JPH05138615A - Production of modified timber - Google Patents

Abstract

PURPOSE:To efficiently obtain modified timber which has high-degree dimensional stability and is excellent in weather resistance such as water resistance and moisture resistance and does not lose ligneous feeling. CONSTITUTION:Both a compound which reacts formaldehyde and can be changed into insoluble setting resin and formaldehyde and/or its derivative are dissolved into a solvent. Timber of a raw material is impregnated with the compounds in a state of this solution or vapor thereof. Moreover insoluble setting resin is produced and fixed in the inside of the structure of timber by heating this timber of the raw material and performing formalizing reaction in the inside of timber.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing modified wood used for housing equipment, building materials and the like.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting dimensional stability to wood as a means for suppressing cracking, warping, and deformation of wood,
For example, the following methods are available. Chemical modification A method of reducing hygroscopicity and dimensional change of wood by substituting hydrophilic groups of cellulose, which is a wood component, with hydrophobic groups by a chemical reaction. Examples of the compound for chemical modification include acid anhydrides, halogenated organic acids, epoxides, alkyl halides, isocyanates, formalin and the like.

WPC A method of impregnating wood with a monomer such as styrene or methyl methacrylate in a solvent, and then heating or electron beam radiation to generate an insolubilized resin in the wood. According to this method, in addition to improving dimensional stability, hardness and wear resistance are also improved.

Bulking with Water-Soluble Resin A method of improving dimensional stability by impregnating a cell wall of wood with a water-soluble resin such as polyethylene glycol or polyethylene glycol monomethacrylate, followed by drying and curing. In this method, since the resin to be impregnated is water-soluble, it is easy to handle, and the resin can be impregnated into the cell wall.

[0005]

However, the above
Each of the above methods had the following problems (a) and (b). (A) In the above method, unreacted substances or reaction residues remain, which may give off an offensive odor or deteriorate the strength of wood due to acid. Moreover, the reaction process is complicated.

(B) In the above method, since the monomer with which the wood is impregnated is hydrophobic, the monomer is not impregnated into the cell wall of the wood. Therefore, in order to impart high dimensional stability, 50 to 1 is added to the weight of wood before impregnation.
It is necessary to impregnate as much as 100% by weight of monomer. As a result, the wood texture on the wood surface is lost. (C) In the above method, since the impregnated resin is still easily soluble in water even after being dried and cured, the resin elutes on the surface of the wood due to water absorption / moisture absorption, and the performance deteriorates. That is, the weather resistance such as water resistance and moisture resistance of the wood becomes low.

As described above, the dimensional stabilization treatment of wood is carried out by various methods, but the ones that achieve high dimensional stabilization with almost no warp are acetylation and WPC.
There is only a combination of (the anti-swelling ability ASE
= 90% or more). However, the modified wood obtained by this method, as described above, loses the wood texture,
It had a defect such as acetic acid odor.

Therefore, the present invention is a method for efficiently obtaining modified wood which has a high degree of dimensional stability, is excellent in weather resistance such as water resistance and moisture resistance, and has not lost the surface wood texture. The challenge is to provide.

[0009]

In order to solve the above problems, the inventors have made various studies. As a result, the raw material wood is impregnated with the compound capable of reacting with formaldehyde to form an insoluble cured resin, and formaldehyde and / or its derivative, and the raw material wood is heated,
If the formalization reaction is carried out in the wood, the bulking effect obtained by filling the hard resin into the cell wall of the wood and the crosslinking between the wood components due to the formalization and the wood component and the resin It was confirmed by experiments that a high degree of dimensional stability can be realized by the effect that the hydrophilic hydroxyl groups of the wood component (cellulose, hemicellulose, lignin, etc.) are made hydrophobic by cross-linking between them, and the present invention was completed.

Therefore, in the method for producing modified wood according to the present invention, a compound capable of reacting with formaldehyde to form an insoluble cured resin (hereinafter, simply referred to as "compound A"), formaldehyde and / or a derivative thereof. Is impregnated into the raw material wood in a state of being dissolved in a solvent or in the state of steam, and this raw material wood is heated to cause a formalization reaction in the wood to generate and fix an insoluble cured resin in the wood tissue. To do so.

The raw material wood for reforming used in the present invention is not particularly limited. For example, raw wood logs,
Lumber products, sliced veneer, rotary veneer, plywood and the like can be mentioned. There is no limitation on the species of the trees. The raw material wood may be impregnated with the compound A and formaldehyde and / or a derivative thereof in the form of a solution dissolved in a solvent or in the form of steam. That is, one of these impregnating components may be impregnated in a solution state and the other may be impregnated in a vapor state, or both may be impregnated in a solution or vapor state. Further, these impregnating components may be impregnated separately, or may be impregnated simultaneously in a mixed solution or mixed vapor state. The impregnation order when impregnating separately is not limited at all.

The compound A used in the present invention is
It is not particularly limited as long as it can be converted into an insoluble hardened resin by reacting with formaldehyde, but it is preferable that it is easily impregnated and adsorbed even into the cell wall of wood, and by the formalization reaction described in detail later, wood It is desirable that the hydrophilic hydroxyl groups of the wood component can be hydrophobized by crosslinking between the component and the resin. In the case of impregnation in the form of a solution, it is necessary that it be soluble in a suitable solvent, and a water-soluble one is particularly preferable. In addition, when impregnating in a vapor state, it is necessary that it is volatile.

