JPH09254106A - Resin composition for timber impregnation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for impregnating a timber with it for sufficiently improving durability of the timber. SOLUTION: A resin composition for impregnating a timber with it can be obtained by mixing a vinyl ester, an amino resin as a triazine derivative, and an unsaturated polyester having as essential components, a polyethylene glycol as an alcohol component and/or a chain aliphatic dibasic acid as an acid component. The resin composition for impregnating the timber with it, which is obtained in such a manner, is integrated with the timber by impregnating it into the timber and curing it. As a result, generation of crack in the timber due to influence of heat and water can be prevented and durability and water resistance of the timber can be sufficiently improved.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a wood composite material obtained by impregnating and curing wood with a thermosetting resin composition, so-called WPC (Wood Plastic Composite).
The present invention relates to a resin composition for impregnating wood used in (s).

[0002]

2. Description of the Related Art Wood is used in various fields including building materials because of its beautiful appearance and feeling of use. However, wood is inferior in durability and has a problem that cracks easily occur due to the influence of heat, water and the like.
Therefore, many attempts have been made to modify wood in order to improve the durability of wood. As such an attempt, for example, a wood composite material, that is, WPC (Wo (Wo)
Various methods for obtaining od Plastic Composites) have been studied.

[0003]

However, as described above, when the WPC is produced by using the unsaturated polyester resin, the methyl methacrylate monomer, etc., the W
It cannot be said that the durability of PC is always sufficient. Therefore, there is a demand for a resin composition for impregnating wood, which can sufficiently improve the durability of wood. The present invention has been made in view of the above conventional problems, and an object thereof is to provide a resin composition for impregnating wood, which can sufficiently improve the durability of wood.

[0004]

Means for Solving the Problems The inventors of the present application have conducted diligent studies to achieve the above object, and as a result,
A resin composition containing an unsaturated polyester and an amino resin which is a triazine derivative, wherein the unsaturated polyester contains polyethylene glycol as an alcohol component and / or a chain aliphatic dibasic acid as an acid component as essential components. The present invention has been completed by finding that a product can sufficiently improve the durability of wood.

That is, the resin composition for impregnating wood according to the invention of claim 1 contains vinyl ester, unsaturated polyester, and amino resin which is a triazine derivative,
Further, the unsaturated polyester is characterized in that at least polyethylene glycol is used as an alcohol component.

The resin composition for impregnating wood according to claim 2 is the resin composition for impregnating wood according to claim 1, wherein the proportion of the polyethylene glycol in the alcohol component is 70 mol% or more. Is characterized by.

A wood impregnating resin composition according to a third aspect of the present invention is the wood impregnating resin composition according to the first or second aspect, wherein the unsaturated polyester is at least a chain aliphatic diamine as an acid component. It is characterized by using a basic acid.

A wood impregnating resin composition according to a fourth aspect of the present invention comprises a vinyl ester, an unsaturated polyester, and an amino resin that is a triazine derivative, and the unsaturated polyester is an acid component. It is characterized by using at least a chain aliphatic dibasic acid.

The resin composition for impregnating wood according to the invention of claim 5 is the resin composition for impregnating wood according to claim 1, 2, 3 or 4, characterized in that the amino resin is a benzoguanamine resin. There is.

According to the above constitution, the resin composition for impregnating wood can prevent the generation of cracks in wood under the influence of heat, water and the like. That is, the durability of wood can be sufficiently improved.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION A resin composition for impregnating wood (hereinafter referred to as a resin composition) according to the present invention comprises a vinyl ester, an unsaturated polyester, and an amino resin which is a triazine derivative (hereinafter simply referred to as an amino resin). The above-mentioned unsaturated polyester is a resin composition containing, as essential components, polyethylene glycol as an alcohol component and / or a chain aliphatic dibasic acid as an acid component. The resin composition can be easily obtained by mixing the vinyl ester, the amino resin, and the unsaturated polyester.

The vinyl ester used in the resin composition for impregnating wood according to the present invention is a reaction product of an epoxy compound having two or more epoxy groups in one molecule and an unsaturated monobasic acid. The vinyl ester can be obtained by reacting a bisphenol type epoxy compound or a mixture of a bisphenol type epoxy compound and a novolac type epoxy compound with an unsaturated monobasic acid in the presence of an esterification catalyst.

Specific examples of the bisphenol type epoxy compound include, for example, a glycidyl ether type epoxy compound obtained by reacting epichlorohydrin or methylepichlorohydrin with bisphenol A or bisphenol F; and an alkylene oxide adduct of bisphenol A. , An epoxy compound obtained by the reaction with epichlorohydrin or methylepichlorohydrin, and the like, are not particularly limited.

Specific examples of the novolac type epoxy compound include, but are not limited to, an epoxy compound obtained by the reaction of phenol novolac or cresol novolac with epichlorohydrin or methyl epichlorohydrin. .

