JP2002088131A - Resin composition for wood composite and method for producing wood composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition for a wood composite, capable of improving a production environment, etc., efficiently producing a wood composite, providing found mental performances such as surface hardness, heat resistance, water resistance, durability, etc., by adjusting various curing conditions, and to provide a method for producing a compounded wood. SOLUTION: This resin composition for a compounded wood comprises a radically polymerizable polymer compound and a polymerizable unsaturated monomer. The radically polymerizable polymer compound is a polymer compound containing two or more radically polymerizable double bonds in one monomer on the average and the polymerizable unsaturated monomer comprises a compound represented by general formula (I) as an essential component to give the resin composition for a compounded wood.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition for composite wood used for composite wood and a method for producing composite wood.

[0002]

2. Description of the Related Art In recent years, in the field of buildings such as houses and offices, the natural feeling of wood has been favored by the tendency of inhabitants to return to nature. Demands for wood-based materials are increasing.

However, if wood is used as it is in such a wood-based building material, the wood has low resistance to heat, water, and mechanical shock, so that it deteriorates with time, deteriorates, decomposes, rots, surface cracks, and breaks. Therefore, the quality as a building material cannot be maintained. Therefore, composite wood is being studied, which maintains the natural aesthetics and feel of use of the wood and has enhanced resistance to heat, water, and mechanical shock.

Among composite wood, WPC (Wood-Pl)
asic-Combination, Wood-Po
(abbreviation of lymer-Composite etc.) is obtained by impregnating wood with a liquid curable resin or a polymerizable monomer and then hardening the wood. ,
Widely used for interior building materials. As a resin composition to be impregnated into wood used for such composite wood, for example, a resin composition containing an unsaturated polyester resin or the like is conventionally used because of its excellent basic performance such as mechanical strength and durability. Have been.

Recently, VOCs of toluene, xylene, styrene monomer and the like contained in paints, adhesives, etc.
There is a movement to regulate (volatile organic matter content). Thereby, the volatile organic substance is prevented from volatilizing in the production process, so that the work environment such as the coating work is not harmed by the odor, and the work can be efficiently performed. The effect on the health of the elderly can also be suppressed. Further, since the emission of organic substances is suppressed, the influence on the natural environment can be suppressed.

In order to meet such demands, reducing the VOC of styrene monomer and the like even in a resin composition containing an unsaturated polyester resin or the like can prevent the working environment from being harmed by odors and reduce the amount of organic substances emitted. Although it is possible to provide a composite resin composition for wood that can be suppressed, the basic performance such as surface hardness, heat resistance, water resistance, and durability can be improved to improve the basic performance and production. There has been room for studying a resin composition for composite wood that achieves both the effect of improving the working environment and the like in the process. In addition, if such a composite wood resin composition is adapted to any of curing conditions such as heat curing and electron beam curing and exhibits sufficient basic performance, it can be used in various production processes. Composite wood can be produced efficiently. Therefore, it is possible to improve the working environment and the like in the production process and efficiently produce composite wood, and
There has been a demand for a resin composition for composite wood that can exhibit excellent basic performance in various production processes.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and it is possible to improve the working environment and the like in a production process to efficiently produce composite wood. It is an object of the present invention to provide a resin composition for composite wood that can exhibit excellent basic performance such as surface hardness, heat resistance, water resistance and durability by adapting to various curing conditions, and a method for producing a composite wood. It is the purpose.

[0008]

The present invention provides a resin composition for composite wood containing a radical polymerizable polymer compound and a polymerizable unsaturated monomer, wherein the radical polymerizable polymer compound is A polymer compound having two or more radically polymerizable double bonds on average per molecule, wherein the polymerizable unsaturated monomer is represented by the following general formula (I):

[0009]

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(Wherein, R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms. R ² represents an alkylene chain having 1 to 9 carbon atoms or an alkylene chain having 1 to 6 carbon atoms via an oxygen atom. R ³ represents a hydrogen atom or a methyl group.), And is a resin composition for composite wood containing an essential component.

[0011] The present invention is also a resin composition for composite wood containing a radical polymerizable polymer compound and a polymerizable unsaturated monomer, wherein the radical polymerizable polymer compound comprises:
Each molecule has two or more radically polymerizable double bonds on average, a polyfunctional epoxy compound, an unsaturated monobasic acid, two or more carboxyl groups on average in the molecule, and carbon number. A vinyl ester obtained by reacting a polybasic acid having a non-aromatic hydrocarbon chain of 12 or more as an essential component, wherein the vinyl ester is a non-aromatic hydrocarbon having 12 or more carbon atoms derived from the polybasic acid. The ratio of the carbon amount of the chain is 22 to 3 of the total carbon amount of the vinyl ester.
4%, and the polymerizable unsaturated monomer is represented by the following general formula (II):

[0012]

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(Wherein, R ⁴ represents an alkylene chain having 1 to 9 carbon atoms or an oxaalkylene chain having an alkylene chain having 1 to 6 carbon atoms bonded through an oxygen atom. R ⁵ represents a hydrogen atom Or a methyl group) as an essential component.
The present invention is also a method for producing a composite wood, wherein the resin composition for composite wood is irradiated with an electron beam and cured.