Examples of the compound A include, but are not limited to, resin monomers and water-soluble resin polymers. The resin monomer is not particularly limited, but examples thereof include compounds having a methylol group, for example, amides, phenols, amines (amino compounds) having a methylol group. Specific examples thereof include, as amides having a methylol group, a methylolation product of acrylamides, for example, methylol acrylamide, methylol methacrylamide, and the like, as phenols having a methylol group, a methylolation product of phenol, for example, methylol. Examples of amines having a methylol group such as phenol and di (tri) methylolphenol include methylolurea, dimethylolurea, dimethylolethyleneurea, and methylolmelamine.

However, the resin monomer is not limited to these. For example, acrylamide, methacrylamide, phenol, cresol, xylitol,
A compound such as resorcinol, hydroquinone, urea, ethylene urea, dihydroxyethylene urea, melamine, acetoguanamine, aminophenol or aminotriazole, which does not have a methylol group but can be converted to a methylol, may be used. This is because these monomers can be converted into methylol and crosslinked by a formalization reaction described below after impregnating wood, and the same effect as when a compound having a methylol group is used can be obtained.

The resin monomer may be used alone or in combination of two or more kinds. As the resin monomer, the above-mentioned compound having a methylol group and a compound capable of being converted to a methylol can be used in combination. Further, instead of the resin monomer, its oligomer may be used,
The initial condensate may be used. The initial condensate of the resin monomer is not particularly limited, and examples thereof include an initial condensate obtained from the reaction of the resin monomer and aldehydes such as formaldehyde.

The above resin monomers, oligomers thereof and initial condensates may be used in combination with each other, or in combination with a water-soluble resin polymer described later. The water-soluble resin polymer which is an example of the compound A is not particularly limited, but examples thereof include polyoxyethers, polyols, polyacrylic acids and the like. Specific examples of polyoxyethers include polyethylene glycol and its derivatives such as polyethylene glycol acrylate and polyethylene glycol methacrylate. Specific examples of the polyols include polyvinyl alcohol and the like. Specific examples of the polyacrylic acids include polyacrylamides such as polyacrylamide, polymethylolacrylamide, polymethacrylamide, polymethylolmethacrylamide, methyl polyacrylate, ethyl polyacrylate, methyl polymethacrylate, and ethyl polymethacrylate. And polyacrylic acid esters of These may be used alone or in combination of two or more.

Regarding the molecular weight of the water-soluble resin polymer,
Although not particularly limited, those having a molecular weight of 10,000 or less are usually used, and a low polymer having a molecular weight of about 200 to 1,000 is desirable. This is because such a low-polymerization material is likely to be impregnated into the cell wall of wood. When compound A having a polymerizable double bond such as acrylamide is used, compound A may be used as necessary.
In addition, a polymerization initiator may be impregnated with a peroxide such as benzoyl peroxide, a persulfate such as potassium persulfate, or the like to polymerize the compound A in wood. Furthermore, chlorides such as ammonium chloride or acid catalysts such as paratoluenesulfonic acid may be impregnated as a material that promotes crosslinking between resins.

When the compound A is impregnated in the vapor state, it is necessary to use the volatile compound A as described above. Examples thereof include, but are not particularly limited to, for example, volatile resin monomers such as phenol or phenol derivatives such as methylolphenol, di (tri) methylolphenol, cresol, xylitol, resorcinol, and initial condensation thereof. Things etc. are mentioned.

The formaldehyde derivative used in the present invention means a formaldehyde supply agent. The formaldehyde supply agent is not particularly limited, but for example, paraformaldehyde, trioxane,
Tetraoxane etc. are mentioned. These can use 1 type (s) or 2 or more types. Also, of these,
Trioxane and tetraoxane are preferable to use trioxane and tetraoxane because they have no formalin odor when solid and easily sublime, and formaldehyde monomer is easily obtained upon decomposition.

The solvent used for the solution impregnation is not particularly limited, but it is preferable to use a polar solvent. This is because the polar solvent causes the wood to swell, so that the voids in the cell wall are expanded and the impregnation into the cell wall is facilitated. Among the polar solvents, water is particularly preferable. Further, the solvent is not limited to one kind, and a mixed solvent of two or more kinds, for example, a mixed solvent of water and another polar solvent may be used. The concentration of the impregnating solution is not particularly limited, but for example, compound A is preferably 1 to 30% by weight.
The concentration of formaldehyde and / or its derivative is also not particularly limited.

Examples of the solution impregnation method include, but are not limited to, various methods such as impregnation under reduced pressure, impregnation under pressure, and permeation diffusion in a warm bath. The impregnation time depends on the impregnation method, but is not particularly limited. When steam impregnation is carried out, the concentration of steam is not particularly limited, but with respect to the compound A, for example, a steam concentration such that the weight increase rate per wood when adsorbed to wood is 5 to 30% is preferable. The vapor concentration of formaldehyde and / or its derivative is not particularly limited depending on the degree of the formalization reaction described below, but is 5 to 5% by weight of wood.
It is desirable that the concentration include 50% formaldehyde monomer, for example, 1 × 10 ⁻³ to 1 × 10 ⁻¹ mol / dm ³ .