These epoxy compounds may be used alone or in admixture of two or more. Further, among the above epoxy compounds, it is preferable to use an epoxy compound having an average epoxy equivalent in the range of 400 to 700. Above average epoxy equivalent is 400
If it is less than the above range, the WPC obtained when the WPC is produced using the resin composition becomes hard and the durability of the WPC becomes insufficient, which is not preferable. On the other hand, if the average epoxy equivalent is more than 700, the viscosity of the resin composition finally obtained becomes high, and it becomes difficult to impregnate the resin composition into wood, which is not preferable.

The unsaturated monobasic acid is not particularly limited, but specific examples thereof include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid and the like. As the unsaturated monobasic acid, unsaturated dibasic acid half esters such as monomethylmalate, monopropylmalate and monobutylmalate may be used. Only one kind of these unsaturated monobasic acids may be used, or two or more kinds thereof may be appropriately mixed and used.

The esterification catalyst is not particularly limited, and conventionally known compounds can be used. As the esterification catalyst, specifically, for example, triethylamine, N, N-dimethylbenzylamine,
Tertiary amines such as N, N-dimethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride; triphenylphosphine,
Examples thereof include phosphonium compounds such as tetraphenylphosphonium chloride, tetraphenylphosphonium bromide and tetraphenylphosphonium iodide. These esterification catalysts may be used alone or in a suitable mixture of two or more kinds.

The reaction conditions and the like for carrying out the above reaction can be carried out under known conditions and are not particularly limited. In the above reaction, it is preferable to add a polymerization inhibitor or molecular oxygen in order to prevent gelation due to polymerization and adjust the storage stability or curability of the resulting vinyl ester.

The polymerization inhibitor is not particularly limited, and conventionally known compounds can be used. Specific examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, and copper naphthenate. To be Only one type of these polymerization inhibitors may be used, or two or more types may be appropriately mixed and used.

As the molecular oxygen, for example, air can be used. In this case, air may be blown into the reaction system (so-called bubbling). In order to sufficiently prevent gelation due to the above polymerization, it is preferable to use a polymerization inhibitor in combination with molecular oxygen.

The method for producing the vinyl ester, that is, the reaction method of the epoxy compound and the unsaturated monobasic acid is not particularly limited, and various conventionally known methods can be used. In addition, each component, that is, an epoxy compound,
The mixing ratio of the unsaturated monobasic acid, the esterification catalyst, the polymerization inhibitor, etc. is not particularly limited, and the presence or absence of other additives and the amount used are also not particularly limited. Furthermore, the reaction time and reaction temperature in the above reaction may be appropriately set so that the above reaction is completed, and are not particularly limited.

Usually, the vinyl ester is preferably used as a vinyl ester resin by diluting it with a polymerizable monomer in consideration of workability. The polymerizable monomer for diluting the vinyl ester is not particularly limited, and specifically, for example, styrene, vinyltoluene, p-methylstyrene, t-butylstyrene, diallylphthalate, methacrylic acid. Methyl,
Examples thereof include triethylene glycol di (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Only one kind of these polymerizable monomers may be used, or two or more kinds thereof may be appropriately mixed and used.

The content of the polymerizable monomer in the vinyl ester resin is preferably in the range of 20% to 70% by weight, more preferably 20% to 60% by weight,
A range of 50% to 50% by weight is particularly preferable. If the amount of the polymerizable monomer blended is less than 20% by weight, the viscosity of the finally obtained resin composition will be high and handling will be difficult, such being undesirable. On the other hand, if the compounding amount of the above-mentioned polymerizable monomer exceeds 70% by weight, the curability at the time of impregnation into wood and curing of the resin composition finally obtained decreases, which is not preferable. Further, at what stage the above-mentioned polymerizable monomer is added is not particularly limited, and it may be before or after the vinyl ester is mixed with the unsaturated polyester or the amino resin.

The unsaturated polyester used in the resin composition for impregnating wood according to the present invention is a compound obtained by a condensation reaction of an acid component and an alcohol component, and includes polyethylene glycol as an alcohol component and / or an acid component. And a chain aliphatic dibasic acid as an essential component.

Among the alcohol components constituting the above unsaturated polyester, polyethylene glycol is represented by the general formula (1)

[0026]

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(In the formula, n represents an integer of 2 or more). Among the above polyethylene glycols, compounds in which the repeating unit represented by n represents an integer of 2 to 8 are preferable, and compounds in which the repeating unit represents an integer of 2 to 4 are more preferable.

Specific examples of the polyethylene glycol include, but are not limited to, diethylene glycol, triethylene glycol, tetraethylene glycol and the like. Only one kind of these polyethylene glycols may be used, or two or more kinds thereof may be appropriately mixed and used.