The present inventors have proposed a resin composition for composite wood used in composite wood which is easy to handle in the production process and can exhibit excellent basic performance by adapting to various production processes. As a result of intensive studies, the compound represented by the general formula (I) has a lower volatility than the styrene monomer or the like by using the resin composition for composite wood as described above. Due to this, it is possible to improve the working environment in the production process, suppress the emission of organic substances, and adapt to any of various curing conditions such as heat curing and electron beam curing. Since the compound represented by the formula (I) has an excellent affinity for wood as compared with a styrene monomer or the like, it can be sufficiently impregnated into the interior of wood, so that surface hardness, heat resistance, Encountered the fact that a dramatic effect that it is possible to exhibit excellent basic performance of sexual like occurs, it is the present invention has been completed. Further, the composite wood resin composition contains a vinyl ester and a compound represented by the general formula (II) as essential components, and has a carbon content of a non-aromatic hydrocarbon chain having 12 or more carbon atoms in the vinyl ester. When the proportion is within a specific range, it has been found that the impregnating property to wood is further improved and the crack resistance is definitely improved. When manufacturing wood, by applying a method of curing by irradiating an electron beam as a curing method,
The present inventors have also found that the effects of these resin compositions for composite wood can be sufficiently exerted and that the productivity of composite wood can be improved, and the present invention has been achieved. Hereinafter, the present invention will be described in detail.

The composite wood resin composition of the present invention contains a radically polymerizable polymer compound and a polymerizable unsaturated monomer. The radical polymerizable polymer compound is a polymer compound having two or more radical polymerizable double bonds on average per molecule. As such a polymer compound,
Although not particularly limited, examples thereof include unsaturated polyester, vinyl ester, urethane (meth) acrylate, polyester (meth) acrylate, and the like. These may be used alone or in combination of two or more. Among such high molecular compounds, since they are excellent in copolymerizability with a polymerizable unsaturated monomer containing the compound represented by the general formula (I) as an essential component, an average of (meth) ) Polymer compounds having two or more acryloyl groups are preferred. In this specification, the term “polymer compound” is used as a generic term for polymers and compounds having a molecular weight distribution, and does not mean that the compound has a specific molecular weight or more.

The high molecular compound having two or more (meth) acryloyl groups on average per molecule is not particularly limited, but examples thereof include vinyl ester, urethane (meth) acrylate, and polyester (meth) acrylate. Can be Among them, vinyl ester is preferred because of its excellent affinity with wood when formed into composite wood.

The number average molecular weight (M
Although n) is not particularly limited, 600 to 10,000
It is preferable that When it is less than 600, the cured resin composition is inferior in flexibility and flexibility, so that the occurrence of cracks in the composite wood cannot be sufficiently suppressed, and the density of ester bonds in the resin composition. Is too high, heat resistance, water resistance, etc. may decrease. If it exceeds 10,000, the viscosity of the resin composition increases, the permeability of the resin composition to wood decreases, and the surface hardness increases. May be inferior.

The chemical equivalent of the (meth) acryloyl group in the vinyl ester, that is, the average molecular weight per (meth) acryloyl group is not particularly limited, but is preferably 300 to 2,000. When it is less than 300, the crosslink density between the vinyl ester and the polymerizable unsaturated monomer increases, so that the flexibility of the composite wood impregnated with the composite wood resin composition is poor, and the resin composition Since the material is inferior in flexibility, the cured resin composition cannot sufficiently follow the shrinkage and swelling of the wood, and there is a possibility that the generation of cracks cannot be sufficiently suppressed. And the impregnation property of the wood may be deteriorated.

The vinyl ester is not particularly restricted but includes, for example, those obtained by reacting a polyfunctional epoxy compound with an unsaturated monobasic acid and / or polybasic acid. Among them, an unsaturated monobasic acid and a polybasic acid are reacted as essential components, and the polybasic acid has two or more carboxyl groups on average in the molecule and has 12 carbon atoms.
It is preferable to use a polybasic acid having the above non-aromatic hydrocarbon chain. That is, a polyfunctional epoxy compound, an unsaturated monobasic acid, and an average of two carboxyl groups in the molecule.
It is preferable to use one obtained by reacting with a polybasic acid having a non-aromatic hydrocarbon chain having 12 or more carbon atoms as an essential component.

The polyfunctional epoxy compound is not particularly limited as long as it has two or more epoxy groups or glycidyl groups in the molecule. For example, bisphenol A
Epoxy compounds, bisphenol F epoxy compounds, bisphenol S epoxy compounds, bisphenol epoxy compounds such as hydrogenated bisphenol epoxy compounds and tetrabromobisphenol A epoxy compounds; phenol novolak epoxy compounds, cresol novolak epoxy compounds And novolak type epoxy compounds such as hydrogenated novolak type epoxy compounds. These may be used alone or in combination of two or more. Among these, a bifunctional bisphenol-based epoxy compound is preferable because it is easily available.