The vapor of the impregnating component is usually the reaction vessel (tank).
The material previously prepared outside is introduced into the reaction vessel to impregnate the raw material wood. In particular, when formaldehyde is impregnated in the form of steam, the formaldehyde derivative may be placed in a reaction vessel and impregnated while decomposing it into formaldehyde monomer vapor in the reaction vessel.
Rather than performing this method, it is preferable to decompose the formaldehyde derivative in advance to form formaldehyde monomer and introduce the formaldehyde monomer vapor thus obtained into the reaction vessel to impregnate the raw material wood. .. According to this method, the time required for decomposing the formaldehyde derivative can be omitted, so that the processing time can be shortened, the cost can be reduced, and the thick wood can be processed. .. Examples of the method of decomposing the formaldehyde derivative into a formaldehyde monomer include a method of heating the formaldehyde derivative in the presence of an acid catalyst. However, the method is not limited to this, and the formaldehyde monomer may be decomposed by another method.
The acid catalyst used for the decomposition into the formaldehyde monomer can also be used as a formalization reaction catalyst described later, and thus may be introduced into the reaction vessel together with the obtained formaldehyde monomer vapor.

When impregnating components are impregnated in a vapor state,
Although not particularly limited, it is preferable to inject the vapor into the reaction vessel under reduced pressure or under pressure. This is because it is possible to promote the permeation and diffusion of steam into the wood by injecting under reduced pressure or injecting under pressure.
In addition, the inside of the reaction vessel can be kept under pressure during the reaction period. When the reaction is carried out under pressure, it is possible to treat the inside of the wood and also shorten the treatment time. As a method of pressurizing, impregnation component, volatile component of wood,
Examples include a method in which the total pressure of the solvent or the like in the reaction vessel is adjusted to 1 atm or more in advance. However, it is not limited to this. For example, it is possible to pressurize by introducing an inert gas such as nitrogen into the reaction vessel.

As described above, the raw material wood is impregnated with the compound A and formaldehyde and / or a derivative thereof, and the raw material wood is heated to react the compound A with formaldehyde in the wood.
In addition, the hydrophilic group of the wood component is hydrophobized by the cross-linking between the wood components and the cross-linking between the wood component and the produced resin (these reactions are collectively referred to as "formalization reaction" in this specification). ..).

The formalization reaction may be carried out using a catalyst, if necessary. The formalization reaction catalyst that can be used is not particularly limited, but examples thereof include chlorides such as hydrogen chloride, zinc chloride and iron chloride, sulfates such as sulfuric acid and iron sulfate, boric acid, borate and acid catalysts such as sulfur dioxide. Etc. can be mentioned. Among the acid catalysts, in particular,
When sulfur dioxide is used, it is preferable to use sulfur dioxide because the deterioration of the strength and discoloration of wood, which will be described later, become relatively small.

Regarding the concentration of the formalization reaction catalyst,
Although not particularly limited, for example, when sulfur dioxide is used, it is 1/20 to 1/2 of the formaldehyde concentration.
Is desirable. In order to accelerate the decomposition of the formaldehyde derivative into formaldehyde monomer, it is possible to add another catalyst and use two or more kinds of catalysts. Also,
The impregnation form of the catalyst is not particularly limited. That is, it may be appropriately impregnated in a solution or vapor state according to the type.

The conditions for the formalization reaction are not particularly limited, but for example, the temperature (heating temperature) is 8
0-150 degreeC is preferable. The longer the reaction time, the higher the reaction rate. Moreover, it is preferable to carry out in a sealed system. It should be noted that this formalization reaction is preferably carried out in a dry state in which excess water in the wood is removed, for example, in a state where the water content of the wood is at or below its fiber saturation point (about 30%). This is because if there is excess water during formalization,
Formaldehyde monomer is easily polymerized by this water to form an oxymethylene chain. If an oxymethylene chain is formed, the effect of improving dimensional stability will be reduced, and discoloration of wood will occur due to the action with an acid catalyst used as necessary. This is because it becomes unfavorable because it becomes large. However, some of the above-mentioned formalization reaction catalysts require water. For example, in the case of sulfur dioxide, water is needed because it reacts with formaldehyde to water to yield hydroxymethyl sulfonic acid, which promotes the aforementioned crosslinking. Therefore, when using a catalyst that requires water, it is preferable to adjust the degree of drying of wood.

Examples of the drying method for adjusting the water content of such wood include air drying, vacuum drying, hot air drying, high frequency heating, and electron beam irradiation, but are not particularly limited. You may use these methods together. Further, it is preferable that the drying is performed in an open system. Compound A may be polymerized and / or crosslinked (cured) at this stage,
Depending on its type, it may be dried in an uncured state and then crosslinked in a subsequent formalization reaction.

As mentioned above, if necessary,
Although an acid catalyst may be used, the acid catalyst promotes deterioration of the strength and discoloration of wood when it is brought into contact with wood for a long time.
In order to suppress this, it is preferable to make the contact time between the acid catalyst and the wood as short as possible. As a method therefor, for example, the above-mentioned method of impregnating the raw material wood with the formaldehyde monomer vapor obtained by previously decomposing the formaldehyde derivative can be mentioned. According to this method, as described above, it is possible to save the decomposition time from the formaldehyde derivative to formaldehyde monomer, so that the formalization treatment time is shortened, and as a result, the contact time between the acid catalyst and wood is shortened. Because you can.