If desired, an alcohol component other than the above polyethylene glycol (hereinafter referred to as other alcohol) can also be used. Specific examples of the above-mentioned other alcohol components include ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol and 1,5-
Pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,2-cyclohexanediol, 1,
4-cyclohexanedimethanol, 2-methylpropane-1,3
Examples thereof include diols, hydrogenated bisphenol A, and adducts of bisphenol A with alkylene oxides such as propylene oxide and ethylene oxide, but are not particularly limited. Only one kind of these other alcohol components may be used, or two or more kinds thereof may be appropriately mixed and used.

The content of the polyethylene glycol in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more. When the content of the polyethylene glycol represented by the general formula (1) in the alcohol component is less than 70 mol%, when the obtained resin composition is impregnated in wood and cured, WPC obtained is It is not preferable because it becomes hard and the durability of the WPC becomes insufficient.

Among the acid components constituting the unsaturated polyester, the chain aliphatic dibasic acid has the general formula (2)

[0032]

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(In the formula, m represents an integer of 2 or more). Among the chain-like aliphatic dibasic acids, compounds in which the repeating unit represented by m represents an integer of 2 to 12 are preferable, and compounds in which the repeating unit represents an integer of 4 to 8 are more preferable.

Specific examples of the chain aliphatic dibasic acid include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and 1,12-docanedioic acid. It is not limited. These chain aliphatic dibasic acids may be used alone or in a suitable mixture of two or more kinds.

As the acid component other than the above-mentioned chain aliphatic dibasic acid, α, β-unsaturated dibasic acid and saturated dibasic acid, or their anhydrides can be used.

Specific examples of the α, β-unsaturated dibasic acid and its anhydride include, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride,
Citraconic acid and the like can be mentioned. These α, β-unsaturated dibasic acids and their anhydrides may be used alone or in an appropriate mixture of two or more.

The saturated dibasic acid and its anhydride include:
Specifically, for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, malonic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,
4'-bisphenyldicarboxylic acid and the like can be mentioned. These saturated dibasic acids and their anhydrides may be used alone or in an appropriate mixture of two or more.

The content of the chain aliphatic dibasic acid in the acid component is preferably in the range of 10 mol% to 50 mol%, more preferably 20 mol% to 30 mol%. When the content of the chain aliphatic dibasic acid is less than 10 mol%, it is not possible to sufficiently improve the durability of the WPC obtained when a WPC is produced using the resin composition, which is preferable. Absent. On the other hand, if the content of the above-mentioned chain aliphatic dibasic acid exceeds 50 mol%, the water resistance of the obtained WPC is lowered, which is not preferable.

The content of the α, β-unsaturated dibasic acid and / or the anhydride thereof in the acid component depends on the kind and the amount of use of the polyethylene glycol, but the polyethylene glycol may be, for example, diethylene glycol. In this case, it is preferably more than 0 and 40 mol% or less, and 10
More preferably, it is in the range of mol% to 40 mol%. When the polyethylene glycol is, for example, triethylene glycol, it is preferably more than 0 and 50 mol% or less, more preferably 10 mol% to 50 mol%. When the content of the α, β-unsaturated dibasic acid and / or its anhydride deviates from the above range, W obtained when the resin composition obtained is impregnated into wood and cured.
It is not preferable because the PC becomes hard and the durability of the WPC becomes insufficient.

The reaction conditions and the like for carrying out the above reaction can be carried out under known conditions and are not particularly limited. In the above reaction, it is preferable to add a polymerization inhibitor in order to prevent gelation due to polymerization and to adjust the storage stability or curability of the resulting unsaturated polyester.

As the above-mentioned polymerization inhibitor, the same compounds as those exemplified in the above vinyl ester production can be used.

The method for producing the above unsaturated polyester is not particularly limited, and a conventional method may be used. Further, the mixing ratio of each component, that is, the acid component and the alcohol component is not particularly limited, and the presence or absence of other additives and the amount used are also not particularly limited. Furthermore, the reaction time and reaction temperature in the above reaction may be appropriately set so that the above reaction is completed,
There is no particular limitation.

Generally, the unsaturated polyester is preferably used as an unsaturated polyester resin by diluting it with a polymerizable monomer in consideration of workability. The polymerizable monomer for diluting the unsaturated polyester is not particularly limited, and the same compounds as those exemplified in the dilution of the vinyl ester can be used.

The amount of the above-mentioned polymerizable monomer to be blended in the unsaturated polyester resin is preferably in the range of 20% by weight to 70% by weight, more preferably in the range of 20% by weight to 60% by weight,
A range of 30% to 50% by weight is particularly preferable. If the amount of the polymerizable monomer blended is less than 20% by weight, the viscosity of the finally obtained resin composition will be high and handling will be difficult, such being undesirable. On the other hand, if the compounding amount of the above-mentioned polymerizable monomer exceeds 70% by weight, the curability at the time of impregnation into wood and curing of the resin composition finally obtained decreases, which is not preferable. Further, at what stage the above-mentioned polymerizable monomer is added is not particularly limited, and it may be before or after the unsaturated polyester is mixed with the vinyl ester or the amino resin.

