KR101024070B1 - Wood modification composition and modified wood prepared therefrom - Google Patents

Abstract

PURPOSE: A wood modification composition and modified wood prepared therefrom are provided to prevent hydrolysis by blocking the contact of water and organic acid anhydrides of the wood modification composition. CONSTITUTION: A wood modification composition includes 0.1-94 weight% of furfuryl alcohol, 0.01-10 weight% of organic acid anhydrides, 0.5-50 weight% of organic solvent, 0.1-30 weight% of surfactants, and 5-95 weight% of water. The wood modification composition is a non-hydrophilic solvent immiscible with water. The wood modification composition forms O/W emulsion by dispersing the organic solvent in water.

Description

Wood modified composition and modified wood prepared therefrom {Wood modification composition and modified wood prepared therefrom}

The present invention relates to a wood reforming composition that can increase the weather resistance, dimensional stability, hardness, etc., which are disadvantages of wood, which is a natural material, and a modified wood produced using the composition.

More specifically, anhydrous organic acid, which is hydrolyzed in an aqueous solvent to produce an acid, is dissolved in an excess of non-hydrophilic solvent, and then dispersed in water with a surfactant to prevent hydrolysis of the organic acid, thereby containing furfuryl alcohol. The present invention relates to a wood reforming composition and a modified wood using the same, in which a condensation reaction of furfuryl alcohol does not occur during preparation of a modifier composition, and thus, a stable wood can be realized for a long period of time, but the penetration of the composition in the wood, polymerization and coloring are uniform.

In order to prevent biological degradation of wood, wood should usually be preserved with a preservative including one or more preservatives, preservatives and insect repellents. Such preservation may for example treat wood in a closed pressurized or vacuum system, heating or impregnating system and similar system, or impregnating or dipping wood into a medicament containing a wood preservative or spraying the medicament. It can be performed by a method or the like.

Conventional representative pressurized wood preservatives used in the wood treatment are water soluble chromated copper arsenides (CCA). The CCA has been widely used because it has a short treatment time and can be used for treatment in a pressure gauge, which is an efficient treatment method. However, the CCA has been banned in Korea since 2007 due to a hazard problem, and its use is restricted worldwide. It is becoming.

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, the copper amine-based preservatives have a problem of causing environmental pollution due to copper dissolution, excellent weather resistance, but, like CCA, there is no effect of increasing the dimensional stability of wood, maintenance and repair costs during the life of the preservation wood This happens a lot.

Wood reforming using furfuryl alcohol does not cause toxic problems and environmental pollution due to copper dissolution, but also improves weather resistance, antiseptic power, hardness, insect repellency, dimensional stability, etc. This has a long advantage. Therefore, as an eco-friendly and economical method to replace the existing preservative wood, reformed wood that changes the structure of the wood using furfuryl alcohol for the improvement of the physical properties of the wood has attracted attention.

Furfuryl alcohol is a resource recycling type eco-friendly material produced by hydrogenation of furfural, a primary product generated from corn cob and sugarcane residue. Furfuryl alcohol can be mixed with water and condenses under high temperature or acidic conditions to form polyfurfuryl alcohol (poly (furfuryl alcohol)).

Wood furfurylation of modifying wood with polyfurfuryl alcohol using condensation of furfuryl alcohol has conventionally used a two-stage treatment method. That is, wood furfurylation was implemented by impregnating zinc chloride as a reaction catalyst in wood and then adding furfuryl alcohol to wood. However, the method of wood furfurylation through a two-stage process has failed commercialization due to the complicated procedure and time-consuming process. In order to overcome the above problem, there have been studies to develop a mixture of furfuryl alcohol and an acid catalyst to realize wood furfurylation through a one-step treatment process until recently.

At present, the main technical goal of wood reforming with furfuryl alcohol is to maintain furfuryl alcohol in the composition containing acid catalyst for a long time without condensation reaction by acid catalyst, and to completely cure after infiltrating the composition with wood. Modified wood produced by) has high color uniformity and excellent physical properties.

The following prior arts involved in the production of modified wood using furfuryl alcohol have been disclosed.

