JPS62248602A - Manufacture of improved wood - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing modified wood that imparts dimensional stability, fire retardancy, and antiseptic and insect repellent properties.

[Background technology]

As a method to obtain modified wood by imparting dimensional stability, fire retardancy, and antiseptic/insect repellent properties to wood, water-soluble inorganic ions react with each other in the wood to generate water-insoluble and non-flammable inorganic substances. A method has been developed.

Next, the flame retardant treatment, antiseptic/insect repellent treatment, and dimensional stabilization treatment of wood will be explained.

There are various methods for making wood flame retardant, but they can be classified into the following categories based on the mechanism of flame retardancy.

(a) Coating with inorganic substances (BL Promotion of carbonization (inhibition of chain reaction in C1 flaming combustion (d) Generation of non-flammable gas (el) Absorption of heat due to decomposition and release of water of crystallization (f) Water-insoluble non-combustible coating on insulation wood with foam layer If a sterile inorganic substance is included, effects due to the mechanisms described above (in addition to Al, depending on the type of insoluble nonflammable inorganic substance) and (C) can also be expected.

Regarding the mechanisms of (a), (b) and (C),
This will be explained in detail next. The inorganic coating in (a) is
Even if the material is flammable, it can be made flame retardant by combining it with a non-flammable inorganic substance at an appropriate blending ratio. For example, the conventionally known wood chip cement board is made by mixing combustible wood with noncombustible cement at a weight ratio of about 1:1 and forming it into a board shape, which is recognized as a quasi-noncombustible material by JIS. It is being (The carbonization promotion reaction of BL has the following mechanism. When wood is heated, it thermally decomposes and generates flammable gas, which causes flaming combustion. However, in the presence of phosphoric acid or boric acid, Thermal decomposition or carbonization of the wood is promoted.The carbonized layer thus formed acts as a heat insulating layer and produces a flame retardant effect.Therefore, if the insoluble, nonflammable inorganic substance contains a phosphoric acid component or a boric acid component, This mechanism provides a flame retardant effect. (C) is a mechanism in which halogen acts as a chain transfer agent in a radical oxidation reaction in a flame, inhibiting the oxidation reaction and producing a flame retardant effect. Therefore, if the insoluble, nonflammable inorganic substance contains halogen, a flame retardant effect can be obtained by this mechanism.If it is insoluble, there is little risk that the wood will emit molten metal.

Next, we will explain how to make wood rot-proof and insect-proof. When fungi cause wood to rot, it is essential that hyphae first invade the inner cavity of the wood. However, if foreign matter is present in the internal cavity of the wood, mycelium cannot enter, and as a result, the wood becomes less susceptible to decay. The foreign matter in the internal cavity of the wood does not need to be a drug with a particular antiseptic effect, and may be anything as long as it does not serve as nutrients for fungi. The same applies to insect repellent as preservative. Therefore, if unnecessary non-combustible inorganic substances are included in the inner cavity of wood, the antiseptic and insect repellent properties of wood can be improved.

Furthermore, dimensional stabilization of wood will be explained.

If wood can be swollen and some substance can be fixed in the wood cell walls, dimensional stability can be achieved due to the bulk effect. Inorganic substances can also be used as immobilizing substances. Therefore, dimensional stability can be improved by fixing insoluble, non-combustible inorganic substances into wood cell walls. Of course, it is difficult to fix inorganic substances in wood cell walls using a treatment solution in which water-insoluble inorganic substances are dispersed in water. Therefore, it is first impregnated into the wood cell wall as water-soluble ions, and then reacted with other ions to make it insoluble in water, producing water-insoluble inorganic substances in the wood cell wall. .

According to the conventional method, fire protection is generally achieved.

It becomes possible to obtain modified wood that has high performance in terms of antiseptic and insect repellent properties. However, although a certain degree of dimensional stability can be obtained, it has not been possible to obtain a very high level of dimensional stability.

[Purpose of the invention]

This invention has been made in view of the above circumstances, and provides a method for producing modified wood that has excellent fire retardancy, rot and insect repellency, and is also excellent in dimensional stability. The purpose is to

[Disclosure of the invention]

In order to achieve the above objectives, the inventors first
We investigated methods that can provide high dimensional stability. As a result, it was found that some organic substances exhibit high dimensional stability due to the bulk effect when used as substances fixed in wood cell walls. However, wood whose dimensions have been stabilized by the bulk effect of organic matter cannot be expected to improve its fire resistance. Therefore, the inventors conducted further research. As a result, they discovered that by simultaneously using both organic and inorganic substances as fixing substances, it is possible to obtain modified wood that has high dimensional stability and is excellent in fire retardant, rot and insect repellent properties. Here we have completed this invention.