The above-mentioned amino resin used in the resin composition for impregnating wood according to the present invention is a methylol compound or an alkyl ether compound of an amino compound having a triazine ring, and specifically, for example, melamine resin and isomeramine. Resins, benzoguanamine resins, acetoguanamine resins, guanylmelamine resins and the like can be mentioned. Only one kind of these amino resins may be used, or two or more kinds thereof may be appropriately mixed and used.

Specific examples of the amino compound having a triazine ring include melamine, isomeramine, benzoguanamine, acetoguanamine, and guanylmelamine, but are not particularly limited. Only one kind of these amino compounds may be used, or two or more kinds thereof may be appropriately mixed and used.

The above methylol compound can be easily obtained by reacting the amino compound with formaldehyde. The alkyl ether compound can be easily obtained by alkylating a methylol compound with an alcohol. Among the above alkyl ether compounds, alkyl etherified benzoguanamine obtained by alkyl etherifying methylolated benzoguanamine which is a methylol compound is preferably used.

The alcohols used in the above alkyl etherification reaction are aliphatic alcohols, and specifically, for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec- Examples thereof include butanol, tert-butanol and the like, but are not particularly limited. These alcohols may be used alone or in an appropriate mixture of two or more.

Among the above amino resins, benzoguanamine resins are preferable because of their compatibility with vinyl esters and unsaturated polyesters, and among them, methylolated benzoguanamines are more preferable because of their condensation reactivity and they are the initial condensates of methylolated benzoguanamines. Dehydrated benzoguanamine is particularly preferred.

The method for producing the amino resin is not particularly limited, and various conventionally known methods can be used. When methylolated benzoguanamine or dehydrated benzoguanamine is obtained as the amino resin, it is preferable to react formaldehyde in a proportion of 1.2 mol to 3.0 mol, preferably 1.5 mol to 2.5 mol, per 1 mol of benzoguanamine. The reaction time and reaction temperature in the above reaction may be appropriately set so that the above reaction is completed, and are not particularly limited.

The average degree of polymerization of the triazine ring of the amino resin is preferably designed to be in the range of 1.5 to 4.0, more preferably 1.5 to 2.5. If the average degree of polymerization is within the above range, the amino resin can be dissolved in the vinyl ester and / or the unsaturated polyester, so that workability in impregnating wood with the finally obtained resin composition is improved. It is preferable because it can improve the impregnation property. On the other hand, when the average degree of polymerization exceeds 4.0, it becomes difficult to dissolve the vinyl ester and / or the unsaturated polyester, which is not preferable.

Further, the above resin composition, if necessary,
A compound other than the above vinyl ester, unsaturated polyester, and amino resin (hereinafter referred to as other compound) may be contained. The other compound may be a compound that does not impair various physical properties required for the resin composition. For example, by using an organic peroxide as the above-mentioned other compound, curing can be more efficiently promoted.

The above-mentioned organic peroxide is not particularly limited, but specifically, for example, benzoyl peroxide, methyl ethyl ketone peroxide, t-butylperoxy-2-ethylhexanoate, 1 , 1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t
-Butyl hydroperoxide and the like can be mentioned. Only one kind of these organic peroxides may be used, or two or more kinds thereof may be appropriately mixed and used.

The blending ratio of the vinyl ester to the unsaturated polyester (vinyl ester / unsaturated polyester) is preferably 3/7 to 9/1 in weight ratio, and 4/6 to
7/3 is more preferable. If the weight ratio of unsaturated polyester to vinyl ester is less than 3/7,
When a WPC is produced using the resin composition, the water resistance of the WPC obtained is not sufficient, which is not preferable. On the other hand, if the weight ratio of unsaturated polyester to vinyl ester is greater than 9/1, the resin composition is used
When a PC is manufactured, the durability of the WPC obtained is not sufficient, which is not preferable.

The amount of the amino resin compounded is 5% by weight to the total amount of the vinyl ester and unsaturated polyester.
The range is preferably 30% by weight, and more preferably 5% by weight to 15% by weight.

When the amount of the above amino resin is less than 5% by weight, sufficient WPC durability cannot be obtained, which is not preferable. On the other hand, if the content of the amino resin is more than 30% by weight, the viscosity of the resin composition increases and the impregnating property with respect to wood decreases, which is not preferable.

When the resin composition contains other compounds, the compounding amount of the other compounds is not particularly limited as long as it does not impair various physical properties required for the resin composition. is not. For example, when the organic peroxide is used as the other compound, the amount of the organic peroxide is not particularly limited, but the total amount of the vinyl ester, the unsaturated polyester and the amino resin is 100% by weight. It is preferably within the range of 0.5 to 2 parts by weight with respect to parts. When the blending amount of the organic peroxide is within the above range, the curing of the resin composition can be promoted more efficiently.