For example, U.S. Patent Application Publication No. 2006/0292366 uses organic or organic acids as condensation catalysts of furfuryl alcohol, stabilizers such as sodium carbonate, sodium bicarbonate, sodium citrate, etc. for the purpose of increasing the long-term stability of wood reforming compositions. The technique of adding is disclosed. The wood modified composition is used by dissolving anhydrous organic acid in water, so that organic anhydride is acidic as organic acid, but by suppressing the condensation reaction of furfuryl alcohol by adjusting the pH to 2.5 to 4.0 using a pH regulator which is a stabilizer To increase the shelf life of wood reforming compositions. However, in the environment of pH 2.5 to 4.0, furfuryl alcohol is condensation reaction within 48 hours, so phase separation between water and polyfurfuryl alcohol, a condensation product, is difficult to use, which requires distribution and storage period of the composition. .

WO 02/30638 A2 discloses a wood modified composition prepared by directly dissolving anhydrous organic acids and organic acids in furfuryl alcohol. The wood reforming composition does not contain water, so the storage stability is high, but the condensation reaction of furfuryl alcohol is rapidly progressed by the acid catalyst when it comes into contact with water in the production process, so it is not easy to manufacture the modified wood, which is applied to wood. Since it is not easy to uniformly mix with water in the process, an excessive amount of polyfurfuryl alcohol remains on the surface of the wood after curing, resulting in low coloring uniformity or dimensional stability of the modified wood.

Therefore, there is still a need for the development of wood modified compositions which are stable for a long time without condensation of furfuryl alcohol, are easy to manufacture, and which can provide penetration, polymerisation and high color uniformity of the composition in wood.

One aspect of the present invention is to provide a wood modified composition which is stable for a long time and provides high color uniformity and excellent physical properties through penetration and polymerization of the composition in wood.

Another aspect of the present invention is to provide a modified timber produced using the wood reforming composition.

Furfuryl alcohol according to one aspect of the present invention; Organic acid anhydride; Organic solvents; Surfactants; And water; wood reforming composition is provided comprising a.

As a modified timber produced using the wood reforming composition according to another aspect of the present invention,

A modified timber having a water-resistant adhesive strength retention of 90% or more according to the water resistance test method specified in KS M 3730 is provided.

In the wood reforming composition according to an aspect of the present invention, anhydrous organic acid dissolved in an organic solvent is blocked from contact with water by an O / W emulsion to prevent hydrolysis, and thus furfuryl alcohol is stably stored in an aqueous solvent for a long time. It can be, and can be implemented in the wood, easy to polymerize and modified wood that is uniform in color. In addition, the modified wood is excellent in weather resistance, weather fastness, water resistance, coating strength and antiseptic.

Figure 1 is an appearance of the modified wood produced in each of Example 10 (a), Example 11 (b) to Example 12 (c).
2 is a stability evaluation result of the wood modified composition prepared in Comparative Example 1 (a) and Example 1 (b), respectively.

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

Wood reforming composition according to one embodiment furfuryl alcohol (furfuryl alcohol); Organic acid anhydride; Organic solvents; Surfactants; And water.

The organic solvent may be a non-hydrophilic solvent that is not miscible with water. That is, when the organic solvent is simply mixed with water, phase separation occurs without mixing with each other. However, in the wood modified composition, an organic solvent may be dispersed in water by a surfactant to form an oil in water (O / W) emulsion. As the organic solvent, any organic solvent that does not miscible with water may be used.

In the present inventors, the organic anhydride is hydrolyzed by water to form an organic acid, but when dissolved in an excess of non-hydrophilic solvent and dispersed in water with a surfactant, the organic anhydride is separated from the water and uniformly dispersed in water without being hydrolyzed. Since present, furfuryl alcohol is found to be stable in water for a long time, and through the impregnation and hardening process, it is found that the modified wood of uniform wood coloring and excellent physical properties can be obtained, and this can be used as the wood reforming composition and the modified wood produced therefrom. The present invention has been completed.

The wood modified composition is a composition stabilized by an organic solvent and a surfactant such that an organic acid is not hydrolyzed by water, and condensation reaction of furfuryl alcohol does not occur even after long-term storage for more than several months, and the components are stable. Is dispersed. Therefore, the wood reforming composition not only secures the market shelf life of the composition, but can also realize the mass production of the reformed wood by using low-cost treatment methods such as dipping and spraying and general vacuum pressurized anti-corrosive production equipment. little. In addition, the wood reforming composition can easily control the content of furfuryl alcohol dissolved in water and the degree of impregnation in the wood can easily produce a variety of modified timber coloring and wood properties. In addition, the wood reforming composition solves the stability problem of the composition of the prior art and at the same time by using the existing pressure-preserved wood production equipment through the curing process to enable the mass production of the modified wood to improve the distribution, storage period of the modified composition Not only is it secured, but it is also competitive in the market distribution by reducing the burden on equipment investment of producers, and it is competitive in price because it uses eco-friendly and inexpensive water as the main solvent.