However, the method for shortening the contact time between the acid catalyst and wood is not limited to the above method. For example, compound A and formaldehyde and /
Alternatively, the raw material wood may be impregnated with the derivative thereof and cured, and then the wood may be impregnated with the acid catalyst. This method is performed as follows, for example. First, the raw material wood is impregnated with the compound A, the water content of the wood is adjusted, and then the wood is placed in a reaction vessel whose temperature has been raised, and further a predetermined amount of a formaldehyde derivative solid such as trioxane is put therein. Then, a depressurized state (for example, 100
The formaldehyde derivative is sublimed by heating under mmHg) to penetrate and diffuse into the wood. At this time, the heating temperature is preferably 50 to 120 ° C., and the time is not limited. Also, at this stage, by pressure treatment, penetration,
It is also possible to promote diffusion. In this way, the formaldehyde derivative is sufficiently permeated and diffused into the wood, and then a predetermined amount of the acid catalyst is introduced into the reaction vessel to allow the reaction to proceed. The introduction of the acid catalyst may be performed after the gas in the reaction vessel is once exhausted.

After completion of the formalization reaction, the gas in the reaction vessel may be exhausted under reduced pressure while being heated, if necessary. By sufficiently performing such exhaust, most of the unreacted gas in the wood can be removed. As described above, after the formalization reaction is performed to generate and fix the insoluble cured resin in the wood, if necessary,
The desired modified wood is obtained by washing the wood surface with water and drying.

[0032]

[Function] A compound capable of reacting with formaldehyde to form an insoluble cured resin and formaldehyde and / or a derivative thereof are impregnated into a raw material wood in a state of being dissolved in a solvent or in a vapor state, and the raw material wood is heated,
When the insoluble hardened resin is generated and fixed in the wood by carrying out the formalization reaction in the wood, the bulking effect obtained by filling the resin in the cell wall of the wood and the wood by the formalization The wood is highly dimensionally stabilized by the cross-linking between the components and the chemical modification effect of making the hydrophilic hydroxyl groups of the wood component hydrophobic by the cross-linking between the wood component and the resin. Since the impregnating component reacts at a high reaction rate, it is not necessary to remove unreacted substances. Since the impregnating component is impregnated in a solution or vapor state, the impregnation component can be efficiently impregnated into the wood cell wall, so that the impregnation amount required for dimensional stabilization is small and the wood surface has a wood texture. To be kept. Moreover, after impregnation, it is insolubilized in water and fixed inside the wood, so there is no risk of it leaching out on the surface due to water absorption / moisture absorption, so the weather resistance such as water resistance / moisture resistance is improved. In addition, antiseptic and insect repellent properties are imparted by the formalization treatment.

[0033]

EXAMPLES Specific examples of the present invention will be described in detail below together with comparative examples, but the present invention is not limited to the following examples. —Example 1— 0.2% of potassium persulfate was added to a 20 wt% aqueous solution of methylol acrylamide (hereinafter, abbreviated as “MAM”).
After the treatment solution containing 1% by weight (relative to MAM) was injected under reduced pressure into a cypress material, it was dried in a dryer at 100 ° C. for 1 hour to polymerize and crosslink (cure) MAM.

Next, trioxane was added in the presence of sulfur dioxide.
Formaldehyde vapor obtained by heating
(2 x 10^-2mol / dm³) And sulfur dioxide vapor (4 × 10^-3
mol / dm ³) And a mixed gas consisting of
Reforming by keeping the temperature inside the dryer at 120 ° C for 24 hours
I got wood. Example 2-In Example 1, instead of a 20 wt% aqueous solution of MAM
A 20% by weight aqueous solution of methylolphenol and persulfate
Use as treatment solution without adding any potassium
Modified wood was obtained in the same manner as in Example 1 except for the above.

Example 3 In Example 1, a 20 wt% aqueous solution of methylolmelamine was used as a treating solution without adding potassium persulfate in place of the 20 wt% aqueous solution of MAM, and instead of trioxane. Modified wood was obtained in the same manner as in Example 1 except that tetraoxane was used.

Example 4-A 20% by weight aqueous solution of phenol was used as a treatment solution under reduced pressure injection into a cypress wood, and dried in a dryer at 100 ° C for 1 hour to adjust the water content of wood. Next, formaldehyde vapor (2 × 10 ^-2 mo obtained by heating tetraoxane in the presence of sulfur dioxide)
l / dm ³ ) and sulfur dioxide vapor (4 × 10 ^-3 mol / dm ³ ) were introduced into the dryer, and the temperature inside the dryer was adjusted to 1
The modified wood was obtained by keeping it at 20 ° C. for 24 hours.

Example 5-In Example 1, instead of the 20% by weight aqueous solution of MAM, methylol methacrylamide (hereinafter referred to as "MMA
Abbreviated as “M”), and using 0.2% by weight of potassium persulfate (against MMAM) added to this aqueous solution as a treatment solution. Modified wood was obtained.

Example 6 To a 10% by weight aqueous solution of MAM, 0.2% of potassium persulfate was added.
Reduce the processing solution that is added by weight% (to MAM) to cypress
After pressure injection, air-drying is performed to adjust the water content of the wood.
went. The treated wood was then placed in the dryer. next,
By heating the trioxane in the presence of sulfur dioxide
The resulting formaldehyde vapor (2 x 10^-2mol / d
m³) And sulfur dioxide vapor (4 × 10^-3mol / dm ³) And from
Inject the mixed gas into the dryer under reduced pressure to increase the temperature inside the dryer.
Modified wood was obtained by keeping at 120 degreeC for 12 hours.

