JPH08142012A - Modifier for wooden material and modifying method - Google Patents

Abstract

PURPOSE: To stabilize the dimension of a wooden material over a long period of time by a method wherein compound having a (meth)allyl group is added. CONSTITUTION: This modifier for a wooden material contains a compound having a (meth)allyl group represented by the formula, in which at least one among R<1> , R<2> and R<3> is a (meth)allyl group, a (meth)allyl oxymethyl group or -CH2 -CH(OR<4> )-CH2 -O-CH2 -C(R<5> )=CH2 and the others are hydrogen atoms or 1-12C alkyl groups, while R<4> represents a hydrogen atom or a group having the structure added with a (meth)allyl glycidyl ether and R<5> represents a hydrogen atom or -CH2 . Further, (n) has a value of from two to two hundreds. If the average molecular weight of the compound is below 200, the proportion occupied by the polyalkyleneoxide portion within one molecule becomes small, resulting in obtaining not enough dimensionally stabilizing effect. Furthermore, R<3> may well be equal to R<1> or R<2> or different from them.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modifier and a method for modifying wood materials such as building materials, housing equipment materials and exterior materials.

[0002]

2. Description of the Related Art Conventionally, as a modifier and a method for imparting dimensional stability to a wood material, there is a modifier composed of a water-soluble compound such as polyethylene glycol or polyethylene glycol methacrylic acid ester, and these are impregnated into the wood material. There was a method of drying and curing.

[0003]

However, since polyethylene glycol remains water-soluble and bleeds out, it has the drawback of poor weather resistance. Also in polyethylene glycol methacrylic acid ester, it is difficult to maintain dimensional stability for a long time because the ester bond is gradually hydrolyzed by water or moisture after polymerization and curing to release polyethylene glycol and bleed out. Met.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies on a modifying agent and a modifying method capable of maintaining the dimensional stability of a woody material for a long period of time. That is, the present invention is a modifying agent for wood materials and a modifying method, which comprises a compound (A) having a (meth) allyl group represented by the following general formula (1). [In the formula, at least one of R ¹ , R ² and R ³ is a (meth) allyl group, a (meth) allyloxymethyl group, or —CH ₂ —CH (OR ⁴ ) —CH ₂ —O—CH. _2- C
(R ⁵ ) = CH ₂ and others are hydrogen atoms or carbon atoms 1
~ 12 alkyl groups. Here, R ⁴ is a hydrogen atom,
Alternatively, it is a group having a structure to which (meth) allyl glycidyl ether is added, and R ⁵ is a hydrogen atom or —CH ₃ . Further, n is 2 to 200, and R ³ may be the same or different. ]

In the present invention, the compound (A) having a (meth) allyl group is represented by the following formula (1):
At least one of R ¹ and R ² is a (meth) allyl group, the other is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ³ is a hydrogen atom, and / or an alkyl group having 1 to 12 carbon atoms. (A-1) may be mentioned, and specific examples thereof include (meth) allyl ether of polyalkylene glycol. For example, polyethylene glycol, polypropylene glycol, or random or block copolymer mono (meth) of ethylene oxide, propylene oxide.
Allyl ether or di (meth) allyl ether, and in the case of mono (meth) allyl ether, one end thereof may be a hydroxyl group or an alkyl ether group having 1 to 12 carbon atoms. Of these, di (meth) allyl ether of polyalkylene glycol is preferable, and more preferably at least 80% or more of R ³ is hydrogen atom, and the rest is —CH ₃ di (meth) allyl of polyalkylene glycol. It is ether.

In the general formula (1), at least one of R ¹ and R ² is --CH ₂ --CH (OR ⁴ )-CH ₂ --O.
^{_{-CH 2 -C (R 5) =}} CH 2, the other is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, when R ³ is hydrogen or / and alkyl group having 1 to 12 carbon atoms, (A-2 Examples of () include (meth) allyl glycidyl ether adducts of polyalkylene glycols. For example,
Polyethylene glycol, polypropylene glycol,
Or a secondary hydroxyl group formed as a result of addition of a mono (meth) allyl glycidyl ether adduct, a di (meth) allyl glycidyl ether adduct, or a (meth) allyl glycidyl ether of a random or block copolymer of ethylene oxide or propylene oxide To (meta)
Di (meta) formed by addition of allyl glycidyl ether
Allyl glycidyl ether adduct It is a polyfunctional adduct above, and in the case of mono (meth) allyl glycidyl ether adduct, one end may be either a hydroxyl group or an alkyl ether group having 1 to 12 carbon atoms. Of these, preferably,
It is a poly (meth) allyl glycidyl ether adduct of polyalkylene glycol, more preferably at least 80% or more of R ³ is a hydrogen atom, and the rest is —CH ₃ di-, tri- or tetra (meth) polyalkylene glycol. It is an allyl glycidyl ether adduct.