Furfuryl alcohol contained in the wood reforming composition is prepared by catalytic reduction of furfural, which is a primary product obtained by acidic hydrolysis and cyclodehydration of biomass such as corncob and sugar cane. Purpuryl alcohol is preferably at least 90% purity. The furfuryl alcohol is a modification component that penetrates into the wood and forms polyfurfuryl alcohol upon curing under an acid catalyst, and after curing and coloring the wood, it improves weather resistance, water resistance, antiseptic property, etc. of the wood, and expensive tropical It is desirable to be able to achieve a color similar to the hardwood ebony.

The content of furfuryl alcohol is preferably 0.1 to 94% by weight of the total weight of the composition. If the furfuryl alcohol is less than 0.1% by weight may not be effective in improving the wood properties, if the content is 94% by weight or more after the hardening of the excessive amount of polyfurfuryl alcohol on the surface of the wood will require post-work .

The organic anhydride in the wood reforming composition may be dissolved in an organic solvent. Since the contact with water is blocked by dissolving the organic anhydride in an organic solvent, generation of an organic acid as an acid catalyst in the composition may be blocked.

The organic anhydride should be dissolved in at least 0.01% by weight in an organic solvent or a mixture of an organic solvent and a surfactant, and hydrolyzed by water when the modified wood treated with the modified composition can be condensed with furfuryl alcohol. It is desirable to be able to act as an acid catalyst and be able to be produced in anhydrous form containing no water from the dehydration of organic acids.

For example, in the wood reforming composition, the organic anhydride may be maleic anhydride, phthalic anhydride, acetic anhydride, succinic anhydride, benzoic anhydride, or monohydric anhydride. Chloroacetic anhydride, citraconic anhydride, glutaric anhydride, glutaric anhydride, methylnadic anhydride, tetrachlorophthalic anhydride, trifluoroacetic anhydride anhydride, trifluoromethanesulfonic anhydride, trimellitic anhydride, 1,2-naphthalic anhydride, 1,8-naphthalic anhydride (1,8) -naphthalic anhydride), 2,2-dimethylglutaric anhydride, 2,3-anthracenedicarboxylic anhydride, 2,3-dimethyl anhydride Maleic acid (2,3-dimethylma leic anhydride), 2,3-naphthalenedicarboxylic anhydride, 2,3-pyridinedicarboxylic anhydride, 2-butene-1- amber acid anhydride (2-buten-1-ylsuccinic anhydride), 2-dodecen-1-ylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride ), 2-octenylsuccinic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-benzophenonetetracarboxylic dianhydride), 3, 3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride (3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride), 3,3-dimethylglutaric anhydride (3,3-dimethylglutaric anhydride) , 3,4,5-trimethoxybenzoic anhydride, 3-fluorophthalic anhydride, 3-methyl-4-cyclohexene-1,2- Dicarboxylic acid (3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride), 3-methylglutarate anhydride ( 3-methylglutaric anhydride), 4,4'-biphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,5-dichlorophthalic anhydride (4,5-dichlorophthalic anhydride), 4-bromophthalic anhydride, 4-chlorophthalic anhydride, 4-ethynylphthalic anhydride, 4- anhydride Florophthalic acid (4-fluorophthalic anhydride), 4-methoxybenzoic anhydride, 4-methoxyphenylacetic anhydride, 4-methyl-4-cyclohexene-1,2 -Dicarboxylic acid (4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride), anhydrous 4-methylcyclohexene-1,2-dicarboxylic acid (4-methylcyclohexane-1,2-dicarboxylic anhydride), 4-methylphthalic anhydride, 4-nitrophthalic anhydride, 4-tert-butylphthalic anhydride, 4-trifluoromethyl anhydride (4 -trifl uoromethylbenzoic anhydride, 5-norbolene-2,3-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, allylsuccinic anhydride, angelic anhydride, benzenesulfonic anhydride (benzenesulfonic anhydride), butylsuccinic anhydride, chlorodifluoroacetic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, croton anhydride Acids (crotonic anhydride), decylsuccinic anhydride, diglycolic anhydride, diphenic anhydride, ethylenediaminetetraacetic dianhydride, heptafluorobutyric anhydride anhydride, heptanoic anhydride, hexanoic anhydride, isobutyric anhydride, isovaleric anhydride, itaconic anhydride de), methyltetrahydrophthalic anhydride, n-octylsuccinic anhydride, nonanoic anhydride, p-toluenesulfonic anhydride, pentafluoropropionic anhydride ( pentafluoropropionic anhydride, phenoxyacetic anhydride, pivalic anhydride, propionic anhydride, pyromellitic dianhydride, tetrabromophthalic anhydride, tetrafluoro anhydride Tetrafluorophthalic anhydride, tetrafluorosuccinic anhydride, trimellitic anhydride chloride, or mixtures thereof are preferred, but are not necessarily limited to these and are organic acids that may be used in the art for sale. If all are available.

