JPH0655509A - Manufacture of modified wood - Google Patents

Abstract

PURPOSE:To provide the manufacturing method of modified wood, the flame retardancy of which is retained and, at the same time, the humidity resistance of which is favorable, in the manufacturing method of modified wood, in which insoluble compound is produced and fixed by reacting cation-containing compound and anion-containing compound with each other in wood. CONSTITUTION:Cation-containing compound and anion-containing compound, both of which react on wood impregnated with water so as to develop insoluble compound, and water-soluble and thermosetting organic compound, which reacts on the wood impregnated with water so as to develop insoluble resin, are infiltrated in wood to be impregnated so as to produce and fix the insoluble and incombustible compound and the insoluble resin in the impregnated wood.

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 building materials and the like.

[0002]

2. Description of the Related Art Conventionally, insoluble incombustible compounds have been used as a modification method for imparting flame retardancy, antiseptic / insect proof, dimensional stability, water / moisture resistance, surface hardness, mechanical strength, and abrasion resistance to wood. There are known methods such as compounding with a compound, compounding with a functional resin, chemical modification by a chemical bond, and impregnation with a chemical such as a preservative.

The compounding with the insoluble incombustible compound is carried out mainly for the purpose of imparting flame retardancy, antiseptic / insect repellent properties, and surface hardness, and among them, especially regarding flame retardancy, modification reaching a quasi incombustible level. Wood has been obtained and is used as a material for fire doors and the like. The compounding with the above-mentioned functional resin is performed mainly for the purpose of imparting water / moisture resistance, surface hardness, mechanical strength, and abrasion resistance, and generally WP
Widely known as C. The chemical modification by the above-mentioned chemical bonding is mainly performed for the purpose of imparting dimensional stability and water / moisture resistance. For example, modified wood by acetylation is used as a water supply material for bathtubs and the like. Also,
The chemical impregnation is mainly performed for the purpose of imparting antiseptic / insect repellent properties and is widely used.

Among these reforming methods for modifying natural wood,
Particularly, in the modification method by the combination with the insoluble incombustible compound, as disclosed in, for example, JP-A-61-246003, a cation and an anion which react with each other to form an insoluble incombustible compound are separately prepared. It is known to modify the wood by impregnating the natural raw material wood with the two kinds of aqueous solutions contained in the above solution in order to generate and fix the insoluble incombustible compound. However, in this method for modifying wood, a reaction between the cation-containing compound and the anion-containing compound occurs outside the wood, so that an insoluble incombustible compound is produced in the aqueous solution in the dipping tank, and as a result, the composition of both aqueous solutions changes. There was a problem.

As a method for solving the above-mentioned problems, for example, a cation-containing compound and an anion-containing compound are sprayed on the opposite surfaces of the raw material wood to be modified, and then an insoluble compound is formed and fixed in the wood. The method is effective. According to this method, since the reaction between the cation-containing compound and the anion-containing compound occurs from the center of the wood, a modified wood having a high concentration of the insoluble incombustible compound in the center can be obtained, but the insoluble non-combustible compound in the wood is obtained. By-products and unreacted substances are generated in the wood when it is generated and fixed.
Since these by-products and unreacted substances easily absorb moisture in the atmosphere, there is a problem in that the modified wood has poor moisture resistance.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object of the present invention is to provide a method for producing a modified wood which retains flame retardancy and has good moisture resistance. To provide.

[0007]

The method for producing modified wood according to claim 1 of the present invention is as follows:
A cation-containing compound, an anion-containing compound, which reacts with each other to produce an insoluble non-flammable compound, and
An impregnating step of impregnating a water-soluble and thermosetting organic compound that produces an insoluble resin, and a producing / fixing step of producing and fixing the insoluble incombustible compound and the insoluble resin in the impregnated wood. It is characterized by having.

Further, in the method for producing modified wood according to claim 4 of the present invention, a cation-containing compound and an anion-containing compound which react with each other to the impregnated wood penetrated with water to produce an insoluble incombustible compound , An impregnating step of impregnating, a generation / fixing step of generating / fixing the insoluble incombustible compound in the impregnated wood, and a water-soluble material that forms an insoluble resin in the impregnated wood after the generation / fixing step And an impregnating step of impregnating a thermosetting organic compound, and a generating / fixing step of generating / fixing the insoluble resin in the impregnated wood.

