JP3211906B2 - Resin-impregnated wood and its manufacturing method - Google Patents

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 wood impregnated with resin, and to a resin-impregnated wood which is dimensionally stable and has excellent weather resistance while retaining the texture of wood for construction, construction, and building materials. An object of the present invention is to provide a manufacturing method thereof.

[0002]

2. Description of the Related Art At present, wood is impregnated with a resin comprising a combination of a (meth) acrylate ester such as a methyl (meth) acrylate monomer or a styrene monomer and an unsaturated polyester resin, and is cured by heat, electron beam, gamma ray or the like. A method for producing a wood-plastic composite is known.

[0003]

However, such a method for producing a resin-impregnated wood has problems of working environment and environmental destruction due to the volatility of the monomer. Further, sufficient performance in terms of dimensional stability of wood cannot be obtained, and the impregnated and hardened appearance lacks the texture of wood and becomes like a plastic.

[0004]

Means for Solving the Problems In view of such circumstances, the present inventors have made intensive studies and found that impregnating and hardening wood with a composition having a specific chemical structure does not impair the texture of wood. In addition, they found that the working environment, environmental destruction, weather resistance of wood, and dimensional stability were significantly improved, and completed the present invention.

[0005] That is, the present invention provides a method for producing ethylene in one molecule.
Having an unsaturated double bond and a carboxylic acid group, and having an acid value of
A compound having an amount of 120 to 214 KOH mg / g as an essential component
Wood impregnated with water-soluble impregnating resin
The present invention further provides a resin-impregnated wood characterized by being cured by heat, an electron beam, or a gamma ray, and a method for producing the resin-impregnated wood.

In the present invention, it is necessary to dilute such a resin for impregnation in order not to impair the texture of wood. In such a case, the impregnation resin can be diluted with a solvent or water. It is preferable to dilute with water in order to uniformly impregnate the wood with respect to the environment.

For this reason, the resin composition of the present invention is further impregnated into wood as a water-soluble composition which is neutralized by adding a base, specifically, an alkali metal or an organic amine compound and dissolved in water. Preferably, it is cured.

[0008] as a resin for wood impregnated referred to here is, 1
Ethylenically unsaturated double bond and carboxylic acid group in the molecule
Has an acid value of 120 to 214 KOH mg / g
It is a water-soluble compound containing a compound as an essential component,
Typical examples thereof include acrylic acid, dimer acrylic acid, a compound obtained by opening epsilon caprolactone with acrylic acid, fumaric acid, fumaric anhydride, a compound having a hydroxyl group and an acryloyl group, and a compound having a carboxylic acid group and an ester. <br/> shall which have a carboxylic acid group in the compound the reaction was run and the like.

Representative examples of the compound having a hydroxyl group and an acryloyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate,
Hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, pentaerythritol tri (meth) acrylate, 3-acryloyloxyglycerin mono (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, 2-hydroxy-1- (meth)
Acryloxy-3- (meth) acryloxypropane, glycerin di (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polyε-caprolactone mono (meth) acrylate, and the like are included.

[0010] The compound having a carboxylic acid group herein, listed below such as various acids or acid anhydrides thereof conventionally known can be used, Typical examples of maleic acid, fumaric acid, itaconic Acid, citraconic acid, tetrahydrophthalic acid, heptic acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenylsuccinic acid, sebacic acid, azelaic acid, 2,
2,4-trimethyl adipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 1, 1
0-decamethylene dicarboxylic acid, muconic acid, oxalic acid,
Examples thereof include malonic acid, glutanic acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, and acid anhydrides thereof.

[0011]

In order to dissolve a compound having an ethylenically unsaturated double bond and a carboxylic acid group in one molecule in water, it is desirable to neutralize the compound with a base. As the base used here, known and used alkali metals and amine compounds can be used. When neutralizing with an alkali metal, a metal salt is easily formed with sodium hydroxide, potassium hydroxide or the like. As the amine compound, various primary to tertiary amines can be used. As these amine compounds, any of known and commonly used compounds can be used. For example, trialkylamines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( (Meth) such as (meth) acrylate
Amine compounds containing acrylate groups are typical.