The content of the organic anhydride is preferably 0.01 to 10% by weight of the total weight of the composition. If the organic anhydride is less than 0.01% by weight, the condensation reaction of furfuryl alcohol does not occur well. If the content is more than 10% by weight, the amount of nonhydrophilic solvent and surfactant must be excessively increased, so the amount of furfuryl alcohol is relatively low. In addition, the weathering, water resistance, antiseptic force, hardness, etc. of the modified wood may be lowered.

The organic solvent may be a non-hydrophilic solvent because it is intended to block the hydrolysis of the organic anhydride by water in addition to the solvent for dissolving the organic acid. In addition, the organic solvent may not include a hydrophilic group such as a hydroxyl group. In addition, the organic solvents may have a structure in which the size of the molecules is small or may easily overlap with each other by the van der Waals bond with the hydrophobic portion of the surfactant. By having such a structure, when the composition is dispersed in water to form an O / W emulsion, surfactants can be densely distributed at the interface between water and a solvent, and as a result, the organic solvent particles in which water is dispersed Since it cannot penetrate inside, the organic anhydride is not hydrolyzed, and thus condensation reaction of furfuryl alcohol can be prevented.

The organic solvent volatilizes within the range of 70 to 140 ° C., which is the preferred curing temperature of the wood treated with the wood reforming composition, or allows the O / W emulsion containing anhydrous organic acid to come into contact with water through adsorption movement into the wood. It is preferred that the furfurylation reaction of furfuryl alcohol can be initiated.

The organic solvent in the wood reforming composition may be one or more compounds selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons and natural oils. The aromatic hydrocarbon may be substituted by aliphatic hydrocarbons. The aliphatic hydrocarbon may include double bonds and may include both straight and branched chains.

For example, the organic solvent may be xylene, benzene, toluene, pine oil, liquid paraffin, liquid isoparaffin, squalane, terpentine oil, orange Orange oil, lemon oil, commercial aromatic hydrocarbon mixtures (eg, Solvesso series or Kocosol series) or mixtures thereof may be used.

The content of the organic solvent may be 0.5 to 50% by weight. When the content of the organic solvent is less than 0.5% by weight, the above-mentioned organic anhydride may be hydrolyzed by reacting with water, so that the modified composition may become unstable. When the content of the solvent is more than 50% by weight, it is anhydrous by an excess of non-hydrophilic solvent. O / W emulsions of organic acids form oil bands so that the modified composition can be phase separated.

The content of the organic solvent in the wood reforming composition may be at least five times the organic anhydride. For example, the content ratio of the organic solvent to the organic anhydride may be 5: 1 to 20: 1.

The surfactant used in the wood modification composition may have an HLB value of greater than 5. For example, the HLB value of the surfactant is preferably greater than 5 to 18, more preferably 8 to 18. When the composition is diluted with water by including the solubilizer having the HLB value, O / W emulsion can be readily obtained instantaneously and the stability of the wood modified composition can be improved.

The surfactant of more than HLB 5 increases the solubility of the organic anhydride with the solvent so that a modified composition containing a higher concentration of the organic anhydride can be obtained. If the HLB value is less than 5, the lipophilicity of the surfactant may be increased to form an oil band without dispersing the non-hydrophilic solvent, and phase separation may occur in the modified composition.

