitrate, phosphate, and acetate Wood preservation composition, characterized in that delete 2. The wood preservative composition of claim 1, wherein said composition further comprises an organic preservative. The method of claim 8, wherein the organic preservative is ciproconazole, tebuconazole, propicoazole, benzothiazole, iodopropylbutylcarbamate (IPBC), methyl isothiazolidone, bifenthrin, deltamethrin Wood preservation composition is at least one compound selected from the group consisting of, permethrin, and cypermethrin. The composition of claim 1, wherein the composition comprises 0.1 to 50 wt% of a copper-based inorganic preservative; 1 to 70% by weight of quaternary ammonium salt compound, 3 to 50% by weight of polyoxyethylene sorbitan fatty acid ester; Wood preservative composition comprising 0.1 to 20% by weight of organic preservative and 5 to 95% by weight of water.

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