The average epoxy equivalent of the polyfunctional epoxy compound is not particularly limited, but is preferably from 150 to 700. If it is less than 150, the resin composition may be inferior in physical properties such as water resistance and mechanical strength.
If it exceeds 0, the viscosity of the resin composition will increase, and the permeability of the resin composition to wood may decrease, resulting in poor surface hardness. More preferably, it is 150 to 500.

The unsaturated monobasic acid is not particularly restricted but includes, for example, acrylic acid and methacrylic acid. These may be used alone or in combination of two or more.

On average, two carboxyl groups are present in the above molecule.
The non-aromatic hydrocarbon chain having 12 or more carbon atoms in the polybasic acid having one or more non-aromatic hydrocarbon chains having 12 or more carbon atoms is not particularly limited, for example,
Examples of the aliphatic hydrocarbon chain and the alicyclic hydrocarbon chain include those having at least one atom group and having 12 or more carbon atoms. As the carbon atoms constituting the non-aromatic hydrocarbon chain, those which constitute one group of carbon atoms constituting the main chain of the polybasic acid and carbon atoms constituting the side chain are shown. . The non-aromatic hydrocarbon chain having 12 or more carbon atoms gives vinyl ester flexibility and flexibility, mechanical strength,
Provides basic performance such as heat resistance and water resistance. When the carbon number of the non-aromatic hydrocarbon chain is 11 or less, the carbon chain constituting the non-aromatic hydrocarbon chain is too short, and the cured resin composition is inferior in flexibility and flexibility. The occurrence of cracks in the composite wood cannot be sufficiently suppressed, and the density of ester bonds in the resin composition becomes too high, so that heat resistance, water resistance, and the like decrease.
The carbon number of the non-aromatic hydrocarbon chain having 12 or more carbon atoms is
It is preferably 55 or less. If the number of carbon atoms exceeds 55, the viscosity of the resin composition increases, and the impregnating property to wood may decrease.

On average, two carboxyl groups are contained in the above molecule.
The polybasic acid having one or more and having a non-aromatic hydrocarbon chain having 12 or more carbon atoms is not particularly limited,
For example, dodecandioic acid, tetradecandioic acid, hexadecandioic acid, eicosantioic acid, 1,16- (6-ethylhexadecane) dicarboxylic acid, 1,18- (7,12-octadecadiene) dicarboxylic acid, 1,12 -(6-ethyldodecane) dicarboxylic acid, 1,12- (6-ethynyldodecane) dicarboxylic acid, 1,18- (7-ethynyloctadecane) dicarboxylic acid, 1,14- (7,8-diphenyltetradecane) dicarboxylic acid , 5- (7-carboxyheptyl) -2-hexyl-3-cyclohexenecarboxylic acid, dimer acid obtained from unsaturated fatty acids such as linoleic acid, trimer acid, hydrogenated dimer acid (hydrogenated dimer acid); SLB-12 , ULB-20, SL-20, SB
-20 (all trade names, manufactured by Okamura Oil Company); Empole 1022, Empole 1024, Empole 1061
(All are trade names, manufactured by Cognis); Versadim 21
6, Versa Dime 228 (all trade names, dimer acid manufactured by Cognis); Harari Dimer # 200 (trade name, dimer acid manufactured by Harima Chemical Industry Co., Ltd.) and the like. These may be used alone or in combination of two or more. Among these, the vinyl ester has a flexible structure, and it is further improved to sufficiently suppress the occurrence of cracks in the composite wood, and the surface hardness is excellent.
(6-ethylhexadecane) dicarboxylic acid, 1,12-
(6-Ethyl dodecane) dicarboxylic acid, dimer acid and hydrogenated dimer acid are preferred.

The above polyfunctional epoxy compound, an unsaturated monobasic acid, and a polybasic acid having on average two or more carboxyl groups in the molecule and having a non-aromatic hydrocarbon chain having 12 or more carbon atoms are essential. In the vinyl ester reacted as a component, the non-aromatic hydrocarbon chain having 12 or more carbon atoms may be incorporated at any of the molecular chain terminals in the middle of the molecular chain of the vinyl ester. In order to have a high degree of flexibility, it is preferable to be incorporated in the middle of the molecular chain. In such a vinyl ester, as a non-aromatic hydrocarbon chain having 12 or more carbon atoms, an atomic group having 12 or more carbon atoms, which is obtained by removing a carboxyl group from the above-mentioned polybasic acid, is incorporated. Or two or more types. Further, those having a non-aromatic hydrocarbon chain having an average carbon number of 18 or more are preferable, and those having a non-aromatic hydrocarbon chain having an average carbon number of 30 or more are more preferable.