Further, the resin composition can be used as it is, but if necessary, conventional additives may be blended and used. Further, the amount of the additive used is not particularly limited.

WPC can be easily obtained by impregnating (inhaling) wood with the resin composition and then curing it by heating under pressure or heating to integrate it with wood.

The method of impregnating wood with the resin composition is not particularly limited, and may be, for example, a dipping method, a reduced pressure injection method, a pressure injection method, depending on the shape and application of the wood.
Wood may be impregnated with the resin composition by a depressurization / pressure injection method, a coating impregnation method (stationary, pressurization) or the like.

Thus, wood is impregnated with the resin composition,
By curing, the resin composition is integrated with wood, and a composite material having excellent durability, that is, WPC can be obtained.

As described above, the resin composition according to the present invention contains a vinyl ester, an unsaturated polyester and an amino resin which is a triazine derivative, and the unsaturated polyester is polyethylene glycol as an alcohol component. And / or a chain aliphatic dibasic acid as an acid component is an essential component.

Thus, by treating the wood with the resin composition of the present invention, that is, by impregnating and curing the resin composition into the wood, the generation of cracks due to the influence of heat and water of the wood is prevented. However, the durability and water resistance of wood can be sufficiently improved.

[0064]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. In the Examples and Comparative Examples, “parts” means “parts by weight”, and “%” means “% by weight”.
Is shown. Further, the durability of the obtained WPC, various physical properties tests (cold heat repeated test, boiling test, cold water) using the test piece obtained by cutting each WPC obtained in each Example and Comparative Example into a predetermined shape It was evaluated by conducting a dipping test and a heat resistance test.

In the cold heat repeated test, the test piece was heated to 80 ° C. ± 3 ° C.
After leaving it in the incubator for 2 hours, leave it in the incubator at −20 ° C. ± 3 ° C. for 2 hours, and repeat this cycle with 1 set to visually check the state of cracks on the surface of the test piece. I observed.

The boiling test was carried out by immersing the test piece in boiling water for 4 hours, then drying it in a thermostat at 60 ° C. ± 3 ° C. for 20 hours, and repeating this cycle of one set to test the surface of the test piece. The state of crack generation was visually observed.

In the cold water immersion test, the test piece was immersed in normal temperature water for 24 hours, and then dried in a thermostat at 60 ° C. ± 3 ° C. for 20 hours,
The state of occurrence of cracks on the surface of the test piece was visually observed.

In the heat resistance test, the test piece was left standing in an incubator at 80 ° C. ± 3 ° C. for 96 hours, and the state of crack generation on the surface of the test piece was visually observed.

Example 1 First, a 4-necked flask equipped with a thermometer, a gas blowing tube, a reflux cooling tube and a stirrer was placed in a bisphenol type epoxy compound “Epototo YD-901” (trade name; Toto Kasei Co., Ltd.). A company-made epoxy resin, an epoxy equivalent of 454.2) 2272 g, methacrylic acid 428 g which is an unsaturated monobasic acid, hydroquinone 0.54 g as a polymerization inhibitor, and triethylamine 11.5 g as an esterification catalyst were charged. Then, the reaction solution was heated to 115 ° C. and reacted for 5.5 hours while blowing air to complete the reaction.

After completion of the reaction, 2300 g of styrene was added to the obtained vinyl ester to give a vinyl ester resin (hereinafter referred to as vinyl ester resin (VE-1)).
I got The acid value of the vinyl ester resin (VE-1) measured by a predetermined method was 3.4 mgKOH / g.

On the other hand, in a four-neck flask similar to the above, polyethylene glycol diethylene glycol 1174 was added.
g, propylene glycol 93 g as another alcohol, and phthalic anhydride which is an anhydride of saturated dibasic acid 9
01g and 440g of adipic acid, a chain aliphatic dibasic acid
And 355 g of maleic anhydride, which is an anhydride of α, β-unsaturated dibasic acid. Then, the temperature was raised to 215 ° C. while blowing an inert gas into this reaction solution, and the reaction was completed by heating dehydration condensation for 15 hours to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method was 20.0 mgKOH / g.

Next, 0.27 g of hydroquinone and 1545 g of styrene were added to the unsaturated polyester to obtain an unsaturated polyester resin (hereinafter referred to as unsaturated polyester resin (UE-1)). The unsaturated polyester resin (UE-1) measured by a predetermined method had a nonvolatile content of 67.0% and an acid value of 13.0 mgKOH / g.

Next, the vinyl ester resin (VE-
1) 50 parts, unsaturated polyester resin (UE-1) 50 parts,
A liquid resin (A ') was obtained by mixing 10 parts of dehydrated benzoguanamine (methylolated benzoguanamine manufactured by Nippon Shokubai Co., Ltd.) which is an amino resin. Table 1 shows the composition of the liquid resin (A ′).