The surfactant preferably comprises a block copolymer of an ethylene oxide (EO) repeat unit, a propylene oxide (PO) repeat unit, a polypropylene glycol (PPG) repeat unit, and / or an ethylene oxide / propylene oxide repeat unit. The number of repeating units present in one molecule of the solubilizer is not particularly limited but is preferably 2 to 100, more preferably 2 to 50, most preferably 2 to 20.

For example, the surfactant may be PEG fatty acid ester, PEG fatty acid diester, or polyethoxylated 1,3-diglyceride. , Polyglyceryl monoester, polyethoxylated sorbitan monoester, PEG (20) tristearate sorbitan (PEG (20) tristearate sorbitan, Span 20), PEG (20 ) Trioleate sorbitan (PEG (20) trioleate sorbitan, Tween 65), PEG (20) monostearate sorbitan (PEG (20) monostearate sorbitan, Tween 85), PEG (20) monooleate sorbitan (PEG (20) monooleate sorbitan, Tween 60), PEG (20) monopalmitate sorbitan (PEG (20) monopalmitate sorbitan, Tween 40), PEG (20) monolaurate sorbitan (PEG (20) monolaurate sorbitan), PEG (8) Stearate (PEG (8) stearate, Myrj 45R), PEG (40) Stearate (PEG (40) stearate, Myrj 52R ), PEG (50) stearate (PEG (50) stearate, Myrj 53R), polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, or mixtures thereof, but Any surfactant that can be used in the formation of O / W emulsion in the art can be used without limitation. That is, cationic, anionic and amphoteric surfactants may also be used. The numbers in parentheses in the surfactant are the number of repeating units.

When the surfactant content is less than 0.1% by weight, the O / W emulsion may be unstable in the above-described content in the organic anhydride, and when the surfactant content is more than 30% by weight, the use of a solvent capable of dissolving the organic anhydride is limited. Due to hydrolysis of the organic acid under the influence of water, condensation of furfuryl alcohol may proceed.

The wood reforming composition is 0.1 to 94% by weight of furfuryl alcohol; 0.01 to 10% by weight of organic anhydride; 0.5-50 wt% organic solvent; 0.1 to 30 wt% surfactant; And 5 to 95% by weight of water; may include. In the composition range, the wood modified composition may provide physical properties such as improved phase stability.

According to another embodiment of the invention, there is provided a modified timber produced using the wood reforming composition described above. The reforming may be carried out in a mass production of the modified wood using a general vacuum pressurized anti-corrosive production equipment as well as a method of dipping, spraying, etc., but in the wood of the modified composition in terms of increasing the life of the wood in a natural environment, such as weather resistance, water resistance, antiseptic force, etc. Highly permeable vacuum pressurized methods are preferred.

Wood treated with the modified composition may be subjected to curing and drying processes. The curing process is preferably about 1 to 48 hours at a temperature of 70 to 140 ℃. More preferably, it is about 1 to 10 hours at the temperature of 100-140 degreeC. Of course, the general wood drying process can optionally be carried out according to the final moisture content target after hardening.

The modified wood is condensed with polyfurfuryl alcohol on the surface of the wood and improved weather resistance, water resistance, etc. can maintain the ebony color of the modified wood for a long time, it can protect the modified wood from microorganisms, insects and the like. The modified wood can be used for a wide range of wood applications, such as deck, flooring, roofing, landscaping, siding materials, such as the improvement of the physical properties of wood.

The modified wood may be 90% or more of the water-resistant adhesive strength retention according to the water resistance test method of the adhesive prescribed in KS M 3730.

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.

(Manufacture of Wood Modified Compositions)

Example 1

The organic solution was prepared by dispersing polyoxyethylene nonylphenyl ether in xylene and dissolving maleic anhydride. On the other hand, furfuryl alcohol was dissolved in water to prepare an aqueous solution. The organic solution was slowly added dropwise while stirring the aqueous solution at 3,000 rpm to prepare an O / W emulsion. The content of each component used for preparing the emulsion is as follows.