[0009]

According to the present invention, the cation-containing compound and the anion-containing compound impregnated in the impregnation step form an insoluble incombustible compound in the formation / fixing step. The impregnated wood is modified in flammability by this insoluble, non-combustible compound. In this case, the wood contains hygroscopic by-products and unreacted substances that are produced together with the insoluble non-combustible compound. The organic compound impregnated in the impregnation step forms an insoluble resin, and this insoluble resin prevents the by-products and unreacted materials from migrating to the wood surface and fills the voids in the wood, thereby It becomes difficult for the burned modified wood to absorb moisture.

The present invention will be described in detail below. The present invention has an impregnation step. In this impregnation step, water-infiltrated wood to be impregnated is a water-soluble and thermosetting compound that forms a cation-containing compound, an anion-containing compound, and an insoluble resin that react with each other to form an insoluble incombustible compound. Of the organic compound.

As long as the wood to be impregnated for modification used in the present invention is water-infiltrated wood, it may be natural wood logs, lumber products, sliced veneers, plywood, etc. The raw material wood may be used, or the raw material wood may be pretreated by impregnating with either a cation-containing compound that produces an insoluble incombustible compound or an anion-containing compound. When the pretreated impregnated wood is used, the content of the insoluble incombustible compound formed in the wood can be increased in the thickness direction, which is effective for improving the performance such as flame retardancy. The impregnation method of this pretreatment is not particularly limited, but for example, either the cation-containing compound or the anion-containing compound may be dissolved in water and the raw material wood may be dipped in this aqueous solution, or the cation-containing compound or the anion-containing compound. After spraying it on the raw wood, it may be sealed and impregnated at high temperature and high humidity. The shape of the raw material wood is not particularly limited, but it is preferable that the area impregnated with the compound is larger than the volume of the wood. The tree species of the above-mentioned raw material wood is not limited at all.

In the present invention, as described above, the impregnated wood is impregnated with both the cation-containing compound and the anion-containing compound, and water is permeated into the raw wood. In this case, permeation to a saturated state is effective in increasing impregnation of the cation-containing compound and the anion-containing compound into the wood. The water penetration rate of the raw material wood is preferably 80% or more, and more preferably 100% or more with respect to the absolute dry weight of the raw material wood. The method of water permeation is not particularly limited, and examples thereof include underwater storage, steaming, impregnation under reduced pressure, and impregnation under pressure.

In the present invention, the insoluble non-combustible compound formed in the impregnated wood is not particularly limited,
For example, borate, phosphate, hydrogen phosphate, carbonate,
Examples thereof include sulfates, hydrogensulfates, silicates, nitrates, and hydroxides. In order to generate and fix the insoluble incombustible compound in wood, a cation-containing compound containing a cation species forming the cation portion of the insoluble incombustible compound and an anion species forming the anion portion of the insoluble incombustible compound are used. And an anion-containing compound containing. These cation-containing compounds and anion-containing compounds react with each other in the wood resulting in the formation of insoluble, non-combustible compounds. The insoluble incombustible compound may be present alone or in combination of two or more in the wood, and is arbitrarily selected according to the desired composition of the insoluble incombustible compound to be produced in the wood.

The cation species of the insoluble incombustible compound is not particularly limited, but for example, Mg, Ca, S
Alkaline earth metal ions such as r and Ba, Al, Fe and C
Examples thereof include metal ions such as u, Co, Ni, Mn, Pb, and Zn. The anionic species of the insoluble incombustible compound is not particularly limited, but for example, OH ⁻ , F ⁻ ,
Cl ⁻ , Br ⁻ , NO ₃ ⁻ , CO ₃ ²⁻ , BO ₃ ²⁻ , PO
₄ ³⁻ , SO ₄ ^{2−, and the} like. These cation species and anion species may be one kind, or two or more kinds may coexist as shown in the examples. Depending on the type of cation and anion, it may form the cation part or the anion part of the insoluble incombustible compound to be produced. Taking aluminum sulfate (Al ₂ (SO ₄ ) ₃ ) as an example, SO ₄ ^2- functions as an anion species for barium chloride (BaCl ₂ ), and diammonium hydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ) On the other hand, Al ³⁺ functions as a cation species. In selecting the cation-containing compound and the anion-containing compound, a combination that easily forms an insoluble nonflammable compound in wood is preferable.