-Example 7-Except that in Example 6, a 5 wt% aqueous solution of methylolphenol was used as a treatment solution without adding potassium persulfate in place of the 10 wt% aqueous solution of MAM. Modified wood was obtained in the same manner as in Example 6. Example 8 In Example 6, a 20 wt% aqueous solution of methylolmelamine was used as a treatment solution without adding potassium persulfate instead of a 10 wt% aqueous solution of MAM, and tetraoxane was used instead of trioxane. Modified wood was obtained in the same manner as in Example 6 except for the above.

Example 9 A 5% by weight aqueous solution of aminophenol was used as a treating solution under reduced pressure injection into cypress wood, and then dried in a dryer at 100 ° C. for several hours to adjust the water content of wood. ..
Next, formaldehyde vapor (2 × 10 ^-2) obtained by heating tetraoxane in the presence of sulfur dioxide was used.
mol / dm ³ ) and sulfur dioxide vapor (4 × 10 ^-3 mol / dm ³ ) were introduced into the dryer, and the temperature inside the dryer was maintained at 120 ° C for 12 hours to obtain modified wood. Got

Example 10 Modified wood was obtained in the same manner as in Example 6 except that a 20 wt% aqueous solution of aminotriazole was used instead of the 10 wt% aqueous solution of MAM. .. -Comparative Example 1-In a 20 wt% aqueous solution of MAM, 0.2 wt% of potassium persulfate (relative to MAM) and 3 wt% of ammonium chloride (relative to MA)
After injecting the treatment solution containing (M) and
By drying in a dryer at 120 ° C for 24 hours,
Modified wood was obtained.

The modified woods obtained in the above Examples 1 to 10 and Comparative Example 1 were subjected to a water saturation treatment and a total dry treatment to obtain the weight and size of each wood, and from the values, the following formula ( The impregnation rate represented by 1) and the anti-swelling ability (ASE) represented by the following formula (2) were determined. Impregnation rate (%) = {(W ₂ −W ₁ ) / W ₁ } × 100 (1) (In the formula (1), W ₁ represents the total dry weight of the raw wood, and W ₂ represents the total of the modified wood. Dry weight.) Anti-swelling capacity (%) = {(S ₁ −S ₂ ) / S ₁ } × 100 (2) (In the formula (2), S ₁ represents the swelling ratio of the raw material wood, and S ₂ Represents the swelling ratio of the modified wood.) The results are shown in Table 1 below. The anti-swelling result is the value (%)
Is less than 40, it is evaluated as Δ, when it is 40 or more and less than 70, it is evaluated as ◯, and when 70 or more, it is evaluated as ⊚.

[0043]

[Table 1]

As shown in Table 1, the modified woods of Examples 1 to 10 obtained by the formalization treatment are compared with the modified woods of Comparative Example 1 obtained without the formalization treatment. Although the impregnation rate was almost the same, it was confirmed that the anti-swelling ability is high and the dimensional stability is extremely excellent. -Example 11- After fixing a cypress material in a reaction container, the reaction container was set to 120
Preheated at ° C.

Next, phenol monomer vapor (2.0 ×
10 ^-1 mol / dm ³ ), a mixed vapor consisting of formaldehyde monomer vapor (2 × 10 ^-2 mol / dm ³ ) which is a decomposition product of trioxane and sulfur dioxide vapor (4 × 10 ^-3 mol / dm ³ ). After preparing each steam by extracting each steam from the cylinder of each substance and mixing, the mixed steam is injected into the reaction vessel under reduced pressure, and the reaction vessel is heated at 120 ° C. for 24 hours to obtain modified wood. It was

Example 12 After fixing the cypress material in the reaction vessel, the reaction vessel was set at 120
Preheated at ° C. Next, a predetermined amount of saligenin (2-methylolphenol) was placed in the reaction container, and the interior of the reaction container was depressurized and heated to impregnate the wood with saligenin vapor.

Then, formaldehyde monomer vapor (2 × 10 ^-2 mol / dm ³ ) which is a decomposition product of trioxane is added.
A mixed vapor consisting of and sulfur dioxide vapor (4 × 10 ⁻³ mol / dm ³ ) was prepared by taking out and mixing each vapor from a cylinder of each substance, and then pressurizing the mixed vapor into the reaction vessel. The modified wood was obtained by injecting and heating the reaction vessel at 120 ° C. for 24 hours.

Example 13 After fixing the cypress material in the reaction vessel, the reaction vessel was set at 120
Preheated at ° C. Next, phenol monomer vapor (2.0 × 10 ^-1 mol / dm ³ ) was injected under reduced pressure into this reaction vessel, and the reaction vessel was heated under pressure for several hours (10 atm).
The wood was impregnated by keeping it at

Then, formaldehyde monomer vapor (4 × 10 ^-2 mol / dm ³ ) which is a decomposition product of trioxane is added.
A mixed vapor consisting of and sulfur dioxide vapor (4 × 10 ⁻³ mol / dm ³ ) was prepared by taking out and mixing each vapor from a cylinder of each substance, and then injecting this mixed vapor into the reaction vessel under reduced pressure. Then, the reaction vessel was heated at 120 ° C. for 24 hours to obtain modified wood.

-Comparative Example 2-After fixing the cypress material in the reaction vessel, the reaction vessel was set at 120
Preheated at ° C. Next, formaldehyde monomer vapor, which is a decomposition product of trioxane (2 × 10 ^-2 mol / dm
³ ) and sulfur dioxide vapor (4 × 10 ⁻³ mol / dm ³ ) were prepared by mixing the vapors of each substance by taking out the vapors from the cylinders and mixing them. Modified wood was obtained by injecting under reduced pressure and heating the reaction vessel at 120 ° C. for 24 hours.