The degree of neutralization may be such that the resin is dissolved or dispersed in water, and any neutral pH can be used without any problem. When preparing an aqueous solution, an alcohol such as methanol, ethanol, isopropyl alcohol and butyl alcohol, a ketone such as acetone and MEK, a solvent such as an ether, and a surfactant may be used in combination. Further, the compound having an ethylenically unsaturated double bond and a carboxylic acid group in one molecule may be used alone or in combination. In order to enhance the crosslinkability, a polyfunctional (meth) acrylate compound and an unsaturated polyester can be partially used. These compounds are
Compounds having a polyoxyalkylene chain, particularly acrylates having a polyoxyethylene chain, can be suitably used from the viewpoint of solubility in water and impregnation into wood. There is no restriction on the resin solid content of the aqueous resin solution for impregnation. However, it is preferable to perform the operation at 90% or less, preferably 60% or less, in terms of workability and appearance of the impregnated wood.

When such an impregnating resin is impregnated into wood, the wood is immersed in the impregnating resin, or before the wood is immersed in the resin, the wood is subjected to decompression, pressurization, microwaves, and heating. The resin can be treated, and by applying pressure, decompression, heating, microwaves or the like at the time of immersion, the resin can be uniformly impregnated and the impregnation can be promoted.

The wood impregnated with the impregnating resin thus obtained is dried at an arbitrary temperature or under reduced pressure for the purpose of volatilizing water and solvent in the aqueous solution, and then cured by heat, electron beam, γ-ray or the like. By doing so, the desired resin-impregnated wood can be manufactured.

In the case of curing by heat, it is preferable to add a polymerization initiation catalyst to the resin from the viewpoint of shortening the curing time. As the polymerization initiation catalyst, known and commonly used catalysts can be used, and only typical ones are exemplified. Ketone peroxides such as methyl ethyl ketone peroxide and cyclohexane peroxide, 1,1-bis (t-butylperoxy) 3,3,3 5-trimethylcyclohexane,
Peroxyketals such as 1,1, bis (t-butylperoxy) cyclohexane; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxoside; and dialkyl perks such as di-t-butylperoxide Oxides, acetyl peroxide, diacyl peroxides such as isobutyl peroxide, diisopropyl peroxycarbonate, peroxycarbonates such as di-n-propylperoxydicarbonate, t-butylperoxyacetate, t-butylperoxy Peroxyesters such as isobutyrate.

In addition, curing can be performed with an electron beam from the viewpoint of shortening the curing time, saving energy, and achieving uniform curing.
The electron beam curing can be easily performed by irradiating the target resin-impregnated wood with an ionizing radiation using an electron beam irradiation apparatus. The energy can be from 160 KV to 5 MV at an accelerating voltage. It is preferable to irradiate an electron beam with energy suitable for the material density and thickness of the object. At this time, the irradiation dose is not subject to any restrictions, but in order to suppress the deterioration of the wood due to the electron beam, the irradiation dose is not limited.
It is preferred to cure at from 10 to 20 Mrad, preferably from 1 to 10 Mrad. Furthermore, when curing with an electron beam, it is also possible to cure with a low dose by using the polymerization initiator described above in combination.

For the purpose of improving the weather resistance and durability of the resin-impregnated wood after curing, additives such as an antioxidant, an ultraviolet absorber and an ultraviolet stabilizer may be added to the impregnating resin. For the purpose of improving the appearance, weather resistance and durability of the resin-impregnated wood, a paint can be applied to the surface of the cured resin-impregnated wood.

The resin-impregnated wood produced by the production method of the present invention is a resin-impregnated wood which has a feeling of wood and has greatly improved dimensional stability and weather resistance.
Has excellent performance suitable for applications such as building materials.

[0020]

Next, the present invention will be described in detail with reference to resin production examples, examples and comparative examples, but the present invention is not limited thereto. In the examples, “parts” and “%” are all based on weight.

(Resin Production Example 1) A flask equipped with a stirrer, thermometer and reflux condenser was charged with 148 parts of phthalic anhydride and 116 parts of hydroxyethyl acrylate, and the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 4 hours. went. At this time, the acid value of the resin was 214 KOH-mg / g. Next, 101 parts of triethylamine was added to this resin, and after stirring for 1 hour,
200 parts of ion-exchanged water was added to obtain an impregnating resin (A1).