Therefore, this invention impregnates wood in which an organic substance effective for stabilizing the dimensions of wood has been fixed in its tissue with one of two aqueous solutions of water-soluble inorganic substances that produce insoluble and non-flammable inorganic substances by mixing. Furthermore, the gist is a method for producing modified wood in which an insoluble, nonflammable inorganic substance is fixed in the structure of the wood by impregnating it with the other aqueous solution.

The present invention will be explained in detail below.

As described above, the present invention uses wood in which organic matter, which is effective for stabilizing the dimensions of the wood, is fixed in its tissue. Examples of organic substances (organic compounds) effective for stabilizing the dimensions of wood include water-soluble compounds such as phenol, phenol derivatives, urea, urea derivatives, melamine, melamine derivatives, polyethylene glycol, and polyethylene glycol derivatives (polyethylene glycol methacrylate, etc.). organic substances, and two or more types may be used in combination. As a method for impregnating wood with an organic substance, for example, after saturating the wood with water as necessary, the organic substance is made into a solution such as an aqueous solution, and the wood is immersed in this solution. The appropriate amount of organic matter is impregnated depending on the type, etc.

Insoluble nonflammable inorganic substances (inorganic compounds) by mixing
Using two types of aqueous solutions of water-soluble inorganic substances that produce , the insoluble and nonflammable inorganic substance is fixed in the structure of the wood containing the above-mentioned organic substances. If the wood is impregnated with an organic substance such as the one described above in advance, the effect of making it easier for the inorganic substance to enter the wood can be obtained. First, one of the aqueous solutions is impregnated into the structure of the wood using a vacuum impregnation method or the like. next,
The other aqueous solution is impregnated by immersion or the like to precipitate the insoluble, nonflammable inorganic substance within the wood structure. Examples of insoluble nonflammable inorganic substances that precipitate in water include calcium carbonate, calcium phosphate, calcium hydroxide,
Examples include calcium sulfate, calcium silicate, magnesium carbonate, magnesium phosphate, magnesium ammonium phosphate, magnesium silicate, aluminum hydroxide, aluminum phosphate, aluminum silicate, barium carbonate, barium sulfate, barium phosphate, apatite, etc. . Two or more types of insoluble, non-combustible inorganic substances may be included in the wood.

For example, when the insoluble nonflammable inorganic substance is calcium carbonate, one aqueous solution A may include calcium bromide, calcium chloride, calcium chlorate, calcium nitrate, calcium nitrite, calcium chromate, calcium acetate, etc.
The other aqueous solution B contains at least one of ammonium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium sodium carbonate, and the like. In the case of calcium phosphate, one aqueous solution A is the same as the aqueous solution A of calcium carbonate, and the other aqueous solution B contains at least one of each of phosphoric acid, sodium phosphate, potassium phosphate, ammonium phosphate, etc. Use what includes. In the case of calcium hydroxide, one aqueous solution A is similar to the calcium carbonate aqueous solution A, and the other aqueous solution B contains at least one of sodium hydroxide, potassium hydroxide, ammonia, etc. use

In the case of calcium sulfate, one aqueous solution A is the same as calcium carbonate aqueous solution A, and the other aqueous solution B is aluminum sulfate, sodium sulfate, sodium hydrogen sulfate, potassium sulfate, potassium hydrogen sulfate, magnesium sulfate, ammonium sulfate. , sodium aluminum sulfate, potassium aluminum sulfate, ammonium aluminum sulfate, potassium magnesium sulfate, etc., are used.

In the case of calcium silicate, one aqueous solution A is similar to the aqueous solution A in the case of calcium carbonate, and the other aqueous solution B contains at least one of sodium silicate, potassium silicate, etc. use In the case of magnesium carbonate, one aqueous solution A contains at least one kind of magnesium chloride, magnesium sulfate, etc., and the other aqueous solution B contains at least one of the same as the calcium carbonate aqueous solution B. In the case of magnesium phosphate, one aqueous solution A is the same as the aqueous solution A in the case of magnesium carbonate, and the other aqueous solution B
As for the aqueous solution B, a solution containing at least one kind similar to the aqueous solution B in the case of calcium phosphate is used.