Reaction of the above polyfunctional epoxy compound, an unsaturated monobasic acid and a polybasic acid having on average two or more carboxyl groups in the molecule and having a non-aromatic hydrocarbon chain having 12 or more carbon atoms In the above, the ratio of these reaction raw materials is not particularly limited, but the total of the epoxy groups and / or glycidyl groups of the polyfunctional epoxy compound is based on 1 equivalent of the carboxyl groups of the unsaturated monobasic acid and the polybasic acid. Is preferably set so as to be 0.9 to 1.1 equivalents. In addition, it is preferable to set the ratio of the reaction raw materials so that the ratio of the carboxyl group of the polybasic acid to the carboxyl group of the unsaturated monobasic acid is 5: 1 to 1: 5 in equivalent ratio. .
When the carboxyl group of the polybasic acid is less than 1: 5, the resin composition may not have flexibility and flexibility, and the carboxyl group of the polybasic acid may have a ratio of 5: 1. If it exceeds, the molecular weight of the vinyl ester becomes large and the viscosity of the resin composition becomes high, so that the impregnation property to wood may be deteriorated.

In the above reaction, it is preferable to use a reaction catalyst because the reaction can be promoted without causing gelation. Examples of the reaction catalyst include zinc organic acids such as zinc octylate, zinc naphthenate, zinc laurate, zinc benzoate, and zinc salicylate; amines such as triethylamine, dimethylbenzylamine, and triethanolamine; tetramethylammonium chloride; Quaternary ammonium salts such as tetramethylammonium bromide, trimethylbenzylammonium bromide, triethylbenzylammonium chloride, triethylbenzylammonium bromide; phosphines such as triphenylphosphine; tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, triphenylmethylphosphonium chloride And the like. These may be used alone or in combination of two or more.

The amount of the above-mentioned reaction catalyst is not particularly limited. In the case of using an organic acid zinc, the amount of the organic acid zinc is 0.005 to 5% by weight based on the total weight of the reaction raw materials. The amount is preferably set to be within a range of from 3.0 to 3.0% by weight, and when other amines other than the organic acid zincs are used, the amount is preferably 0.005 to 5% based on the total weight of the reaction materials. It is preferable to set so as to be within the range of 3.0% by weight.

In the above reaction, if necessary, a polymerizable unsaturated monomer or a solvent inert to the reaction may be used. The reaction temperature and reaction time of the reaction are not particularly limited, and may be set as appropriate. In the above reaction, it is preferable to add a polymerization inhibitor or molecular oxygen to the reaction system in order to prevent gelation due to polymerization.

Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, toluhydroquinone, trimethylhydroquinone, p-benzoquinone, naphthoquinone, methoxyhydroquinone, phenothiazine, methylbenzoquinone. , 2,5-di-t-butylhydroquinone, 2,5-di-t-butylbenzoquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and the like. These may be used alone or in combination of two or more.

Examples of the molecular oxygen include air and a mixed gas of an inert gas such as air and nitrogen.
In this case, blowing into the reaction system (so-called bubbling)
It may be used in such a manner. In order to sufficiently prevent gelation due to the above polymerization, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

In the compound represented by the general formula (I) in the present invention, a hydrocarbon group having 1 to 18 carbon atoms, an alkylene chain having 1 to 9 carbon atoms and an alkylene chain having 1 to 6 carbon atoms are linked via an oxygen atom. The bonded oxaalkylene chain is not particularly limited, and may be a straight-chain or branched one. The hydrocarbon group having 1 to 18 carbon atoms is not particularly limited.
And an alkyl group having 8 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms. These groups may or may not have a substituent.

The compound represented by the above general formula (I) is not particularly limited. For example, methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) ) Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate and the like. These may be used alone or in combination of two or more.

Although the compound represented by the general formula (I) is an essential component of the resin composition for composite wood of the present invention, as long as the effects of the present invention are not impaired, the compound may be used as a polymerizable unsaturated monomer. Compounds other than the compound represented by the general formula (I) can also be used. The polymerizable unsaturated monomer other than the compound represented by the general formula (I) is not particularly limited. For example, aromatic vinyl compounds such as styrene, vinyltoluene, chlorostyrene, and diallyl phthalate; methyl (meth) acrylate (Meth) acrylic acid such as butyl (meth) acrylate, octyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate Esters and the like. These may be used alone or in combination of two or more.

In the resin composition for composite wood of the present invention, since the impregnating property to wood is further improved, as the polymerizable unsaturated monomer, R ^{1 in the} formula (I) is used.
May also be one that represents a hydrogen atom. Such a polymerizable unsaturated monomer is represented by the general formula (II).

The polymerizable unsaturated monomer represented by the general formula (II) is not particularly limited.
Hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methyl (α-hydroxymethyl) acrylate, ethyl (α-hydroxymethyl) acrylate, butyl (α-hydroxymethyl) acrylate and the like. Can be These may be used alone or in combination of two or more.

When the polymerizable unsaturated monomer represented by the general formula (II) is used as the polymerizable unsaturated monomer in the present invention, the vinyl ester used in combination has an average of carboxyl in the molecule used as the raw material. The ratio of the carbon content of the non-aromatic hydrocarbon chain having 12 or more carbon atoms derived from the polybasic acid having two or more groups and having the non-aromatic hydrocarbon chain having 12 or more carbon atoms is the total carbon amount of the vinyl ester. Quantity 2
Preferably it is in the range of 2 to 34%. The ratio of the carbon content of the non-aromatic hydrocarbon chain having 12 or more carbon atoms derived from the polybasic acid is 22% of the total carbon content of the vinyl ester.
If it is less than 1, the crack resistance of the composite wood using the resin composition may be reduced. In addition, the viscosity of the resin composition having a carbon content of more than 34% is increased, and the impregnating property to wood may be reduced.