(Resin Production Example 2) Tetrahydrophthalic anhydride 15 was placed in a flask equipped with a stirrer, thermometer and reflux condenser.
2 parts and 298 parts of pentaerythritol triacrylate were charged, the temperature was raised to 100 ° C. while stirring, and the reaction was carried out for 4 hours. At this time, the acid value of the resin was 125 KOH-mg / g. Next, 100 parts of triethylamine was added to this resin, and the mixture was stirred for 1 hour, and then 350 parts of ion-exchanged water was added to obtain an impregnating resin (A2).

(Resin Production Example 3) A flask equipped with a stirrer, thermometer and reflux condenser was charged with 148 parts of phthalic anhydride and 116 parts of hydroxyethyl acrylate, and the temperature was raised to 100 ° C. with stirring, and the reaction was carried out for 4 hours. went. At this time, the acid value of the resin was 214 KOH-mg / mg. Next, 40 parts of sodium hydroxide was added to this resin, and after stirring for 1 hour,
310 parts of ion-exchanged water were added to obtain an impregnating resin (A3).

(Resin Production Example 4) A flask equipped with a stirrer, thermometer and reflux condenser was charged with 148 parts of phthalic anhydride and 340 parts of epsilon caprolactone-modified hydroxyethyl acrylate (hydroxyl value: 165), and stirred while stirring.
The temperature was raised to 00 ° C., and the reaction was performed for 4 hours. At this time, the acid value of the resin was 120 KOH-mg / g. Next, 100 parts of triethylamine was added to this resin, and after stirring for 1 hour, 380 parts of ion-exchanged water was added to obtain an impregnating resin (A4).

[0025]

(Embodiment 1) An injection device capable of increasing and decreasing pressure
Add 2 x 105 x 250 mm bait gauze board and add 30
The pressure was reduced by torr for 30 minutes, and the impregnating resin (A1) was injected. Thereafter, the system was pressurized to 15 kg / cm ² and left for 3 hours. Thereafter, the pressure in the system was reduced to 30 torr and left for 30 minutes. This was left at 40 ° C. for 24 hours for moisture adjustment. Further, the treated wood was irradiated with an electron beam having a voltage of 4 MeV and a current of 10 mA for 2 Mrad to obtain a target impregnated wood (W1).

(Embodiment 2) An injection device capable of increasing and decreasing pressure
Add 2 x 105 x 250 mm bait gauze board and add 30
The pressure was reduced by torr for 30 minutes, and the impregnating resin (A2) was injected. Thereafter, the system was pressurized to 15 kg / cm ² and left for 3 hours. Thereafter, the pressure in the system was reduced to 30 torr and left for 30 minutes. This was left at 40 ° C. for 24 hours for moisture adjustment. The treated wood was further subjected to a voltage of 4 MeV and a current of 10 MeV.
The target was impregnated with wood (W2) by irradiation with an electron beam of 2 Mrad.

(Embodiment 3) An injection device capable of increasing and decreasing pressure
Add 2 x 105 x 250 mm bait gauze board and add 30
The pressure was reduced by torr for 30 minutes, and the impregnating resin (A3) was injected. Thereafter, the system was pressurized to 15 kg / cm ² and left for 3 hours. Thereafter, the pressure in the system was reduced to 30 torr and left for 30 minutes. This was left at 40 ° C. for 24 hours for moisture adjustment. The treated wood was further subjected to a voltage of 4 MeV and a current of 10 MeV.
It was irradiated with 2 Mrad of an electron beam of mA to obtain a target impregnated wood (W3).

(Embodiment 4) An injection device capable of increasing and decreasing pressure
Add 2 x 105 x 250 mm bait gauze board and add 30
The pressure was reduced by torr for 30 minutes, and the impregnating resin (A4) was injected. Thereafter, the system was pressurized to 15 kg / cm ² and left for 3 hours. Thereafter, the pressure in the system was reduced to 30 torr and left for 30 minutes. This was left at 40 ° C. for 24 hours for moisture adjustment. The treated wood was further subjected to a voltage of 4 MeV and a current of 10 MeV.
Irradiation of 2 Mrad was performed with an electron beam of mA to obtain a target impregnated wood (W4).