In the case of magnesium hydroxide, one aqueous solution A is:
The same aqueous solution A in the case of magnesium carbonate and the same aqueous solution B as the other aqueous solution B are used, respectively, containing at least one kind of solution similar to the B solution in the case of calcium hydroxide. In the case of ammonium magnesium phosphate, one aqueous solution A is the same as the aqueous solution A for calcium carbonate, and the other aqueous solution B is a magnesium mixture (mixture of magnesium chloride, ammonium chloride, ammonia), etc. , containing at least one kind. In the case of magnesium silicate, one aqueous solution A is the same as the aqueous solution used in the case of magnesium carbonate, and the other aqueous solution B is the same as the aqueous solution B in the case of calcium silicate. Use those that contain seeds. In the case of aluminum hydroxide, one aqueous solution A is aluminum chloride, aluminum bromide, aluminum iodide, aluminum nitrate, aluminum sulfate, etc., and the other aqueous solution B is the same as aqueous solution B in the case of calcium hydroxide. A material containing at least one of the following is used. In the case of aluminum phosphate, one aqueous solution A is the same as the aqueous solution A in the case of aluminum hydroxide, and the other aqueous solution B is the same as the aqueous solution B in the case of calcium phosphate. Use what includes. In the case of aluminum silicate, one aqueous solution A is the same as the aqueous solution A in the case of aluminum hydroxide, and the other aqueous solution B
As for the aqueous solution B, a solution containing at least one kind similar to the aqueous solution B in the case of calcium silicate is used.

In the case of barium carbonate, one aqueous solution A is barium chloride, barium bromide, barium iodide, barium nitrate, barium hydroxide, etc., and the other aqueous solution B is the same as aqueous solution B in the case of calcium carbonate. ,Each,
Use one containing at least one kind. In the case of barium sulfate, one aqueous solution A is the same as the aqueous solution A in the case of barium carbonate, and the other aqueous solution B is the same as the aqueous solution B in the case of calcium sulfate, each of which contains at least one kind. use something In the case of barium phosphate, one aqueous solution A is the same as the aqueous solution A in the case of barium carbonate, and the other aqueous solution B is the same as the aqueous solution B in the case of calcium phosphate, respectively.
Use one containing at least one kind.

One of the two types of aqueous solutions may be, for example, an aqueous solution containing a small amount (all of one type) of cations such as alkali metals, alkaline earth metals, and aluminum;
For example, BOs ion.

The apatite for which an aqueous solution containing at least one of the anions of PO4 ion and SO4 ion is used is M. (204) h This is a general term for a group of compounds belonging to the hexagonal space group P6z/m with the basic composition of Xi. Simply speaking, apatite often refers to those in which M=Ca and Z=P, and a typical example is hydroxyapatite Ca1°(PO4)6(OH)g, but in this invention, apatite is Refers to all compounds with a basic composition. In addition, it is known that a wide variety of constituent ion species enter the M site, which also contains crystal water, with 1 to 3 valences, the Z site with 3 to 7 valences, and the X site with 0 to 3 valences. There is. Furthermore, molecules such as H2O can also enter the X site. A specific example is given below.

M: (:a, pb, Cd, Sr, ・Ni, Eu, A
1, Y, La, Ce, Na, Ba Z: P, As, V, Cr, Si, C, Al, S, Re
, B X: OH, F, CI, Br, I, O, N, C03,
Hz O, Vacancy (Vacancy) The M, Z, and X listed here are not limited to any possible combinations, but are limited by the ionic radius, etc. Each of M, Z, and X may contain two or more types at the same time.

The apatite is preferably selected from MIJ < Ba, Al, Z is B, P, is Ca, .(PO4)h (O
H)21 Ca+o (PO4)b C12, Ca+
o (PO4)h Fz , Ca+o (PO4)h
FX C12-X, Bate (PO4)s
(BO4) 口z, Caq Ni (PO4)b
F2 , Ca1lAlt (PO4) s (A
10s) Ft etc.

To generate apatite as described above in an aqueous solution,
The constituent ions are mixed in the stoichiometric molar ratio of the product, P
It can be obtained by curing at H8.5 or higher, and the method for producing it in wood is as follows, for example.

First, Ca, Ba2'''+ A l 3+, N i
Wood is impregnated with an aqueous solution C containing at least one of the ions that can be M such as z * and at least one of the ions or molecules that can be X such as C1- and F- as necessary. Later, PO43-, BO, '-, AI
Z Impregnate into wood. The aqueous solution C2D is prepared by dissolving in water a water-soluble inorganic substance capable of producing the above-mentioned ions or molecules. Then, if necessary, the wood is cured to generate apatite in the wood and fix it. The order of impregnation with aqueous solutions C and D may be reversed. Further, it is also possible to impregnate the aqueous solution D', which has the same structure as the aqueous solution but is not alkaline, and then impregnate the alkaline treatment liquid. Aqueous solution C may be made alkaline.

The modified wood obtained in this way has high dimensional stability as well as organic substances that are effective in stabilizing the dimensions of the wood, as well as insoluble and nonflammable inorganic substances. It will also be excellent.

Next, examples will be described.