In the general formula (1), one of R ¹ and R ² is a (meth) allyl group and the other is --CH ₂ --CH (O
Specific examples of _{^{R 4) -CH 2 -O-CH}} 2 -C (R 5) = CH 2, when R ³ is hydrogen or / and alkyl group having 1 to 12 carbon atoms (A-3) is An example is a (meth) allyl glycidyl ether adduct of mono (meth) allyl ether of polyalkylene glycol. For example, polyethylene glycol, polypropylene glycol, or a random or block copolymer mono (meth) allyl ether mono (meth) allyl glycidyl ether adduct of ethylene oxide or propylene oxide, (meth)
Di (meth) allyl glycidyl ether adduct formed by addition of (meth) allyl glycidyl ether to the secondary hydroxyl group formed as a result of addition of allyl glycidyl ether, and the like include polyfunctional adducts. Of these, preferred are (meth) allyl glycidyl ether adducts of poly (alkylene glycol) mono (meth) allyl ether, and more preferred is that at least 80% or more of R ³ is a hydrogen atom and the rest is —CH ₃ . It is a mono- or di (meth) allyl glycidyl ether adduct of mono (meth) allyl ether of polyalkylene glycol.

In the general formula (1), at least one R ³ is a (meth) allyloxymethyl group and the other is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 3
^{When 1} , R ² is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (A-4), specific examples thereof include a copolymer of alkylene oxide and (meth) allyl glycidyl ether. Examples include copolymers of ethylene oxide, propylene oxide and (meth) allyl glycidyl ether.

Of (A-1) to (A-4), (A-1), (A-2) and (A-3) are preferable,
More preferably, at least 80% or more of R ³ is a hydrogen atom and the rest is —CH ₃ (A-1), (A-2) and (A-3).

The content of the (meth) allyl group in the compound (A) having a (meth) allyl group of the present invention is usually 0.5 to 40.
% By weight, preferably 2 to 30%.

The average molecular weight of the compound (A) having a (meth) allyl group of the present invention is usually 200 to 10,000, and preferably 200 to 10,000, although it can be shown that n in the general formula (1) is 2 to 200. It is 300 to 4000. If the average molecular weight is less than 200, the proportion of the polyalkylene oxide moiety in one molecule is small, and a sufficient dimensional stability effect cannot be obtained. On the other hand, when the average molecular weight exceeds 10,000, impregnation into the woody material is not sufficiently performed.

As the method for producing the compound (A) having a (meth) allyl group of the present invention, in the case of (A-1), a polyalkylene glycol is etherified with a (meth) allyl halide in the presence of an alkaline compound. How to do, (meta)
There is a method in which an alkylene oxide is added to allyl alcohol or an alcohol having 1 to 12 carbon atoms and then etherified with a (meth) allyl halide in the presence of an alkaline compound.

In the case of (A-2), there is a method of adding (meth) allyl glycidyl ether to polyalkylene glycol in the presence of a Lewis acid catalyst or an alkaline catalyst.

As the manufacturing method in the case of (A-3),
There is a method of adding an alkylene oxide to (meth) allyl alcohol or an alcohol having 1 to 12 carbon atoms and then adding (meth) allyl glycidyl ether in the presence of a Lewis acid catalyst or an alkaline catalyst.

As the method for producing (A-4), a random copolymerization method in which a mixture of an alkylene oxide and a (meth) allyl glycidyl ether is copolymerized using an alkali or acid catalyst which is commonly used for the polymerization of alkylene oxides. Block copolymerization method of alkylene oxide and (meth) allyl glycidyl ether. The molar ratio of alkylene oxide and (meth) allyl glycidyl ether in these copolymers is usually 1: 0.001 to 0.
5, and preferably 1: 0.01 to 0.2.
When the amount of (meth) allyl glycidyl ether is less than 0.001, the number of cross-linking points is small and the dimensional stabilizing effect of the present invention cannot be obtained. On the other hand, when it is more than 0.5, the proportion of polyalkylene chains is small and the dimensional stability effect of the present invention cannot be obtained.