[0030]

Example 5 A cedar material of 12 × 105 × 250 mm was placed in an injection device capable of increasing and decreasing the pressure, and the mixture was subjected to a reduced pressure treatment at 30 torr for 30 minutes, and the impregnating resin (A1) was injected. Then, the inside of the system is 15 kg / cm2
And left for 3 hours. Thereafter, the pressure in the system was reduced to 30 torr and left for 30 minutes. This is adjusted to 40
Left at 24 ° C. for 24 hours. Further, the treated wood was irradiated with an electron beam having a voltage of 4 MeV and a current of 10 mA for 2 Mrad to obtain a target impregnated wood (W 5 ).

Example 6 A cedar material of 12 × 105 × 250 mm was placed in an injection device capable of increasing and decreasing the pressure, and the mixture was subjected to a pressure reduction treatment at 30 torr for 30 minutes, and the impregnating resin (A2) was injected. Then, the inside of the system is 15 kg / cm2
And left for 3 hours. Thereafter, the pressure in the system was reduced to 30 torr and left for 30 minutes. This is adjusted to 40
Left at 24 ° C. for 24 hours. Further, the treated wood was irradiated with an electron beam having a voltage of 4 MeV and a current of 10 mA for 2 Mrad to obtain a target impregnated wood (W 6 ).

Example 7 A 12 × 105 × 250 mm cedar board material was placed in an injection device capable of increasing and decreasing the pressure, and subjected to a pressure reduction treatment at 30 torr for 30 minutes, and the impregnating resin (A3) was injected. After that, the inside of the system is 15kg / c
m2 and left for 3 hours. After that, 30 to
The pressure was reduced to rr, and the mixture was left for 30 minutes. To adjust the moisture,
It was left at 40 ° C. for 24 hours. Further, the treated wood was irradiated with an electron beam having a voltage of 4 MeV and a current of 10 mA for 2 Mrad to obtain a target impregnated wood (W 7 ).

(Embodiment 8 ) A 12 × 105 × 250 mm cedar mesh material was placed in an injection device capable of increasing and decreasing the pressure, and the mixture was subjected to a reduced pressure treatment at 30 torr for 30 minutes. The impregnating resin (A1) and polyethylene glycol diacrylate were used. An aqueous solution obtained by uniformly mixing a 50% aqueous solution (molecular weight: about 500) with the same weight and by weight was injected. Then, the inside of the system is 15kg /
It was pressurized to cm 2 and left for 3 hours. After that, 30
The pressure was reduced to torr and left for 30 minutes. This was left at 40 ° C. for 24 hours for moisture adjustment. Further, the treated wood was treated with an electron beam having a voltage of 4 MeV and a current of 10 mA for 2 Mra.
Irradiation was performed to obtain the target impregnated wood (W 8 ).

(Comparative Example 1) An injection device capable of increasing and decreasing pressure
Add 2 x 105 x 250 mm bait gauze board and add 30
Reduce the pressure with torr for 30 minutes, then the inside of the system is 15kg / c
m ² and left for 3 hours. After that, 30 torr
The pressure was reduced to r, and the mixture was left for 30 minutes. To adjust the moisture,
It was left at 40 ° C. for 24 hours. This was used as untreated wood (b1) for comparison.

(Comparative Example 2) An injection device capable of increasing and decreasing pressure
Put cedar wood of 2 × 105 × 250mm and 30 at 30torr
Then, the system was pressurized to 15 kg / cm ² and left for 3 hours. Thereafter, the pressure in the system was reduced to 30 torr and left for 30 minutes. This was added at 40 ° C for water adjustment.
Left for 4 hours. The untreated wood for comparison (b)
2).

(Comparative Example 3) Injection apparatus capable of increasing and decreasing pressure
Add 2 x 105 x 250 mm bait gauze board and add 30
The pressure was reduced by torr for 30 minutes, and methyl methacrylate was injected. Then, pressurize the system to 15 kg / cm ² to 3
Left for hours. The treated wood was irradiated with an electron beam having a voltage of 4 MeV and a current of 10 mA for 2 Mrad to obtain a desired injected wood (b3).