The ratio of the carbon content of the non-aromatic hydrocarbon chain having 12 or more carbon atoms in the vinyl ester to the total number of carbon atoms of the vinyl ester is calculated, for example, from the amount of raw materials used in synthesizing the vinyl ester. Alternatively, it can be determined by measuring ¹³ C-NMR (nuclear magnetic resonance spectrum) of the vinyl ester.

As described above, a polymerizable unsaturated monomer represented by the general formula (II) is used, and a vinyl ester is a non-aromatic carbon having 12 or more carbon atoms derived from a polybasic acid. In the case of using a resin having a hydrogen chain carbon content in a specific range, the composite wood resin composition of the present invention comprises a radical polymerizable polymer compound and a polymerizable unsaturated monomer. A resin composition for composite wood containing,
The radically polymerizable polymer compound has two or more radically polymerizable double bonds on average per molecule, and a polyfunctional epoxy compound, an unsaturated monobasic acid, and a carboxyl on average in the molecule. A vinyl ester obtained by reacting a polybasic acid having two or more groups and having a non-aromatic hydrocarbon chain having 12 or more carbon atoms as an essential component, wherein the vinyl ester is a carbon derived from the polybasic acid. The proportion of the carbon content of the non-aromatic hydrocarbon chain having a number of 12 or more is in the range of 22 to 34% of the total carbon content of the vinyl ester, and the polymerizable unsaturated monomer is represented by the general formula (II) ) Is a resin composition for composite wood containing as an essential component the compound represented by formula (1). Such a resin composition for composite wood improves the working environment and the like in the production process and improves the efficiency of composite wood. Production In addition to being able to exhibit excellent basic properties such as surface hardness, heat resistance, water resistance, and durability by adapting to various curing conditions, the impregnation into wood is further improved. At the same time, the effect of reliably improving the crack resistance is exhibited. Such a composite resin composition for wood is also one aspect of the present invention.

In the resin composition for composite wood of the present invention, a polymerizable polymer containing a radical polymerizable polymer compound and a compound represented by the general formula (I) or a compound represented by the general formula (II) as essential components. Although the ratio with the saturated monomer is not particularly limited, the radical polymerizable polymer compound is preferably in the range of 20 to 80 parts by weight with the total of both being 100 parts by weight, It is preferred that the amount of the monomer be in the range of 80 to 20 parts by weight. When the amount of the radical polymerizable polymer compound is less than 20 parts by weight and the amount of the polymerizable unsaturated monomer exceeds 80 parts by weight, the composite wood obtained using the resin composition may be affected by heat, water, or the like. There is a possibility that the occurrence of cracks may not be sufficiently suppressed, and the radical polymerizable polymer compound exceeds 80 parts by weight,
When the amount of the polymerizable unsaturated monomer is less than 20 parts by weight, the viscosity of the resin composition becomes high, and the impregnating property to wood may decrease. Further, the proportion of the compound represented by the general formula (I) or the compound represented by the general formula (II) in the polymerizable unsaturated monomer is not particularly limited, but is preferably 40 to
It is preferably in the range of 100% by weight. If the ratio is less than 40% by weight, durability such as crack resistance of the composite wood obtained using the resin composition may be reduced. More preferably, it is in the range of 60 to 100% by weight. The ratio of the total weight of the radical polymerizable polymer compound and the polymerizable unsaturated monomer in the composite wood resin composition of the present invention is not particularly limited, but is preferably 40 to 100% by weight.
Is preferably within the range. More preferably, it is in the range of 60 to 100% by weight.

The resin composition for composite wood of the present invention contains other resin components, plasticizers, etc. in order to improve the basic performance required for composite wood for various uses and the permeability to wood. Additives, solvents and the like can be blended. To the resin composition for composite wood of the present invention, a polymerization initiator may be added in order to polymerize the radical polymerizable polymer compound and the polymerizable unsaturated monomer to cure the resin composition. When irradiating with an active energy ray for polymerization, a photosensitizer may be added. Further, in order to increase the polymerization rate and improve the production efficiency, a polymerization accelerator may be added. The polymerization initiator, the photosensitizer and the polymerization accelerator may be added to the composite wood resin composition in advance,
Although it may be added when impregnating wood with the resin composition,
The timing of addition is set in consideration of the storage stability of the resin composition.

The polymerization initiator is not particularly limited.
For example, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide;
Hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; 1,1-bis (t-butylperoxy) -3,3,5 -Peroxy ketals such as trimethylcyclohexanone; peroxy esters such as t-butyl peroxybenzoate and t-butyl peroxy octoate; dialkyl peroxides such as dicumyl peroxide; dimyristyl peroxy dicarbonate Peroxides such as peroxydicarbonates are exemplified. These may be used alone or in combination of two or more.