The modifier for wood materials of the present invention may further contain a vinyl monomer (B), if necessary. By incorporating the vinyl monomer (B), copolymerization with the compound (A) having a (meth) allyl group occurs, resulting in (A)
The unpolymerized component of is reduced and the long-term dimensional stability effect is improved.

As the vinyl monomer (B) in the present invention, unsaturated carboxylic acids such as acrylic acid (salt), methacrylic acid (salt), maleic acid (salt), fumaric acid (salt), and itaconic acid (salt). Acid (salt) type monomer, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, polyalkylene glycol mono or di (meth) acrylate, maleic acid ,
Unsaturated carboxylic acid ester monomers such as fumaric acid and itaconic acid mono- or dialkyl esters, unsaturated amide monomers such as (meth) acrylamide, methylol (meth) acrylamide, vinyl sulfonic acid (salt), styrene Unsaturated sulfonic acid (salt) type monomers such as sulfonic acid (salt) and acrylamido-2-methylpropanesulfonic acid (salt), vinyl ester type monomers such as vinyl acetate and vinyl propionate, dimethylaminoethyl ( Examples thereof include unsaturated cationic monomers such as (meth) acrylate and a quaternary ammonium salt thereof, diethylaminoethyl (meth) acrylate and a quaternary ammonium salt thereof, and the like. Of these, unsaturated carboxylic acid (salt) monomers are preferable, and maleic acid (salt) is more preferable.

When the vinyl monomer (B) in the present invention is a salt such as an unsaturated carboxylic acid salt or a sulfonic acid salt, the salt is lithium, sodium, potassium,
Alkali metals such as cesium, alkaline earth metals such as magnesium, calcium, strontium and barium, ammonia, monomethylamine, dimethylamine,
Examples thereof include salts of amines such as trimethylamine, triethylamine and dimethylethanolamine.

In the present invention, the weight ratio of the compound (A) having a (meth) allyl group and the vinyl monomer (B) is 1:
It is 0 to 1: 1 and preferably 1: 0 to 1: 0.8. When (B) is larger than 1: 1, the proportion of the polyalkylene oxide chain portion in the cured product is small,
Sufficient dimensional stability effect cannot be obtained.

The modifier for wood materials of the present invention may further contain a polymerization initiator (C), if necessary. A usual radical polymerization initiator can be used as the polymerization initiator (C). For example, persulfates such as sodium persulfate, ammonium persulfate and potassium persulfate, azo compounds such as azobisisobutyronitrile, peroxides such as hydrogen peroxide and dicumyl peroxide, sodium persulfate + bisulfite Examples include redox initiators such as sodium hydrogen, hydrogen peroxide and iron salts. Among these, persulfate is preferable in that it is water-soluble.

The addition amount of the polymerization initiator (C) of the present invention is 0.3% to 30% based on the total weight of the compound (A) having a (meth) allyl group and the vinyl monomer (B). Yes, preferably 1 to 15%. If it is less than 0.3%, polymerization hardly occurs, and if it exceeds 30%, an unreacted polymerization initiator or its decomposition product remains in the wood material, which adversely affects the dimensional stability.

The method for using the modifier for a wood material of the present invention is as follows: a compound (A) having a (meth) allyl group, optionally a vinyl monomer (B), and optionally a polymerization initiator (C). ) Are used in a solventless system in which they are uniformly dissolved, a method in which they are dissolved in an organic solvent and used in an organic solvent system, and a method in which they are dissolved in water and used in an aqueous system. Among these methods, work environment, economy,
The method is preferably used in an aqueous system because of its impregnation / permeability into wood materials.

When used in an aqueous system, (A) of the present invention,
The total concentration of (B) and (C) is usually 5 to 70%, preferably 10 to 40%. If it is less than 5%, the weight of the modifier remaining after curing and drying becomes small even if the wood material is sufficiently impregnated with the aqueous solution, so that sufficient dimensional stability cannot be obtained. Also, if it exceeds 70%, the viscosity becomes high,
It becomes difficult to impregnate the wood material. In addition, in order to improve the permeability of the modifier into the wood material, use a water-soluble organic solvent such as ethanol, methanol, isopropanol, or acetone, or a surfactant having a permeability improving effect in the aqueous solution. Good.

The woody material which can be used as the modifier of the present invention is an ordinary woody material mainly made of wood such as rod-shaped, plate-shaped, block-shaped wood, plywood, particle board, wood powder and wood chips. In the case of wood powder, wood chips, etc., these may be treated with the modifier of the present invention and cured, and then molded using a binder or the like.