For the modified woods obtained in Examples 11 to 13 and Comparative Example 2 above, the impregnation rate and the anti-swelling ability (ASE) were determined in the same manner as above. The results are shown in Table 2 below.

[0052]

[Table 2]

As shown in Table 2, Examples 11 to 1 obtained by impregnating a volatile monomer and performing a formalization treatment
The modified wood of 3 has higher anti-swelling ability and higher dimensional stability than the modified wood of Comparative Example obtained by only formalizing the wood without impregnating the volatile monomer. It was confirmed to be extremely excellent. -Example 14-A 20% by weight aqueous solution of polyethylene glycol (molecular weight: about 300) was impregnated into a cypress material (specific gravity: 0.4) under reduced pressure, air-dried, and then dried in a dryer at 100 ° C for several hours. ..

Next, this cypress material was placed in a reaction vessel for formalization, and formaldehyde vapor (2 × 10 ^-2 mol / dm ³ ) prepared by heating trioxane in the presence of sulfur dioxide in advance. A modified gas was obtained by introducing a mixed gas composed of sulfur dioxide vapor (4 × 10 ⁻³ mol / dm ³ ) into the reaction vessel and maintaining the temperature in the reaction vessel at 120 ° C. for 24 hours.

Example 15 In Example 14, polyvinyl alcohol (molecular weight: 5) was used instead of the 20% by weight aqueous solution of polyethylene glycol.
Modified wood was obtained in the same manner as in Example 14 except that the 10% by weight aqueous solution of (00) was used. -Example 16-In Example 14, 20 weight% of polyacrylamide is replaced with 20 weight% of polyethylene glycol aqueous solution.
Modified wood was obtained in the same manner as in Example 14 except that the aqueous solution was used.

Comparative Example 3 A 30% by weight aqueous solution of polyethylene glycol (molecular weight 2000) was impregnated into a cypress material (specific gravity 0.4) under reduced pressure and then dried at 100 ° C. for 24 hours in a dryer for modification. I got wood. With respect to the modified wood obtained in Examples 14 to 16 and Comparative Example 3 above, the impregnation rate and the anti-swelling ability (ASE) were obtained and evaluated in the same manner as described above.
The water resistance was checked. The water resistance is ⊚ when the resin fixing rate calculated according to the following formula (3) is 90% or more, ◯ when 80% or more and less than 90%, and Δ when 50% or more and less than 80%. , Less than 50% was evaluated by x.

Fixation ratio (%) = (G ₂ / G ₁ ) × 100 (3) (In the formula (3), G ₁ represents the impregnation ratio of the modified wood before the water saturation treatment, and G ₂ represents the water saturation. It represents the impregnation rate of the modified wood after treatment.) The results are shown in Table 3 below.

[0058]

[Table 3]

As shown in Table 3, the modified woods of Examples 14 to 16 obtained by the formalization treatment are compared with the modified woods of Comparative Example 3 obtained without the formalization treatment. Although the impregnation rate was almost the same, it was confirmed that the anti-swelling ability was high, the dimensional stability was extremely excellent, and the water resistance was also excellent. Example 17-20 parts by weight methylol acrylamide, 5 parts by weight trioxane, 0.5 parts by weight potassium persulfate and 10 parts by weight.
After impregnating cypress wood with an aqueous solution consisting of 0 parts by weight of water under reduced pressure, it is dried in an open system at 110 ° C. to obtain a water content of 5 to 5.
Adjusted to 10%. Then, the sealed system was heated at 120 ° C. to obtain modified wood.

Example 18 A hinoki material was impregnated under reduced pressure with an aqueous solution containing 20 parts by weight of methylolmelamine, 5 parts by weight of trioxane and 100 parts by weight of water. After that, the same operation as in Example 17 was performed to obtain modified wood. -Example 19- An aqueous solution of 20 parts by weight of phenol, 5 parts by weight of tetraoxane and 100 parts by weight of water was impregnated into a cypress material under reduced pressure. After that, the same operation as in Example 17 was performed to obtain modified wood.

Example 20 A hinoki material was impregnated under reduced pressure with an aqueous solution containing 20 parts by weight of methylolmethacrylamide, 5 parts by weight of tetraoxane, 0.5 part by weight of potassium persulfate and 100 parts by weight of water. After that, perform the same operation as in Example 17,
Modified wood was obtained.

Example 21 A hinoki material was impregnated under reduced pressure with an aqueous solution containing 20 parts by weight of saligenin, 5 parts by weight of tetraoxane and 100 parts by weight of water. After that, the same operation as in Example 17 was performed to obtain modified wood. -Comparative Example 4- 20 parts by weight of methylol acrylamide, 0.5 parts by weight of potassium persulfate, and 100 parts by weight of water were impregnated into a hinoki material under reduced pressure, followed by drying at 110 ° C to modify. I got wood.

The modified woods obtained in Examples 17 to 21 and Comparative Example 4 were evaluated for antiswelling ability (ASE) in the same manner as above. The results are shown in Table 4 below.

[0064]

[Table 4]

As shown in Table 4, the modified woods of Examples 17 to 21 obtained by the formalization treatment are compared with the modified woods of Comparative Example 4 obtained without the formalization treatment. It was confirmed that the anti-swelling ability was high and the dimensional stability was extremely excellent. -Example 22-After fixing a cypress material in a reaction container, the reaction container was set to 120
Preheated at ° C.