(Comparative Example 4) An injection device capable of increasing and decreasing pressure
Add 2 x 105 x 250 mm bait gauze board and add 30
Vacuum treatment with torr for 30 minutes, methyl methacrylate 10
A resin obtained by mixing 0 parts and 0.5 parts of AIBN was injected. Thereafter, the system was pressurized to 15 kg / cm ² and left for 3 hours. This was left at 60 ° C. for 24 hours for moisture adjustment and curing to obtain the desired injected wood (b4).

The impregnated woods W1 to W obtained in the above examples
8 and the untreated wood and the injected woods b1 to b4 obtained in Comparative Examples were evaluated for appearance and odor. The results are shown in Table 1 below.

The impregnated wood W1 to W obtained in the above example
8 and the untreated wood and the injected woods b1 to b4 obtained in the comparative example were forcibly dried at 105 ° C. for 48 hours, and the absolute dry volume was measured. Then, they were immersed in water, and were immersed in 30 torr at 1 torr.
The pressure was reduced for a period of time, and the volume after standing for 24 hours was measured. The dimensional change in these treatments was compared as dimensional stability (ASE) with respect to the change in untreated wood (b1, b2) by the following formula (I). The results are shown in Table 1 below.

[0041]

Further, the impregnated wood W1 obtained in the above example was used.
Untreated wood obtained in Comparative Example and W 8 from and injection timber b
For 1 to b4, an experiment for accelerated weathering resistance was performed using a weatherometer. The results of evaluating the appearance after 400 hours are shown in Table 1 below.

[0043]

[Table 1]

With respect to the appearance in Table 1, those having the appearance of wood were evaluated as excellent, and those having a brown color were evaluated as poor.

[0045]

As described above, according to the present invention,
Has an acid value in a specific range of 120 to 214 KOH mg / g.
Impregnation by using a compound having a carboxylic acid group
The resin for water use to increase the impregnation of the resin into wood
Can be Therefore, according to the present invention, a method for producing a resin-impregnated wood excellent in applications such as wood for building materials and the like, which can dramatically improve the performance thereof without impairing the appearance of the wood, and a method for producing the resin-impregnated wood. Resin-impregnated wood can be provided.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahiro Minoura 4-7-128 Kitahama, Chuo-ku, Osaka-shi, Osaka Inside Sumitomo Forestry Co., Ltd. (72) Inventor Hironori Watanabe 4-7-1 Kitahama, Chuo-ku, Osaka-shi, Osaka No. 28 Sumitomo Forestry Co., Ltd. (56) References JP-A-57-84777 (JP, A) JP-A-1-253401 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B27K 3/15-3/52

Claims (6)

(57) [Claims] 1. A ethylenically unsaturated double bond in a molecule and
And a mosquito carboxylic acid group, and an acid value 120~214KO
Water containing Hmg / g compound as an essential component
A method for producing a resin-impregnated wood, comprising impregnating wood with a water- soluble impregnating resin and then curing the wood. 2. A ethylenically unsaturated double bond in a molecule
And a mosquito carboxylic acid group, and an acid value 120~214KO
A method for producing a resin-impregnated wood, comprising impregnating wood with a water-soluble impregnating resin containing an Hmg / g compound further neutralized with a base as an essential component, and then curing the wood. 3. A molecule ethylenically unsaturated double bond in
And a mosquito carboxylic acid group, and an acid value 120~214KO
A water-soluble impregnating resin composition obtained by further mixing and dissolving a compound having an ethylenic double bond and a polyoxyethylene chain in a molecule with a water-soluble compound obtained by further neutralizing a compound of Hmg / g with a base. A method for producing resin-impregnated wood, wherein the wood is impregnated and then hardened. 4. The method according to claim 3, wherein the polyoxyalkylene chain is a polyoxyethylene chain. 5. The method for producing resin-impregnated wood according to claim 1, wherein the curing means is a means for curing with an electron beam. 6. manufactured by the manufacturing method according to any one of claims 1 to 5, 1 has in its molecule an ethylenically unsaturated double bond and Ca carboxylic acid group, and the acid value 120 to
A resin-impregnated wood obtained by impregnating wood with a water-soluble impregnating resin of 214 KOH mg / g and then curing the wood.