The photosensitizer is not particularly limited, and for example, a usual one used when polymerizing a resin composition by irradiation with an active energy ray can be used. The polymerization accelerator is not particularly limited, for example,
Cobalt salts, tertiary amines and the like can be mentioned. These may be used alone or in combination of two or more. The amounts of the polymerization initiator, the photosensitizer, and the polymerization accelerator to be added are not particularly limited, and may be appropriately set according to, for example, the composition of the resin composition.

By using the resin composition for composite wood of the present invention, it is possible to obtain a composite wood by impregnating the resin composition in a completely dry state, for example, after impregnating the resin composition with the resin. it can. The method of impregnating the wood is not particularly limited. For example, the shape and use of the wood may be determined by a dipping method, a reduced pressure injection method, a pressure injection method, a reduced pressure / pressure injection method, a coating impregnation method (static, pressure), or the like. Can be appropriately selected according to the conditions. Further, the amount of impregnation of the wood with the resin composition for composite wood of the present invention is not particularly limited, but in order to impart sufficient surface hardness to the composite wood, the resin composition is sufficiently impregnated into the interior of the conduit of the wood. It is preferable to set the amount to be used. The method for curing wood impregnated with the resin composition for composite wood of the present invention is not particularly limited.
Pressing and heating may be performed by a hot press at about 145 ° C., or active energy rays such as ultraviolet rays, electron beams, and radiation may be irradiated. Among these curing methods, the curing time is short, and a method of curing by irradiating with an electron beam is preferable because the productivity of the composite wood is improved. The method for producing a composite wood, which is cured by irradiating the same, is also one of the present inventions.

Examples of the electron beam irradiation device used for the above-mentioned electron beam irradiation include a scanning electro-curtain type, a curtain type, a Lamirror type, an area beam type, a broad beam type, a pulse beam type and the like. The irradiation condition of the electron beam is not particularly limited.
-100 mA, acceleration voltage 50-1000 kV, irradiation dose 30-400 kGy.

The resin composition for composite wood of the present invention can be applied to various types of composite wood. In particular, there are many opportunities to be exposed to wind and rain, especially for Japanese-style house building materials in which the texture of wood is emphasized. It can be applied favorably to interior building materials such as porches, terraces, and floorings that are easily impacted on a daily basis.

[0047]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Note that “parts” indicates “parts by weight”.

Preparation Example 1 A four-necked flask equipped with a thermometer, an air blowing tube, a reflux condenser and a stirrer was used as a reactor, and as a polyfunctional epoxy compound, a bisphenol A type epoxy compound (trade name "Araldide AER250", Asahi Kasei Corporation) 2531 parts of epoxy resin, average epoxy equivalent 185), dimer acid as polybasic acid (trade name "Versa Dime 228", Cognis Co., Ltd., acid value 194 mgKOH / g, number average molecular weight 619)
1976 parts, as an unsaturated monobasic acid, methacrylic acid 58
9 parts, 15 parts of triethylamine as an esterification catalyst,
And 0.75 part of hydroquinone was charged as a polymerization inhibitor. Subsequently, the mixture was stirred in an air stream and reacted at 115 ° C. for 6 hours. As a result, a vinyl ester having an acid value of 4.8 mgKOH / g and a number average molecular weight of 1560 was obtained as a reaction product. The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain (hereinafter, abbreviated as the ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain) to be the total number of carbon atoms of the vinyl ester was about 40%. As the polymerizable unsaturated monomer represented by the general formula (I), methoxydiethylene glycol methacrylate 5
By mixing 096 parts, a resin composition (1) for composite wood according to the present invention was obtained.

Preparation Example 2 In the same manner as in Preparation Example 1, a vinyl ester was obtained as a reaction product. By mixing 5096 parts of phenoxyethyl methacrylate as the polymerizable unsaturated monomer represented by the general formula (I) with the vinyl ester, a resin composition (2) for composite wood according to the present invention was obtained.

Preparation Example 3 In the same reactor as in Preparation Example 1, 940 parts of a bisphenol A type epoxy compound (trade name “Araldide AER6021, manufactured by Asahi Kasei Epoxy Co., Ltd., average epoxy equivalent 470”) and 172 parts of methacrylic acid were used as polyfunctional epoxy compounds. ,
5 parts of triethylamine and 0.2 parts of hydroquinone were charged. Subsequently, the mixture was stirred in an air stream and reacted at 115 ° C. for 6 hours. As a result, a vinyl ester having an acid value of 4.0 mgKOH / g and a number average molecular weight of 1210 was obtained as a reaction product. As the polymerizable unsaturated monomer represented by the general formula (I), methoxydipropylene glycol methacrylate 7
By mixing 41 parts, a resin composition (3) for composite wood according to the present invention was obtained.