Next, a predetermined amount of saligenin was placed in the reaction vessel, and the interior of the reaction vessel was depressurized and heated to impregnate the wood with saligenin vapor. This wood was impregnated with an aqueous solution consisting of 5 parts by weight of tetraoxane and 100 parts by weight of water under reduced pressure, and then dried at 110 ° C. in an open system,
The water content of the wood was adjusted to 5-10%. Then, the sealed system was heated at 120 ° C. to obtain modified wood.

-Example 23- After fixing a cypress material in a reaction vessel, the reaction vessel was placed at 120
Preheated at ° C. Next, phenol monomer vapor (2.0 × 10 ^-1 mol / dm ³ ) was injected under reduced pressure into this reaction vessel, and the reaction vessel was heated under pressure for several hours (10 atm).
The wood was impregnated with phenol vapor by keeping

This wood was impregnated with an aqueous solution of 5 parts by weight of tetraoxane and 100 parts by weight of water under reduced pressure, and then dried at 110 ° C. in an open system to obtain a water content of 5 to 1 for the wood.
Adjusted to 0%. Then, the sealed system was heated at 120 ° C. to obtain modified wood. -Comparative Example 5-After fixing the cypress material in the reaction vessel, the reaction vessel was set to 120
Preheated at ° C.

Next, phenol monomer vapor (2.0 × 10 ^-1 mol / dm ³ ) was injected under reduced pressure into this reaction vessel, and the inside of the reaction vessel was kept under pressure (10 atm) under heating for several hours. As a result, modified wood was obtained. The modified wood obtained in Examples 22 to 23 and Comparative Example 5 above was evaluated for antiswelling ability (ASE) in the same manner as above.

The results are shown in Table 5 below.

[0071]

[Table 5]

As shown in Table 5, the modified woods of Examples 22 to 23 obtained by the formalization treatment are compared with the modified woods of Comparative Example 5 obtained without the formalization treatment. It was confirmed that the anti-swelling ability was high and the dimensional stability was extremely excellent. -Example 24-A 3% by weight aqueous solution of saligenin was vacuum-injected and dipped and impregnated in a hemlock hemlock material, and then the wood was once air-dried, then placed in a drier and dried at 100 ° C for several hours.
The water content was adjusted.

Next, the treated wood thus obtained was placed in a reaction vessel for formalization, and the temperature inside the vessel was raised and kept at 120.degree. Then, the inside of the tank was depressurized (50 mmHg), and the formaldehyde monomer vapor (1.5 × 10 ^-2 mol / dm ³⁾ prepared by heating trioxane in the presence of sulfur dioxide in another reaction tank in advance. ) And sulfur dioxide vapor (1 x
By introducing a mixed gas of 10 ⁻³ mol / dm ³ ) into the reaction vessel for formalization and maintaining the temperature at 120 ° C. for 8 hours,
Modified wood was obtained.

Example 25 A 3% by weight aqueous solution of saligenin was vacuum-injected and impregnated into a hemlock moth, and then wood was once air-dried and then placed in a drier and dried at 100 ° C. for several hours. Due to
The water content was adjusted. Next, the treated wood thus obtained was placed in a reaction vessel for formalization, and the temperature inside the vessel was raised and kept at 80 ° C.
Then, the inside of the tank was depressurized (50 mmHg), and formaldehyde monomer vapor (1.0 × 10 ^-2 mol / dm ³⁾ prepared by heating trioxane in the presence of sulfur dioxide in another reaction tank in advance. ) And sulfur dioxide vapor (1 × 10 ⁻³ mol / dm ³ ) were introduced into the formalization reaction tank. With the temperature kept at 80 ° C., nitrogen was further introduced to pressurize the tank to about 3 atm, and this state was kept for 8 hours to obtain modified wood.

-Example 26-After a 3% by weight aqueous solution of saligenin was injected under reduced pressure and impregnated and impregnated into a hemlock hemlock, wood was once air-dried, then placed in a drier and dried at 100 ° C for several hours. Due to
The water content was adjusted. Next, the obtained treated wood was placed in a reaction vessel for formalization, and the temperature inside the vessel was raised and kept at 120 ° C. Then, the inside of the tank was depressurized (50 mmHg), and formaldehyde monomer vapor (1.0 × 10 ^-2 mol / dm ³⁾ prepared by heating trioxane in the presence of sulfur dioxide in another reaction tank in advance. ) And sulfur dioxide vapor (1 × 10 ⁻³ mol / dm ³ ) were introduced into the formalization reaction tank. While keeping the temperature at 80 ℃, 4
After standing for a period of time, nitrogen was introduced to pressurize the tank to about 3 atm, and this pressurized state was maintained for 4 hours to obtain modified wood.

Example 27 A 3% by weight aqueous solution of saligenin was vacuum-injected into and impregnated into a hemlock shrimp material, and then the wood was once air-dried and then placed in a drier and dried at 100 ° C. for several hours. Due to
The water content was adjusted. Next, the treated wood thus obtained was placed in a reaction vessel for formalization, and the temperature inside the vessel was raised and kept at 80 ° C.
After adding trioxane (solid) in an amount of 1.5 × 10 ⁻² mol / dm ³ in terms of formaldehyde monomer vapor into the reaction tank, the inside of the tank was depressurized (50 mmHg) and kept for 4 hours. After that, sulfur dioxide vapor (1 × 10 ^-3 mol /
dm ³ ) was introduced into the tank, the temperature inside the tank was raised to 120 ° C,
By holding this state for 4 hours, modified wood was obtained.