Then, 1 part of "Percure O" (trade name; manufactured by NOF CORPORATION), which is an organic peroxide, was added to 100 parts of the liquid resin (A ').
A resin composition (referred to as a resin composition (A)) was obtained.

Next, a 0.5 mm thick oak wood veneer was heated at 80 ° C. for 3 hours.
After drying for an hour, it was placed in a vacuum vessel and degassed under a reduced pressure of 15 torr for 30 minutes. Next, the resin composition (A) was sucked into the oak wood veneer, deaerated, returned to normal pressure, and allowed to stand for 6 hours. Then, the oak wood veneer impregnated with the resin composition (A) is drained and then placed on a 15 mm-thick plywood coated with a urethane adhesive, and further PET (polyethylene terephthalate) is placed on the plywood. A WPC was obtained by placing the film and curing it with a hot press at 125 ° C. at 10 kgf / cm ² for 5 minutes. The durability of the obtained WPC was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

[Example 2] In a four-necked flask similar to Example 1, 2383 g of "Adaldide XAC-5007" (trade name; epoxy resin manufactured by Ciba-Geigy Co., Ltd., epoxy equivalent 660) which is a bisphenol type epoxy compound ,
Methacrylic acid (318 g), hydroquinone (0.54 g), and triethylamine (11.5 g) were charged. Then, the reaction solution was heated to 115 ° C. and reacted for 5.0 hours while blowing air to complete the reaction.

After completion of the reaction, 2300 g of styrene was added to obtain a vinyl ester resin (hereinafter referred to as vinyl ester resin (VE-2)). The acid value of the vinyl ester resin (VE-2) was 3.2 mgKOH / g.

Next, the vinyl ester resin (VE-
2) 50 parts, unsaturated polyester resin (UE-1) 50 parts,
Liquid resin (B ') mixed with 10 parts of dehydrated benzoguanamine
I got The composition of the liquid resin (B ') is shown in Table 1.

Then, 1 part of "Percure O" was added to 100 parts of the above liquid resin (B '),
A resin composition (hereinafter referred to as resin composition (B)) was obtained.

Then, using the resin composition (B), WPC was obtained in the same manner as in Example 1. WP obtained
The durability of C was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

Example 3 In a four-necked flask similar to that used in Example 1, 729 g of "Epototo YD-901", 1588 g of "Adaldide XAC-5007", methacrylic acid 353
g, hydroquinone 0.54 g, and triethylamine 1
1.6g was charged. Then, the reaction solution was heated to 115 ° C. and reacted for 5.5 hours while blowing air to complete the reaction.

After completion of the reaction, 2300 g of styrene was added to obtain a vinyl ester resin (hereinafter referred to as vinyl ester resin (VE-3)). The acid value of the vinyl ester resin (VE-3) was 3.6 mgKOH / g.

Then, the vinyl ester resin (VE-
3) 50 parts, unsaturated polyester resin (UE-1) 50 parts,
Liquid resin (C ') mixed with 10 parts of dehydrated benzoguanamine
I got The composition of the liquid resin (C ′) is shown in Table 1.

Then, 1 part of "Percure O" was added to 100 parts of the above liquid resin (C '),
A resin composition (referred to as a resin composition (C)) was obtained.

Then, using the resin composition (C), WPC was obtained in the same manner as in Example 1. WP obtained
The durability of C was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

Example 4 In a four-necked flask similar to that of Example 1, a phenol novolac type epoxy compound “Adaldide EPN-1138” (trade name; epoxy resin manufactured by Ciba-Geigy Co., Ltd., epoxy equivalent 180) was used. 3
21 g, "Adaldide XAC-5007" 1071 g, methacrylic acid 303 g, hydroquinone 0.45 g, and triethylamine 9.6 g were charged. Then add 1 part of this reaction solution.
The reaction was completed by raising the temperature to 15 ° C. and reacting for 6.0 hours while blowing air.

After completion of the reaction, 1350 g of styrene was added to obtain a vinyl ester resin (hereinafter referred to as vinyl ester resin (VE-4)). The acid value of the vinyl ester resin (VE-4) was 4.0 mgKOH / g.

Next, the vinyl ester resin (VE-
4) 50 parts, unsaturated polyester resin (UE-1) 50 parts,
Liquid resin (D ') mixed with 10 parts of dehydrated benzoguanamine
I got Table 1 shows the composition of the liquid resin (D ′).

Then, 1 part of "Percure O" was added to 100 parts of the liquid resin (D ') to give
A resin composition (hereinafter referred to as resin composition (D)) was obtained.

Then, using the resin composition (D), a WPC was obtained in the same manner as in Example 1. WP obtained
The durability of C was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

Example 5 In a four-necked flask similar to that of Example 1, 2642 g of triethylene glycol, which is polyethylene glycol represented by the above general formula (1), 1139 g of phthalic anhydride, 624 g of adipic acid, and α were used. , 595 g of fumaric acid, which is a β-unsaturated dibasic acid, was charged. Next, the temperature was raised to 215 ° C. while blowing an inert gas into this reaction solution, and the reaction was completed by heating dehydration condensation for 17 hours to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method is 22.0 mgKOH.
/ G.