Preparation Example 4 1800 parts of bisphenol A type epoxy compound, 774 parts of dimer acid and 5 parts of acrylic acid were placed in the same reactor as in Preparation Example 1.
40 parts, triethylamine 5 parts, hydroquinone 0.3
The department was charged. Subsequently, the above mixture was stirred in an air stream and reacted at 115 ° C. for 6 hours. As a result, a vinyl ester having an acid value of 4.8 mgKOH / g and a number average molecular weight of 1140 was obtained as a reaction product. The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain of the vinyl ester is about 2
6%. By mixing this vinyl ester with 1677 parts of hydroxypropyl acrylate as a polymerizable unsaturated monomer represented by the general formula (II), a resin composition (4) for composite wood according to the present invention was obtained. .

Preparation Example 5 In a reactor similar to that of Preparation Example 1, 1800 parts of a bisphenol A type epoxy compound, 1114 parts of dimer acid, 461 parts of acrylic acid, 5 parts of triethylamine, and 5 parts of hydroquinone were added.
I put in three parts. Subsequently, the above mixture was stirred in an air stream and reacted at 115 ° C. for 6 hours. As a result, a vinyl ester having an acid value of 4.9 mgKOH / g and a number average molecular weight of 1320 was obtained as a reaction product. The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain of the vinyl ester was about 34%. The vinyl ester has the general formula (II)
By mixing 2250 parts of hydroxypropyl acrylate as the polymerizable unsaturated monomer represented by the formula, a composite wood resin composition (5) according to the present invention was obtained.

Preparation Example 6 1800 parts of bisphenol A type epoxy compound, 681 parts of dimer acid and 5 parts of acrylic acid were placed in the same reactor as in Preparation Example 1.
62 parts, triethylamine 5 parts, hydroquinone 0.3
The department was charged. Subsequently, the above mixture was stirred in an air stream and reacted at 115 ° C. for 6 hours. As a result, a vinyl ester having an acid value of 4.6 mgKOH / g and a number average molecular weight of 910 was obtained as a reaction product. The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain of the vinyl ester is about 23.
%Met. By mixing this vinyl ester with 1304 parts of hydroxyethyl acrylate as a polymerizable unsaturated monomer represented by the general formula (II), a resin composition (6) for composite wood according to the present invention was obtained. .

Comparative Preparation Example 1 In the same manner as in Preparation Example 1, a vinyl ester was obtained as a reaction product. Styrene monomer 509 was added to this vinyl ester.
By mixing 6 parts, a comparative composite resin composition for wood (1) was obtained.

Comparative Preparation Example 2 In the same manner as in Preparation Example 3, a vinyl ester was obtained as a reaction product. Styrene monomer 741
Was mixed to obtain a comparative composite resin composition for wood (2).

Examples 1-3 and Comparative Examples 1-2Preparation of test piece 1  The resin composition for composite wood according to the present invention (1) to
(3) and a comparative composite resin composition for wood (1) and
(2) 100 parts of curing agent Percure O (product
Name, Nippon Oil & Fats Co., Ltd.)
An additive resin composition was obtained. Next, 0.2 mm thick oak wood
After drying the veneer at 80 ° C. for 3 hours, put it in a vacuum container,
Degas under reduced pressure of 15 Torr for 30 minutes. Furthermore, this
The above hardener-added resin composition is inhaled into a veneer veneer veneer,
It returned to pressure and let stand for 6 hours. Then, veneer after resin impregnation
And then apply urethane adhesive beforehand.
Place on the coated plywood of 15mm thickness, and further put PE on it
Place the T-film and hot press at 125 ° C, 9.8
× 10^FiveN / m^TwoBy heating for 5 minutes
A less-cured WPC was obtained. 15cm × from the obtained WPC
Cut a 15cm test piece and conduct the following physical property tests
Was. The results are shown in Table 1.

Examples 4 to 7 and Comparative Examples 3 to 4Preparation of test piece 2  The composite resin composition for wood according to the present invention (1) and
(2) to (4) and Comparative Resin Composition for Composite Wood
(1) and (2) were replaced with 15 oak veneer veneers 0.2 mm thick.
8 g / size on composite plywood bonded to plywood^TwoTona
And left to stand for one hour. Then Eliasby
Using an electron beam irradiation system with an accelerating voltage of 350 kV
Radiation dose 200kGy, conveyor speed 5m / mi
n, by irradiating one-pass electron beam in a nitrogen atmosphere
The resin composition was cured to obtain an electron beam cured WPC. Get
Cut a 15cm x 15cm test piece from the WPC
The following physical property test was performed. Table 2 shows the results.
Was.

Physical property evaluation method and evaluation criteriaHeat resistance test  Leave the specimen in a thermostat at 80 ° C ± 3 ° C, every 24 hours
And visually observe the state of cracks on the surface of the test piece.
Confirmed in. ◎: No cracks generated ○: Minor cracks that are difficult to visually confirm △: Small cracks generated ×: Large cracks generated

[0059]Water resistance test  After immersing the test piece in water temperature 25 ℃ ± 3 ℃ for 24 hours,
Dry in a thermostat at 60 ° C ± 3 ° C for 20 hours.
Let's say Icle. The cracks on the specimen surface
The state of occurrence was visually checked. The standard is the same as the heat resistance test.
Was.