Example 28-After a 3% by weight aqueous solution of saligenin was injected under reduced pressure and impregnated into a hemlock slug, the wood was once air-dried, then placed in a drier and dried at 100 ° C. for several hours. Due to
The water content was adjusted. Next, the treated wood thus obtained was placed in a reaction vessel for formalization, and the temperature inside the vessel was raised and kept at 80 ° C.
After adding trioxane in an amount of 1.5 × 10 ⁻² mol / dm ³ in terms of formaldehyde monomer vapor into the reaction tank, the inside of the tank was depressurized (50 mmHg) and kept for 4 hours. Then, sulfur dioxide vapor (1 × 10 ⁻³ mol / dm ³ ) was introduced into the tank, the temperature inside the tank was raised to 120 ° C., and nitrogen was introduced to pressurize the tank to about 3 atm. By holding this state for 4 hours, modified wood was obtained.

-Example 29- After a 3% by weight aqueous solution of saligenin was injected under reduced pressure and dipped and impregnated in a hemlock slug, the wood was once air-dried, then placed in a drier and dried at 100 ° C for several hours. Due to
The water content was adjusted. Next, the treated wood thus obtained was placed in a reaction vessel for formalization, and the temperature inside the vessel was raised and kept at 80 ° C.
After adding trioxane in an amount of 1.5 × 10 ⁻² mol / dm ³ in terms of formaldehyde monomer vapor into the reaction tank, the inside of the tank was depressurized (50 mmHg) and kept for 4 hours. Then, the gas in the tank was once exhausted, and then sulfur dioxide vapor (0.5 × 10 ⁻³ mol / dm ³ ) was introduced into the tank to raise the temperature in the tank to 120 ° C. Further, nitrogen was introduced to pressurize the tank to about 3 atm, and this state was maintained for 4 hours to obtain modified wood.

Comparative Example 6 After a 3% by weight aqueous solution of saligenin was vacuum-injected into and impregnated into a hemlock hemlock, wood was once air-dried, then placed in a drier and dried at 100 ° C. for several hours. Due to
The water content was adjusted. Next, the obtained treated wood was placed in a reaction vessel for formalization, and the temperature inside the vessel was raised and kept at 120 ° C. After adding trioxane in an amount of 1.5 × 10 ^-2 mol / dm ³ in terms of formaldehyde monomer vapor into the reaction vessel, the inside of the vessel was depressurized (50 mmHg) and sulfur dioxide vapor (1 × 10 ^-3 mol / dm ³ dm ³ ) was introduced into the tank. Then, the temperature was kept at 120 ° C. for 8 hours to obtain modified wood.

With respect to the modified woods obtained in Examples 24 to 29 and Comparative Example 6, the anti-swelling ability (ASE) was determined in the same manner as described above. Further, using a color difference meter, the color difference change ΔE before and after the treatment of each piece of wood was determined. The results are shown in Table 6 below.

[0081]

[Table 6]

As shown in Table 6, the modified woods of Examples 24 to 29 have higher anti-swelling ability than the modified wood of Comparative Example 6 and have very excellent dimensional stability.
It was confirmed that there was little discoloration of the wood.

[0083]

EFFECTS OF THE INVENTION According to the method for producing modified wood according to the present invention, it is possible to efficiently obtain modified wood which is highly dimensionally stabilized and whose surface wood texture is not lost. Also,
The active ingredient generated inside the obtained modified wood is insoluble in water, so there is no risk of exuding to the wood surface due to water, moisture, etc. and degrading the performance. It also has excellent weather resistance such as water resistance and moisture resistance.

Further, since the above-mentioned active ingredient is formalized, the modified wood obtained is given antiseptic and insect repellent properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoru Konishi 1048, Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Inventor, Kenji Onishi, 1048, Kadoma, Kadoma, Osaka Prefecture

Claims (8)

[Claims] 1. A raw material wood is impregnated with a compound A capable of reacting with formaldehyde to form an insoluble hardened resin and formaldehyde and / or a derivative thereof, and the raw material wood is heated. Then, the modified wood is produced by causing a formalization reaction in the wood to generate and fix the insoluble cured resin in the wood tissue. 2. The method for producing modified wood according to claim 1, wherein the compound A is at least one resin monomer selected from the group consisting of acrylamides, phenols and amines and / or an oligomer thereof. 3. The compound A is at least one volatile resin monomer selected from the group consisting of phenol and its derivatives and / or its initial condensate.
A method for producing the modified wood described. 4. The method for producing modified wood according to claim 1, wherein the compound A is at least one water-soluble resin polymer selected from the group consisting of polyoxyethers, polyols and polyacrylic acids. 5. The method according to claim 1, wherein when the formalization reaction is performed, the wood is dried below the fiber saturation point in an open system and then the wood is heated in a closed system. Of modified wood in Japan. 6. The method for producing a modified wood according to claim 1, wherein the solvent is water. 7. The method for producing modified wood according to claim 1, wherein the raw material wood is impregnated with the formaldehyde monomer vapor obtained by previously decomposing the formaldehyde derivative. 8. A compound A, formaldehyde and / or
The raw material wood is impregnated with the derivative or its derivative, and after curing, the raw material wood is impregnated with an acid catalyst.
The method for producing modified wood according to any one of 1 to 7.