Next, 0.27 g of hydroquinone and 2361 g of styrene were added to the unsaturated polyester to obtain an unsaturated polyester resin (hereinafter referred to as unsaturated polyester resin (UE-2)). The nonvolatile content of the unsaturated polyester resin (UE-2) is 65.0%, and the acid value is
It was 14.0 mg KOH / g.

Then, the vinyl ester resin (VE-
3) 50 parts, unsaturated polyester resin (UE-2) 50 parts,
Liquid resin (E ') mixed with 10 parts of dehydrated benzoguanamine
I got The composition of the liquid resin (E ′) is shown in Table 1.

Then, 1 part of "Percure O" was added to 100 parts of the above liquid resin (E '),
A resin composition (referred to as a resin composition (E)) was obtained.

Then, using the resin composition (E), a WPC was obtained in the same manner as in Example 1. WP obtained
The durability of C was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

Example 6 In a four-necked flask similar to that of Example 1, triethylene glycol 2653 g, saturated dibasic acid isophthalic acid 1583 g, and maleic anhydride 764 were used.
g. Next, the temperature was raised to 220 ° C. while blowing an inert gas into the reaction solution, and the reaction was completed by heating dehydration condensation for 22 hours to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method was 18.1 mgKOH / g.

Next, 0.27 g of hydroquinone and 3065 g of styrene were added to the unsaturated polyester to obtain an unsaturated polyester resin (hereinafter referred to as unsaturated polyester resin (UE-3)). The unsaturated polyester resin (UE-3) has a nonvolatile content of 62.0% and an acid value of
It was 11.2 mg KOH / g.

Then, the vinyl ester resin (VE-
1) 50 parts, unsaturated polyester resin (UE-3) 50 parts,
Liquid resin (F ') mixed with 10 parts of dehydrated benzoguanamine
I got Table 1 shows the composition of the liquid resin (F ′).

Then, 1 part of "Percure O" was added to 100 parts of the liquid resin (F '),
A resin composition (hereinafter referred to as resin composition (F)) was obtained.

Then, using the resin composition (F), a WPC was obtained in the same manner as in Example 1. WP obtained
The durability of C was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

Example 7 In the same four-necked flask as in Example 1, 2592 g of dipropylene glycol which is another alcohol, 1384 g of adipic acid, 281 g of phthalic anhydride,
Then, 743 g of maleic anhydride was charged. Next, the temperature was raised to 215 ° C. while blowing an inert gas into this reaction solution, and the reaction was completed by heating dehydration condensation for 17 hours to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method is 21.2 mgKOH.
/ G.

Next, 0.27 g of hydroquinone and 2143 g of styrene were added to the unsaturated polyester to obtain an unsaturated polyester resin (hereinafter referred to as unsaturated polyester resin (UE-4)). The nonvolatile content of the unsaturated polyester resin (UE-4) is 70.0%, and the acid value is
It was 14.7 mg KOH / g.

Then, the vinyl ester resin (VE-
1) 50 parts, 50 parts of unsaturated polyester resin (UE-4),
Liquid resin (G ') mixed with 10 parts of dehydrated benzoguanamine
I got Table 1 shows the composition of the liquid resin (G ′).

Then, 1 part of "Percure O" was added to 100 parts of the above liquid resin (G '),
A resin composition (referred to as a resin composition (G)) was obtained.

Then, using the resin composition (G), WPC was obtained in the same manner as in Example 1. WP obtained
The durability of C was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

[Comparative Example 1] The same four-necked flask as in Example 1 was charged with 1208 g of propylene glycol as another alcohol, 740 g of phthalic anhydride, and 980 g of maleic anhydride. Next, the temperature was raised to 215 ° C. while blowing an inert gas into this reaction solution, and the reaction was completed by heating dehydration condensation for 13 hours to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method was 14.0 mg KOH / g.

Next, by adding 0.22 g of hydroquinone and 1488 g of styrene to the unsaturated polyester, an unsaturated polyester resin for comparison (hereinafter referred to as unsaturated polyester resin (UE-5)) was obtained. The nonvolatile content of the unsaturated polyester resin (UE-5) was 66.0%, and the acid value was 10.0 mgKOH / g.

Then, the above vinyl ester resin (VE-
1) 50 parts, unsaturated polyester resin (UE-5) 50 parts,
A liquid resin (H ') for comparison was obtained by mixing 10 parts of dehydrated benzoguanamine. Table 1 shows the composition of the liquid resin (H ′).

Then, 1 part of "Percure O" was added to 100 parts of the above liquid resin (H '),
A resin composition for comparison (hereinafter referred to as resin composition (H)) was obtained.