In the present invention, as described above, the organic compound is water-soluble and is cured by heat to form an insoluble resin in wood. The organic compound is not particularly limited, but examples thereof include amino compounds and urea compounds. Among these organic compounds, compounds modified with phosphorus or sulfur impart flame retardancy to the insoluble resin formed in the wood, and are therefore advantageous for improving the flame retardancy of the modified wood. The organic compound may be impregnated by mixing with the cation-containing compound or the anion-containing compound used in the impregnation step.

Further, in the present invention, after the step of impregnating the cation-containing compound and the anion-containing compound and the step of forming and fixing the insoluble noncombustible compound in the impregnated wood,
Impregnation with an organic compound may be performed.

In the present invention, the impregnation method in the impregnation step of the cation-containing compound, the anion-containing compound and the organic compound is not particularly limited,
For example, a method of spraying a powdery cation-containing compound and an anion-containing compound on opposite sides is effective in that an insoluble nonflammable compound is not produced outside wood as described above. In this case, the insoluble non-combustible compound is formed in the center of the wood. To give an example of a specific method of impregnation, impregnated wood having the cation-containing compound sprinkled on one side, and impregnated wood having the anion-containing compound sprinkled on one side,
Orient the surface where these compounds are sprayed in the same direction,
The method of performing impregnation by alternately stacking the impregnated wood in which the cation-containing compound is sprayed and the impregnated wood in which the anion-containing compound is sprayed is a method of impregnating a plurality of impregnated wood at a time,
It is effective as an industrial method with good production efficiency.

The present invention has a production / fixing step after the impregnation step. The generation / fixation is realized by curing the impregnated wood impregnated with the cation-containing compound, the anion-containing compound and the organic compound in the impregnation step described above under heating. This heating method is not particularly limited. The heating after the cation-containing compound and the anion-containing compound are impregnated in the impregnation step accelerates the generation and fixation of the insoluble incombustible compound as the reaction of the cation-containing compound and the anion-containing compound proceeds in the wood. Upon heating after impregnation with the organic compound, the organic compound hardens in the wood to form an insoluble resin. Since this insoluble resin fills the voids in the wood, it prevents the by-products and unreacted products generated in the wood from moving in the wood, and as a result, the by-products and unreacted products in the wood are blocked. The objects settle and the wood which has been modified in flammability has better moisture resistance. Produces the above insoluble incombustible compounds
The heating step of fixing and the heating step of forming the insoluble resin may be performed simultaneously or separately. The temperature, time, method and the like of the above-mentioned curing conditions are not particularly limited, and are appropriately determined depending on the properties and amounts of the cation-containing compound, the anion-containing compound, and the organic compound.

It is preferable that the curing in the above-mentioned generation / fixing step is performed so that water in the wood is not volatilized and the wood is not dried. This method is not particularly limited, and examples thereof include a method of sealing the impregnated wood on which the cation-containing compound and the anion-containing compound are dispersed with a sheet.

After the above-mentioned impregnation of the cation-containing compound, the anion-containing compound, and the organic compound, and the production and fixing of the insoluble incombustible compound and the insoluble resin, the wood surface is washed with water, etc., if necessary. Dried,
Obtain the target modified wood.

[0021]

EXAMPLES Examples and comparative examples of the present invention will be given below.

Example 1 As raw material wood, a plurality of 3 mm thick Agatisu veneer
I prepared. After permeating water into this veneer to make it saturated,
As a pretreatment prior to the impregnation step in the invention, al sulfate
Minium (Al₂(SO_Four)₃・ 13H₂O) powder
1320 g / m ²Evenly spread these veneers at a rate of
Laminate with the spray surface facing up, and place aluminum sulfate on top.
A veneer on which um was not sprayed was placed. Obtained veneer laminate
Seal the body and cure at 60 ° C for 24 hours to obtain impregnated wood
It was Sprayed aluminum sulphate at the end of curing
Did not remain outside the impregnated wood.