20% by weight of furfuryl alcohol

2% by weight of maleic anhydride

Xylene 10% by weight

5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

63% by weight of water

Example 2

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

20% by weight of furfuryl alcohol

2% by weight of maleic anhydride

Xylene 12% by weight

5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

61% by weight of water

Example 3

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

20% by weight of furfuryl alcohol

2% by weight of maleic anhydride

Xylene 14 wt%

5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

59% by weight of water

Example 4

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

20% by weight of furfuryl alcohol

Phthalic anhydride 2% by weight

Xylene 10% by weight

5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

63% by weight of water

Example 5

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

20% by weight of furfuryl alcohol

2% by weight of benzoic anhydride

Xylene 10% by weight

5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

63% by weight of water

Example 6

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

20% by weight of furfuryl alcohol

2% by weight of citraconic anhydride

Xylene 10% by weight

5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

63% by weight of water

Example 7

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

10% by weight of furfuryl alcohol

1% by weight of maleic anhydride

Xylene 5 wt%

2.5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

81.5% by weight of water

Example 8

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

20% by weight of furfuryl alcohol

1% by weight of maleic anhydride

Xylene 5 wt%

2.5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

Water 71.5% by weight

Example 9

An emulsion was prepared in the same manner as in Example 1, except for the following difference in composition.

30% by weight furfuryl alcohol

1% by weight of maleic anhydride

Xylene 5 wt%

2.5% by weight of polyoxyethylene nonylphenyl ether (HLB value 10) (Jilin Zhongxin Chemical Co., Ltd., NP-10)

61.5% by weight of water

Comparative Example 1

Furfuryl alcohol, maleic anhydride and water of the following composition were mixed to prepare a wood modified composition aqueous solution.

20% by weight of furfuryl alcohol

2% by weight of maleic anhydride

78% by weight of water

Comparative Example 2

Furfuryl alcohol, maleic acid and water of the following composition were mixed to prepare a wood modified composition in an aqueous solution.

20% by weight of furfuryl alcohol

2% by weight of maleic acid

78% by weight of water

Comparative Example 3

Furfuryl alcohol, phthalic anhydride, and water having the following composition were mixed to prepare an aqueous solution of a wood modified composition.

20% by weight of furfuryl alcohol

Phthalic anhydride 2% by weight

78% by weight of water

(Manufacture of Modified Wood)

Examples 10-12

The wood modified composition prepared in Examples 7 to 9 was treated with a wood treatment for a hamlock (lumber of 10.5 cm x 10.5 cm x 400 cm standard) in an exhaust machine (600 mmHg, 30 minutes), pressurized (15 kg / m ³ , 3 hours), followed by post exhaust (600 mmHg, 30 minutes) and stop (30 minutes). The pressurized wood was cured at 120 ° C. for 10 hours to produce modified wood.

As shown in Figure 1 Examples 10 to 12 (modified wood produced in Examples 10, 11, 12 from left to right) is the color of the furfuryl alcohol is increased as the content of the furfuryl alcohol increases and uniform coloration is made. In Example 12, color was similar to that of expensive tropical ebony species.

Evaluation Example 1: Stability Evaluation

The wood modified compositions of Examples 1 to 9 in which the organic solvent was dispersed by the surfactant were stable even after 60 days had elapsed.

In the wood modified compositions of Comparative Examples 1 to 3, oil phase separation was observed after 30 minutes, and precipitates formed after 5 hours. Comparative Examples 1 to 3 were unstable because the condensation reaction of furfuryl alcohol proceeded rapidly.

As shown in FIG. 2, the wood modified composition of Comparative Example 1 was observed with a clear oil phase separation after 30 minutes, but the composition prepared in Example 1 remained stable even after 60 days.

Evaluation Example 2: Weather Resistance Test

The modified wood produced in Examples 10 to 12 was tested according to the natural weather resistance test method of paints and varnishes (outer wood paints and coating systems) prescribed in KS M ISO 16053.

The determination of weather resistance was made by evaluating the color stability. The color stability indicates how much the color of the wood has changed with the initial color over time, and the smaller the value, the higher the color stability. The test results are shown in Table 1 below.

Elapsed time after manufacture Example 10 Example 11 Example 12


Color stability
(ΔE)


Immediately after manufacture - - - 1 month 0.1 0.1 0.1 2 months 0.1 0.1 0.1 4 months 0.2 0.1 0.1 6 months 0.2 0.1 0.1 8 months 0.2 0.2 0.1 10 months 0.2 0.2 0.1 12 months 0.3 0.2 0.2

If the ΔE value is less than 0.5, it almost corresponds to a trace and the color change cannot be visually identified, and when 1.1 or more, the color change can be visually identified.

As shown in Table 1, the modified wood of Examples 10 to 12 showed excellent weatherability even after 12 months.