Then, using the resin composition (H), a WPC for comparison was obtained in the same manner as in Example 1. The durability of the obtained WPC was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

Comparative Example 2 The vinyl ester resin (V
E-1) 50 parts, unsaturated polyester resin (UE-1) 50
Only a part was mixed to obtain a liquid resin (I ') for comparison. Table 1 shows the composition of the liquid resin (I ′).

Then, 1 part of "Percure O" was added to 100 parts of the liquid resin (I ') to obtain a resin composition (I) for comparison.

Then, using the resin composition (I), a WPC for comparison was obtained in the same manner as in Example 1. The durability of the obtained WPC was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

Comparative Example 3 Only 100 parts of the unsaturated polyester resin (UE-1) and 10 parts of dehydrated benzoguanamine were mixed to obtain a liquid resin (J ') for comparison. Table 1 shows the composition of the liquid resin (J ′).

Then, 1 part of "Percure O" was added to 100 parts of the liquid resin (J ') to obtain a resin composition (J) for comparison.

Then, using the resin composition (J), a WPC for comparison was obtained in the same manner as in Example 1. The durability of the obtained WPC was evaluated by conducting the above-mentioned various physical property tests. The results are shown in Table 2.

[0117]

[Table 1]

[0118]

[Table 2]

As is clear from the results shown in Table 2, each WPC obtained by impregnating and curing each resin composition obtained in this example has excellent heat resistance and water resistance, and is resistant to heat and water. It is possible to prevent the occurrence of cracks due to the influence. On the other hand, each WPC impregnated with each resin composition obtained in the comparative example has a remarkable generation of cracks. Therefore, the WPCs obtained in this example are all WPs obtained in the comparative example.
It is more durable than C. In addition, Examples 1 to 5
As shown in, by using an unsaturated polyester composed of an alcohol component containing polyethylene glycol and an acid component containing a chain aliphatic dibasic acid, a WPC having even more excellent durability can be obtained.

[0120]

As described above, the resin composition for impregnating wood according to claim 1 of the present invention contains the vinyl ester, the unsaturated polyester, and the amino resin which is a triazine derivative, and further contains the above unsaturated compound. The polyester is a structure in which at least polyethylene glycol is used as the alcohol component.

As described above, the resin composition for impregnating wood according to claim 2 of the present invention is the resin composition for impregnating wood according to claim 1, wherein the proportion of the polyethylene glycol in the alcohol component is 70 mol. % Or more.

As described above, the resin composition for impregnating wood according to claim 3 of the present invention is the resin composition for impregnating wood according to claim 1 or 2, wherein the unsaturated polyester is at least as an acid component. This is a structure using a chain aliphatic dibasic acid.

As described above, the resin composition for impregnating wood according to claim 4 of the present invention contains the vinyl ester, the unsaturated polyester and the amino resin which is a triazine derivative, and the unsaturated polyester is As the acid component, at least a chain aliphatic dibasic acid is used.

As described above, the resin composition for impregnating wood according to claim 5 of the present invention is the resin composition for impregnating wood according to claim 1, 2, 3 or 4, wherein the amino resin is a benzoguanamine resin. It is a certain structure.

According to the above constitution, the resin composition for impregnating wood according to the present invention can be integrated with wood by impregnating and curing the wood to obtain WPC having excellent durability. As a result, it is possible to prevent the occurrence of cracks in the wood due to the influence of heat, water, etc., and it is possible to sufficiently improve the durability and water resistance of the wood.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C08L 67/06 LNZ C08L 67/06 LNZ (72) Inventor Ken Emura 2 Nakanoshima, Kita-ku, Osaka City, Osaka Prefecture -3-18 Daiken Kogyo Co., Ltd. (72) Inventor Akinori Morimoto Nakanoshima, Kita-ku, Osaka City, Osaka 2-3-18 Daiken Kogyo Co., Ltd. (72) Inventor Hiroshi Sugimoto Nakanoshima, Kita-ku, Osaka City, Osaka 2-3-18 Daiken Industry Co., Ltd.

Claims (5)

[Claims] 1. A wood impregnated product comprising a vinyl ester, an unsaturated polyester, and an amino resin which is a triazine derivative, wherein the unsaturated polyester comprises at least polyethylene glycol as an alcohol component. Resin composition. 2. The resin composition for wood impregnation according to claim 1, wherein the proportion of the polyethylene glycol in the alcohol component is 70 mol% or more. 3. The resin composition for impregnating wood according to claim 1, wherein the unsaturated polyester comprises at least a chain aliphatic dibasic acid as an acid component. 4. A vinyl ester, an unsaturated polyester, and an amino resin which is a triazine derivative, wherein the unsaturated polyester contains at least a chain aliphatic dibasic acid as an acid component. A characteristic resin composition for impregnating wood. 5. The resin composition for wood impregnation according to claim 1, 2, 3 or 4, wherein the amino resin is a benzoguanamine resin.