The impregnation step of the present invention was carried out as follows.
On the upper surface of this impregnated wood, impregnated with the above impregnated wood
Aluminum sulfate SO_Four ^2-Against cation
Barium chloride (BaCl)₂・ 2H₂O),
This aluminum sulfate Al ³⁺As an anion species
Work, SO_Four ^2-Hydroxide acts as a cationic species against
Barium (Ba (OH)₂・ 8H₂O) 1 to 1 mole
1800g of the powder mixed in the ratio and as an organic compound,
Mix 400g of dimethylolurea powder,
0 g / m²Was sprayed evenly. This scattered cover
The impregnated wood was designated as (a). The upper surface of the remaining impregnated wood
As an anion-containing compound,
Mu ((NH_Four)₂HPO_Four) Powder 880g, organic
As a compound, 400 g of dimethylol urea powder
Mixed, 1280 g / m²Was sprayed evenly.
This scattered impregnated wood was designated as (b).

The production / fixing process of the present invention was performed as follows. Aiming at the spray surface of these impregnated woods (a),
(B), (a) ... The obtained laminate of impregnated wood was sealed and cured at 60 ° C. for 24 hours. After the curing was completed, the wood was washed with water and dried to obtain modified wood.

Examples 2 to 4 In Example 1, the type and thickness of the veneer, the conditions of the pretreatment prior to the impregnation of the present invention, the cation-containing compound used in the impregnation step, the anion-containing compound, and the organic compound. Modified wood was obtained in the same manner as in Example 1 except that the types and spraying amounts of No. 1 and the curing conditions were as shown in Table 1 below.

[0026]

[Table 1]

Example 5 As raw material wood, a plurality of 1 mm thick agatis wood veneers were prepared. After this veneer penetrate the water water-saturated state, as a pretreatment prior to the impregnation step in the present invention, the powder ratio of 440 g / m ² of aluminum sulfate _{(Al 2 (SO 4) 3} · 13H 2 O) Then, they were evenly sprayed, and the veneered surfaces of these veneers were laminated so that they faced upward, and the veneers on which aluminum sulfate was not sprayed were placed on the top. The obtained veneer laminate was sealed and cured at 80 ° C. for 24 hours to obtain impregnated wood.
When the curing was completed, the sprayed aluminum sulfate did not remain outside the impregnated wood.

The impregnation step of the cation-containing compound and the anion-containing compound of the present invention was performed as follows. Barium chloride (BaCl ₂ · 2H ₂ O) was applied to the upper surface of the impregnated wood.
If, barium hydroxide _{(Ba (OH) 2 · 8H} 2 O) 1
The powder mixed in a molar ratio of 1: 1 was evenly distributed at a rate of 600 g / m ² . This dispersed impregnated wood (a)
And On the upper surface of the remaining impregnated wood, diammonium hydrogen phosphate ((NH ₄ ) ₂
The powder of HPO ₄ ) was uniformly sprayed at a rate of 300 g / m ² . This scattered impregnated wood was designated as (b).

The production / fixing process of the present invention was performed as follows. Aiming at the spray surface of these impregnated woods (a),
(B), (a) ... The resulting laminate of impregnated wood was sealed and aged at 80 ° C. for 24 hours to produce an insoluble, non-combustible compound in the wood.

Next, the organic compound impregnation step and the formation / fixing step were performed as follows. The impregnated woods (a) and (b) that have produced the above insoluble non-combustible compound have an upper surface of an organic compound of melamine phosphate and methylol melamine mixed at a weight ratio of 1: 1 to obtain a powder of 900 g / m ² . so,
The woods (a) and (b) to be impregnated, which were sprayed uniformly and produced insoluble incombustible compounds, were also laminated with the spray surface of the organic compound facing upward. The obtained laminate of impregnated wood was sealed and cured at 40 ° C. for 24 hours. After the curing was completed, the wood was washed with water and dried to obtain modified wood.

[0031]

[Table 2]

Comparative Example 1 As raw material wood, a plurality of 1 mm thick Agatis wood veneers were prepared. Water was infiltrated into this veneer to make it saturated and used as impregnated wood. Barium chloride (BaCl ₂ · 2H ₂ O) was added as a cation-containing compound on the upper surface of the impregnated wood.
It was sprayed uniformly at a rate of 30 g / m ² . This scattered impregnated wood was designated as (a). On the upper surface of the remaining impregnated wood, magnesium sulfate (M
gSO ₄ ) was uniformly sprayed at a rate of 210 g / m ² . This scattered impregnated wood was designated as (b). Aiming at the spreading surface of these impregnated woods (a), (b), (a)
.. were alternately laminated in this order. The resulting impregnated wood laminate was sealed and aged at 60 ° C. for 24 hours to produce an insoluble non-combustible compound in the wood.