Evaluation Example 3 Daylight Fastness Test

The modified wood produced in Examples 10 to 12 was tested according to the outdoor exposure method specified in KS K 0703. Determination of daylight fastness was performed using a colorimeter to determine color fading for specimens (modified wood) exposed to long time. Daylight fastness mainly evaluates the effect of ultraviolet light. The decrease in lightness (L) over time shows low daylight fastness.

Elapsed time after manufacture Example 10 Example 11 Example 12 brightness
(lightness)


0 days 18.18 15.41 8.85 5 days 18.20 15.39 8.82 10 days 18.12 15.42 8.84 20 days 18.24 15.31 8.78 30 days 18.21 15.12 8.75

As shown in Table 2, the modified wood of Examples 10 to 12 of the present invention showed a good daylight fastness due to the slight difference in brightness even after 30 days.

Evaluation Example 4: Water Resistance Test

The modified wood produced in Examples 10 to 12 was tested according to the water resistance test method of the adhesive specified in KS M 3730. The water-resistant adhesive strength retention which is an evaluation criteria of water resistance is calculated from the following formula (1). The state peel strength was measured for the peeling strength of the modified wood cured for 10 hours at 120 ℃ after penetrating the composition into the wood by the pressure method. The peel strength was measured for 72 hours after immersion in water of 97 to 100 ° C. for the modified wood cured at 120 ° C. for 10 hours after penetrating the composition into the wood by pressure.

&Quot; (1) "

Water resistance adhesive strength retention rate [%] = [water resistance peel strength / state peel strength] * 100

Example 10 Example 11 Example 12 Water resistance
Retention rate [%] 92 95 98

As shown in Table 3, the modified timbers of Examples 10 to 12 of the present invention were excellent in water resistance, and the water resistance was increased when the content of furfuryl alcohol was increased.

Evaluation example 5: scratch test (hardness test)

The modified wood produced in Examples 10 to 12 was tested according to the paint and varnish scratch test (hardness test) method defined in KS M ISO 1518. The scratch test was judged as pass / fail according to the degree of scratching of the surface according to the standard.

Example 10 Example 11 Example 12 Scratch determination pass pass pass

As shown in Table 4, the modified wood of Examples 10 to 12 of the present invention formed a good coating film.

Evaluation Example 6: Antiseptic Test

The preserved state of the wood surface was evaluated after leaving the outdoor for 12 months for the modified wood prepared in Examples 10 to 12. The evaluation results are shown in Table 5 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 state which the microbial contamination was observed locally visually, ie, the state which the microbial contamination was visually observed in the range which the contamination of the wood surface by microorganisms is less than 10% of the wood surface area.

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

XX: A condition where the surface of the wood is contaminated with microbial contamination within 30% or more of the surface of the wood.

Elapsed time after manufacture Example 10 Example 11 Example 12


Wood preservation



Immediately after manufacture ○ ○ ○ 1 month ○ ○ ○ 2 months ○ ○ ○ 4 months ○ ○ ○ 6 months ○ ○ ○ 8 months ○ ○ ○ 10 months ○ ○ ○ 12 months △ ○ ○

As shown in Table 5, the modified wood of Examples 10 to 12 using the composition of the present invention showed excellent antiseptic force.

Claims (13)