The method of treating and impregnating the woody material with the modifier for woody material of the present invention includes a coating method, a dipping method, a pressure injection method, a reduced pressure injection method and a reduced pressure-pressure injection method. It can be processed by either method.

As a method of curing the wood material after treating it, there are an ultraviolet curing method, an electron beam curing method, a heat curing method and the like, but when the wood material is thin or only the surface is cured, The ultraviolet curing method is preferable in that the curing speed is fast, while the heat curing method is preferable when the thickness of the wood material is large and the interior of the wood material is cured. In the case of the thermosetting method, the impregnated wood material can be cured by heating it in a dryer at 40 to 150 ° C. for 10 minutes to 6 hours. When a large amount of the polymerization initiator (C) is used or when the total concentration of (A) + (B) + (C) in the solution is high, even at normal room temperature for several hours to
It can be cured in a few weeks.

If desired, the wood-based material modifying agent of the present invention may be used in combination with a preservative, a fungicide, an insecticide, a termite, or the like.

The wood material treated with the modifier for wood materials of the present invention and cured exhibits high dimensional stability for a long period of time, and therefore, a material requiring dimensional stability, for example, wood is used as a raw material. It can be used for various building materials, housing equipment materials, and other exterior materials.

[0029]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, "part" means "part by weight".

The (meth) allyl compound (A) shown in Table 1 was synthesized according to the following Production Examples 1-5.

Production Example 1 (Production of a in Table 1) 400 parts of polyethylene glycol having an average molecular weight of 600 was charged into a 1 liter autoclave and caustic soda 80 was added.
Added parts. The space was replaced with nitrogen, the temperature was raised to 80 ° C., and 113 parts of allyl chloride was gradually added from a dropping funnel. Then, after aging for about 12 hours, cool to 30 ° C,
Water was added and washed with water. The upper layer, which was left standing and separated, was heated and stirred at 80 ° C. under reduced pressure to remove low volatile components, and filtered to obtain 430 parts of a pale yellow transparent liquid substance a.

Production Example 2 (Production of b in Table 1) By the same method as in Production Example 1 except that 45 parts of caustic soda and 60 parts of allyl chloride were used, 418 parts of a slightly yellow transparent liquid substance b was obtained. It was

Production Example 3 (Production of c in Table 1) A slightly yellow color was obtained in the same manner as in Production Example 1, except that 400 parts of polyethylene glycol having an average molecular weight of 220, 200 parts of caustic soda and 300 parts of allyl chloride were used. 530 parts of a transparent liquid material c was obtained.

Production Example 4 (Production of d in Table 1) By the same method as in Production Example 1 except that 400 parts of allyl alcohol ethylene oxide adduct having an average molecular weight of 1010, 30 parts of caustic soda and 38 parts of allyl chloride are used. , 400 parts of a slightly yellow solid substance d was obtained.

Production Example 5 (Production of e in Table 1) In Production Example 1, 400 parts of an ethylene oxide / propylene oxide random copolymer having an average molecular weight of 640,
By the same method, except that 75 parts of caustic soda and 106 parts of allyl chloride were used, 425 parts of a slightly yellow liquid substance e was obtained.

Production Example 6 (Production of f in Table 1) A 1-liter four-neck reaction flask was charged with 400 parts of polyethylene glycol having an average molecular weight of 400, 0.6 part of boron trifluoride diethyl ether complex was added, and the mixture was heated to 50 ° C. Then, 125 parts of allyl glycidyl ether was gradually added dropwise over 2 hours. When it was aged at 65 ° C. for 5 hours and cooled, 520 parts of a pale yellow transparent liquid substance f was obtained.

Production Example 7 (Production of g in Table 1) In Production Example 6, 400 parts of polyethylene glycol having an average molecular weight of 2200 and 4 parts of allyl glycidyl ether were used.
By the same method except that 3 parts were used, a slightly yellow solid substance g
440 parts were obtained.

Production Example 8 (Production of h in Table 1) In Production Example 6, 400 parts of allyl alcohol ethylene oxide adduct having an average molecular weight of 400, 0.4 part of boron trifluoride diethyl ether complex, and 61 parts of allyl glycidyl ether. 460 parts of a slightly yellow transparent liquid substance h was obtained by the same method except that

Production Example 9 (Production of i in Table 1) In a container similar to that of Production Example 1, 50 parts of ethylene glycol and 1.5 parts of caustic potash were charged, and after sufficiently substituting with nitrogen, allyl glycidyl ether / ethylene oxide = 1 / 500 parts of the mixture with a molar ratio of 25 was added dropwise at 90-100 ° C over about 5 hours. After further aging for 5 hours and cooling, 551 parts of a pale yellow transparent liquid substance i was obtained.