(Example 1) A 3xvr thick rotary veneer made of beech wood was immersed in water at room temperature and left for 5 hours under reduced pressure of about 3QTorr to saturate it with water. This saturated veneer was treated with an aqueous solution of polyethylene glycol methacrylate (PEGMA) (first treatment liquid).
After that, it was immersed in a mixed aqueous solution of BaC1□ and H2BO2 (second treatment liquid), and then (N Ha )
z HP It was immersed in a bath containing a mixed aqueous solution of Oa and H3BO3 (third treatment liquid). And finally, pH8
-10 was immersed in a fourth treatment bath containing an alkaline aqueous solution. Through these treatments, modified wood containing 70 wood products per 100 wood bone dry weight was obtained. This modified wood has excellent dimensional stability and
It also had excellent fire retardant, rot and insect repellent properties.

(Example 2) In the same manner as in Example 1, a 3-fin thick rotary veneer made of beech wood was subjected to water saturation treatment to obtain a water saturated veneer. This veneer is PEGM
Treatment with aqueous solution of A (first treatment solution), BaCl,,l
(, B□, treatment with a mixed aqueous solution (second treatment liquid), and treatment with a mixed aqueous solution of CNHa)tHPOa, H3B Ox (third treatment liquid). After this, the veneer was impregnated with an alkaline aqueous solution under reduced pressure. Through these treatments, modified wood containing 70 wood products per 100 wood bone dry weight was obtained. This modified wood had excellent dimensional stability, and was also excellent in fire retardant, rot and insect repellent properties.

(Example 3) Instead of 1 g of BaC and a mixed aqueous solution of H, BO3,
Modified wood was obtained using the same materials and methods as in Example 1, except that a mixed aqueous solution of CaClt and H3BO3 was used. This modified wood had excellent dimensional stability, and was also excellent in fire retardant, rot and insect repellent properties.

(Example 4) In the same manner as in Example 1, a 3-double thick veneer of beech wood was made into a water-saturated veneer, and then immersed in an aqueous solution of PEGMA (first treatment liquid). After this, All (S.

4): immersed in 1 aqueous solution (second treatment liquid), and
(N Ha ) z HP It was immersed in a mixed aqueous solution (third treatment liquid) of Oa and H3BO. Next, pH8
It was immersed in a fourth treatment bath containing an alkaline aqueous solution of ~10. Through these treatments, modified wood containing 70 wood endogenous acids per 100 wood bone dry weight was obtained. This modified wood has excellent dimensional stability and
It also had excellent fire retardant, rot and insect repellent properties.

(Example 5) A 31-thick rotary veneer made of beech wood was immersed in an aqueous solution of PEGMA (first treatment liquid) and impregnated under reduced pressure.

Thereafter, in the same manner as in Example 4, it was impregnated with the second treatment liquid and the third treatment liquid, and then immersed in the fourth treatment bath. Through these treatments, modified wood with excellent dimensional stability, as well as excellent fire retardant, rot and insect repellent properties was obtained.

〔Effect of the invention〕

The method for producing modified wood according to the present invention is one of two types of aqueous solutions of water-soluble inorganic substances that produce insoluble and non-combustible inorganic substances by mixing with wood in which organic substances effective for stabilizing the dimensions of wood have been fixed in the tissue. By impregnating the wood with one aqueous solution and then impregnating it with the other aqueous solution, an insoluble, non-combustible inorganic substance is fixed in the structure of the wood, so it has excellent dimensional stability, fire retardant properties, and antiseptic and insect repellent properties. can be obtained.

Claims (4)

[Claims] (1) Wood in which organic substances effective for stabilizing the dimensions of wood have been fixed in its tissue is impregnated with one of two aqueous solutions of water-soluble inorganic substances that produce insoluble and nonflammable inorganic substances when mixed, and further, A method for producing modified wood that fixes an insoluble, nonflammable inorganic substance within the structure of the wood by impregnating it with another aqueous solution. (2) Claim 1, wherein the organic substance is at least one selected from the group consisting of phenol, phenol derivatives, urea, urea derivatives, melamine, melamine derivatives, polyethylene glycol, and polyethylene glycol derivatives. Process for producing modified wood. (3) One of the two aqueous solutions contains at least one of cations of alkali metals, alkaline earth metals, and aluminum, and the other contains anions of BO_3 ions, PO_4 ions, and SO_4 ions. The method for producing modified wood according to claim 1 or 2, wherein the method is an aqueous solution containing at least one of the above. (4) The insoluble nonflammable inorganic substance is M_1_0 (ZO_4)
_6X_2 (M: Ba, Al, Z: B, P, X: OH,
The method for producing modified wood according to claim 1 or 2, wherein the modified wood is apatite having a basic structure of Cl, Br).