Furfuryl alcohol; Organic acid anhydride; Organic solvents; Surfactants; And water;
0.1-94% by weight of furfuryl alcohol; 0.01 to 10% by weight of organic anhydride; 0.5-50 wt% organic solvent; 0.1 to 30 wt% surfactant; And 5 to 95% by weight of water; Wood reforming composition comprising. The wood modified composition according to claim 1, wherein the organic solvent is an immiscible non-hydrophilic solvent. The wood reforming composition of claim 1, wherein the organic solvent is dispersed in water to form an O / W emulsion. The wood reforming composition of claim 1, wherein the organic anhydride is dissolved in an organic solvent. According to claim 1, wherein the organic anhydride is maleic anhydride (phthalic anhydride), phthalic anhydride (acetic anhydride), acetic anhydride (succinic anhydride), benzoic anhydride (benzoic anhydride), monochloroacetic anhydride ( chloroacetic anhydride, citraconic anhydride, glutaric anhydride, methylnadic anhydride, tetrachlorophthalic anhydride, trifluoroacetic anhydride, Trifluoromethanesulfonic anhydride, trimellitic anhydride, 1,2-naphthalic anhydride, 1,8-naphthalic anhydride ), 2,2-dimethylglutaric anhydride, 2,3-anthracenedicarboxylic anhydride, 2,3-dimethylmaleic anhydride (2 , 3-dimethylmaleic anhydride), anhydrous 2, 3-naphthalenedicarboxylic acid (2,3-naphthalenedicarboxylic anhydride), 2,3-pyridinedicarboxylic anhydride, 2-butene-1- amber acid (2-buten-1- ylsuccinic anhydride), 2-dodecen-1-ylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride, 2-octenyl anhydride 2-octenylsuccinic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-benzophenonetetracarboxylic dianhydride), 3,3 ', 4,4' -Diphenylsulfontetracarboxylic dianhydride (3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride), 3,3-dimethylglutaric anhydride (3,3-dimethylglutaric anhydride), 3,4,5 -Trimethoxybenzoic anhydride, 3-fluorophthalic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic acid (3- methyl-4-cyclohexene-1,2-dicarboxylic anhydride), 3-methylglutaric anhydride ), 4,4'-biphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,5-dichlorophthalic anhydride (4,5) -dichlorophthalic anhydride, 4-bromophthalic anhydride, 4-chlorophthalic anhydride, 4-ethynylphthalic anhydride, 4-fluorophthalic anhydride 4-fluorophthalic anhydride), 4-methoxybenzoic anhydride, 4-methoxyphenylacetic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxyl Acid (4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride), 4-methylcyclohexene-1,2-dicarboxylic acid (4-methylcyclohexane-1,2-dicarboxylic anhydride), 4-methyl anhydride Phthalic acid (4-methylphthalic anhydride), 4-nitrophthalic anhydride, 4-tert-butylphthalic anhydride, 4-trifluoromethylbenzoic anhydrid e), 5-norbornene-2,3-dicarboxylic anhydride, allylsuccinic anhydride, angelic anhydride, benzenesulfonic anhydride ( benzenesulfonic anhydride, butylsuccinic anhydride, chlorodifluoroacetic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, crotonic anhydride (crotonic anhydride), decylsuccinic anhydride, diglycolic anhydride, diphenic anhydride, ethylenediaminetetraacetic dianhydride, heptafluorobutyric anhydride ), Heptanoic anhydride, hexanoic anhydride, isobutyric anhydride, isovaleric anhydride, itaconic anhydride, methyl anhydride Phthalic acid (methyltetrahydrophthalic anhydride), n-octylsuccinic anhydride, nonanoic anhydride, p-toluenesulfonic anhydride, pentafluoropropionic anhydride, phenoxy anhydride Phenoxyacetic anhydride, pivalic anhydride, propionic anhydride, pyromellitic dianhydride, tetrabromophthalic anhydride, tetrafluorophthalic anhydride Wood modification composition, at least one compound selected from the group consisting of tetrafluorosuccinic anhydride, anhydrous trimellitic anhydride chloride. The wood reforming composition of claim 1, wherein the organic solvent is at least one compound selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons and natural oils. The wood reforming composition of claim 1, wherein the organic solvent is at least one compound selected from the group consisting of xylene, benzene, toluene, pine oil, liquid paraffin, liquid isoparaffin, squalane, terpentin oil, orange oil, and lemon oil. . The wood modified composition of claim 1, wherein the HLB value of the surfactant is greater than 5 to 20. The method of claim 1, wherein the surfactant is a PEG fatty acid ester, PEG fatty acid ester dimer, polyethoxylated 1,3-diglyceride, polyglyceryl monoester, polyethoxylated sorbitan monoester, PEG (20) Tristearate sorbitan, PEG (20) trioleate sorbitan, PEG (20) monostearate sorbitan, PEG (20) monooleate sorbitan, PEG (20) monopalmitate sorbitan, mono Wood modification composition, characterized in that at least one compound selected from the group consisting of laurate sorbitan, PEG (8) stearate, PEG (40) stearate, PEG (50) stearate and polyoxyethylene octylphenyl ether. delete A modified timber produced using the wood modified composition according to any one of claims 1 to 9. 12. The modified timber according to claim 11, wherein the modified timber has a water-resistant adhesive strength retention of 90% or more according to the water resistance test method of the adhesive specified in KS M 3730. The modified timber according to claim 11, wherein the use of the modified timber is deck material, floor material, roof material, landscaping material or siding material.

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