Next, the organic compound was not used, and unreacted
Mg, a thione species⁺, Ba⁺To react with
Impregnated wood (a) that has produced an insoluble and incombustible compound,
In both (b), phosphoric acid was used as the anion-containing compound on the upper surface.
Diammonium hydrogen ((NH_Four) ₂HPO_Four) Powder
100 g / m²Disperse evenly at the ratio of
Layered toward the top. Close the resulting laminate of impregnated wood
It was sealed and cured at 60 ° C. for 24 hours.

Comparative Example 2 Comparative Example 1 is the same as Comparative Example 1 except that the type and thickness of the veneer, the type and spraying amount of the cation-containing compound and the anion-containing compound, and the curing condition are the conditions shown in Table 3 below. A modified wood was obtained in the same manner as above.

[0035]

[Table 3]

The obtained Examples 1-5 and Comparative Examples 1-2
The moisture absorption rate was measured as the content of the insoluble incombustible compound and the insoluble resin, the flame retardancy, and the moisture resistance of the modified wood.

The content rate was determined according to the following formula. - content _{(%) = {(W 2} -W 1) / W 1} ×
100 · W ₁ represents the absolute dry weight before water penetration. · W ₂ represents the absolute dry weight of the resulting modified wood.

The flame retardance was evaluated by carrying out a surface combustion test according to JIS-A-1321 and showing the performance of a quasi non-combustible level by ◯.

The moisture absorption rate was determined based on the JAS test.
Two 5 cm square test pieces were prepared and treated at a temperature of 40 ° C. and a relative humidity of 75% for 48 hours, and a weight W ₃ was added, and at a temperature of 40 ° C. and a relative humidity of 95% for 24 hours, a weight W _{4 was applied.} It was determined weight increase (W ₄ -W ₃₎ from. The weight increase (W ₄ -W ₃ ) for both of them is 0.4 g / 5 cm square or less. ○ 1 is 0.4 g / 5 cm square or less and 1 is 0.4
Items exceeding g / 5 cm square are △, both are 0.4 g / 5c
Those that exceeded the m-square were marked with x.

The results are shown in Table 4.

[0041]

[Table 4]

As is clear from the above examples and comparative examples,
The flame retardancy was good in both Examples and Comparative Examples. Examples are
By forming and fixing an insoluble resin by impregnation with an organic compound, the moisture resistance was improved as compared with the comparative example.

[0043]

EFFECTS OF THE INVENTION According to the production method of the present invention, a cation-containing compound, an anion-containing compound, and an organic compound are used, and both an insoluble noncombustible compound and an insoluble resin are produced and fixed in wood, so that flame retardancy is excellent. In addition, modified wood having improved moisture resistance can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryusuke Honda 1048 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd. (72) Hiroyuki Ishikawa, 1048 Kadoma, Kadoma City, Osaka Matsushita Electric Works Co., Ltd. 72) Inventor Arihiro Adachi 1048 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd.

Claims (4)

[Claims] 1. A water-soluble and thermosetting compound which forms a cation-containing compound, an anion-containing compound, and an insoluble resin, which react with each other to impregnated wood penetrated with water to form an insoluble nonflammable compound. The method for producing modified wood, comprising: an impregnating step of impregnating the organic compound of 1) with an impregnating wood, and a generating / fixing step of generating / fixing the insoluble incombustible compound and the insoluble resin in the impregnated wood. 2. The modified wood according to claim 1, wherein in the impregnating step, the cation-containing compound and the anion-containing compound are sprayed and impregnated on the opposite surfaces of the impregnated wood in powder form. Manufacturing method. 3. The impregnated wood is obtained by impregnating raw wood with either the cation-containing compound or the anion-containing compound.
Of modified wood in Japan. 4. An impregnating step of impregnating impregnated wood impregnated with water with a cation-containing compound and an anion-containing compound which react with each other to generate an insoluble incombustible compound, Produces insoluble and incombustible compounds
A forming / fixing step of fixing, and an impregnating step of impregnating a water-soluble and thermosetting organic compound that forms an insoluble resin in the impregnated wood after the forming / fixing step, and A method for producing modified wood, comprising a production / fixing step of producing / fixing the insoluble resin.