[0060]Surface hardness test  Specified in 8.4.1 of JIS K5400 (1995)
Apply a 1 kg load according to the pencil scratch test
Scratch the surface of the WPC with the pencil lead,
The number of times that the test can be performed less than 2 times in 5 tests
The density number of the hardest pencil was defined as the surface hardness.

[0061]

[Table 1]

[0062]

[Table 2]

As is apparent from Table 1, in Examples 1 to 3, each of the composite wood resin compositions (1) to (3) was impregnated into a thin oak veneer by a vacuum injection method, and then pressed and heated. The composite wood hardened and cured had better heat resistance and water resistance than the composite wood using the comparative resin compositions (1) and (2) for composite wood. Furthermore, it was hard to be damaged and had excellent surface hardness. In addition, in the composite wood resin compositions (1) to (3), the content of the styrene monomer is reduced (in the composite wood resin compositions (1) to (3), the content of the styrene monomer is reduced). 0% by weight), so that sufficient basic performance can be exhibited and the working environment in the production process of composite wood can be improved by suppressing the odor caused by the styrene monomer. I understood.

As is clear from Table 2, in Examples 4 to 7, the resin compositions (1) and (4) to
The composite wood obtained by impregnating (6) each in a veneer veneer by coating and impregnating it and curing with electron beam is better than the composite wood using the composite resin compositions (1) and (2) for composite wood. The heat resistance and water resistance were excellent, the generation of cracks was suppressed, and the durability was excellent. Furthermore, it was hard to be damaged and had excellent surface hardness. Further, in the composite wood resin compositions (1) and (4) to (6), the content of the styrene monomer is reduced (the composite wood resin compositions (1) and (4) to (6)). In), the content of styrene monomer is 0% by weight.) Therefore, sufficient basic performance can be exhibited, and odor due to styrene monomer is suppressed to improve the working environment in the production process of composite wood. It turned out to be something that could be done.

[0065]

As described above, the resin composition for composite wood of the present invention has the above-mentioned constitution, so that it is possible to improve the working environment and the like in the production process and to produce the composite wood efficiently.
In addition, the surface hardness and heat resistance,
Exhibits excellent basic performance such as water resistance, sufficiently suppresses the occurrence of cracks due to the effects of heat, water, etc., has excellent durability, and is a Japanese-style building material that emphasizes the texture of wood such as flooring, porch, terraces, etc. Etc. can be applied favorably.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2B230 CB01 CB06 CB08 EA20 EB01 EB08 4J027 AB01 AB36 AE01 AE02 AE03 AE05 AE06 AG01 BA08 BA20 BA21 BA24 BA27 CA10 CB03 CC06 CD09

Claims (5)

[Claims] 1. A composite wood resin composition comprising a radically polymerizable polymer compound and a polymerizable unsaturated monomer, wherein the radically polymerizable polymer compound has an average of radicals per molecule. A polymer compound having two or more polymerizable double bonds, wherein the polymerizable unsaturated monomer is represented by the following general formula (I): (In the formula, R ¹ represents a hydrocarbon group having 1 to 18 carbon atoms.
R ² is an alkylene chain having 1 to 9 carbon atoms or 1 to 6 carbon atoms.
Represents an oxaalkylene chain in which the alkylene chain is bonded via an oxygen atom. R ³ represents a hydrogen atom or a methyl group. A composite resin composition for wood, comprising the compound represented by the formula (1) as an essential component. 2. The radically polymerizable polymer compound comprises:
2. The resin composition for composite wood according to claim 1, wherein the resin composition is a polymer compound having two or more (meth) acryloyl groups on average per molecule. 3. The radical polymerizable polymer compound comprises a polyfunctional epoxy compound, an unsaturated monobasic acid, a non-aromatic carbon compound having an average of two or more carboxyl groups in the molecule and having 12 or more carbon atoms. 3. The resin composition for composite wood according to claim 1, wherein the resin composition is a vinyl ester obtained by reacting a polybasic acid having a hydrogen chain as an essential component. 4. A composite resin composition for wood containing a radically polymerizable polymer compound and a polymerizable unsaturated monomer, wherein the radically polymerizable polymer compound has an average of radicals per molecule. Having two or more polymerizable double bonds, and
A polyfunctional epoxy compound, an unsaturated monobasic acid, and a polybasic acid having an average of two or more carboxyl groups in the molecule and a non-aromatic hydrocarbon chain having 12 or more carbon atoms are reacted as essential components. Vinyl ester,
The vinyl ester has 1 carbon atom derived from the polybasic acid.
The ratio of the carbon content of the two or more non-aromatic hydrocarbon chains is in the range of 22 to 34% of the total carbon content of the vinyl ester;
The polymerizable unsaturated monomer is represented by the following general formula (II): (In the formula, R ⁴ represents an alkylene chain having 1 to 9 carbon atoms or an oxaalkylene chain having an alkylene chain having 1 to 6 carbon atoms bonded through an oxygen atom. R ⁵ represents a hydrogen atom or a methyl group. Wherein the compound represented by the formula (1) is contained as an essential component. 5. A method for producing composite wood, wherein the resin composition for composite wood according to claim 1 is irradiated with an electron beam and cured.