[0040]

[Table 1]

Example 1 20 parts of the compound a shown in Table 1, 5 parts of maleic acid and 3 parts of sodium persulfate were dissolved in water so that the solid content concentration became 20% to prepare a modifier aqueous solution. Eight pieces of cypress wood pieces (30 × 30 × 5 mm) that had been absolutely dried at 105 ° C. were immersed in a modifier aqueous solution and impregnated under a reduced pressure of −50 cmHg for 3 hours. After taking out the wood piece, it was heat-cured at 110 ° C. for 1 hour. Then, the wood piece was immersed in water for 24 hours, taken out, and then dried in a dryer at 105 ° C. for 20 hours. After that, an accelerated weather resistance test was carried out for 600 hours in a sunshine weatherometer, then, it was again immersed in water for 24 hours, and further dried in a drier at 105 ° C. for 20 hours. 8
As a result of obtaining the impregnation rate obtained from the following formula for the piece of wood, the average value was 42%. In addition, the following shrinkage ratio of the untreated material (impregnated only with water) used in the simultaneous comparison and the shrinkage ratio of the wood piece treated with the modifier aqueous solution of the present example were determined, and the following anti-shrinkage ratio was determined from these. As a result, the anti-shrinkage rate in the first immersion-drying was 65%, and the anti-shrinkage rate in the immersion-drying after the accelerated weathering test was 54%. Impregnation rate (%) = [(W ₂ −W ₁ ) / W ₁ ] × C W ₁ : Weight (g) of completely dry wood piece before test W ₂ : Weight of wood piece after impregnation with the aqueous modifier solution ( g) C: solid content concentration (% by weight) of the modifier solution Shrinkage (%) = [(L ₁ −L ₂ ) / L ₁ ] × 100 L ₁ : Volume of wood piece after immersion in water (cm ³ : L ₂ : Volume of wood piece after drying at 105 ° C (cm ³ : Length x width x)
Thickness) Anti-shrinkage rate (%) = [(D ₀ −D) / D ₀ ] × 100 D ₀ : Shrinkage rate of untreated material (%) D: Shrinkage rate of treated material (%)

In the same manner as in Examples 2 to 16 and Comparative Examples A and B, an aqueous modifier solution was prepared as shown in Table 2, and the same tests as in Example 1 were conducted. The results are shown in Table 3.

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

The modifier of the present invention has the following effects. (1) The dimensional stability of the wood material is exhibited for a long period of time, and the wood material is prevented from cracking and distortion. Because of the above effects, the modifier of the present invention is useful for various building materials, housing equipment materials, and other exterior materials.

Claims (9)

[Claims] 1. A modifier for wood materials, comprising a compound (A) having a (meth) allyl group represented by the following general formula (1). [In the formula, at least one of R ¹ , R ² and R ³ is a (meth) allyl group, a (meth) allyloxymethyl group, or —CH ₂ —CH (OR ⁴ ) —CH ₂ —O—CH. _2- C
(R ⁵ ) = CH ₂ and others are hydrogen atoms or carbon atoms 1
~ 12 alkyl groups. Here, R ⁴ is a hydrogen atom,
Alternatively, it is a group having a structure to which (meth) allyl glycidyl ether is added, and R ⁵ is a hydrogen atom or —CH ₃ . Further, n is 2 to 200, and R ³ may be the same or different. ] 2. The modifier for a wood material according to claim 1, further comprising a vinyl monomer (B). 3. The modifier for woody materials according to claim 1 or 2, which further comprises a polymerization initiator (C). 4. The modifier for woody materials according to claim 1, wherein (A) is a di (meth) allyl ether of polyalkylene glycol. 5. The modifier for woody materials according to claim 1, wherein (A) is a poly (meth) allyl glycidyl ether adduct of polyalkylene glycol. 6. The modifier for woody materials according to claim 1, wherein (A) is a (meth) allylglycidyl ether adduct of mono (meth) allyl ether of polyalkylene glycol. 7. The modifier for woody materials according to claim 2, wherein (B) is an unsaturated carboxylic acid or an unsaturated carboxylic acid salt. 8. The modifier for woody materials according to claim 2, wherein (B) is maleic acid or maleate. 9. A method for modifying a wood material, which comprises treating the wood with the wood material modifier according to any one of claims 1 to 8 and then curing the wood.