JP2000317909A - Resin composition for to-be-composited wood - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for to-be-composited wood which has a high permeability into wood and is excellent in durability and surface hardness. SOLUTION: In a resin composition for to-be-composited wood which contains a vinyl ester having a (meth)acryloyl group and a at least 12c nonaromatic hydrocarbon chain, and a polymerizable unsaturated monomer, in the (meth) acryloyl group contained in the vinyl ester, there are at least two groups on the average per molecule. In the at least 12c nonaromatic hydrocarbon chain, an amount of carbon in the hydrocarbon chain is at least 35% of the total carbon amount of the vinyl ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for composite wood used for 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)
Astic composites are obtained by impregnating wood with a liquid curable resin or a polymerizable monomer and then curing the same.

As a resin for impregnating wood used in composite wood, for example, unsaturated polyester resin and the like have been conventionally used. However, when composite wood is produced using unsaturated polyester resin, the balance between mechanical strength and flexibility of the resin itself is not sufficient, and it cannot follow shrinkage or swelling of wood due to the influence of heat or water. Cracks may occur, and the durability of the composite wood as basic performance was not sufficient. Therefore, when combined with wood for composite wood, one that is excellent in durability against the effects of heat, water, and the like is desired.

By the way, in researching the performance improvement of composite wood, wood has a large number of conduits for metabolizing it as a plant from the surface to the inner layer. It has been found that a resin composition which is of high quality and can be sufficiently impregnated into the inside of such a conduit is indispensable for producing composite wood having excellent durability, uniformity and high performance. .

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and has high permeability to wood.
It is an object of the present invention to provide a composite wood resin composition having excellent durability and surface hardness.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a composite wood containing a vinyl ester having a (meth) acryloyl group and a non-aromatic hydrocarbon chain having 12 or more carbon atoms, and a polymerizable unsaturated monomer. Resin composition, wherein the vinyl ester has at least two (meth) acryloyl groups per molecule on average, and a non-aromatic hydrocarbon chain having 12 or more carbon atoms has a carbon atom of the hydrocarbon chain. An amount of the resin composition for composite wood is 35% or more of the total carbon content of the vinyl ester. Hereinafter, the present invention will be described in detail.

The resin composition for composite wood of the present invention contains a vinyl ester and a polymerizable unsaturated monomer. The vinyl ester has an average of two or more (meth) acryloyl groups per molecule and a non-aromatic hydrocarbon chain having 12 or more carbon atoms.

The (meth) acryloyl group undergoes a polymerization reaction with a polymerizable unsaturated bond of the polymerizable unsaturated monomer,
Crosslink the vinyl ester with the polymerizable unsaturated monomer. The (meth) acryloyl group may be composed of an acryloyl group or a methacryloyl group, or may be composed of an acryloyl group and a methacryloyl group.

The number average molecular weight (Mn) of the vinyl ester in the present invention is not particularly limited, but may be from 600 to 1
0000 is preferred. If it is less than 600,
Inferior in flexibility and flexibility of the cured resin composition,
Since 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, heat resistance, water resistance, and the like may be reduced, and exceeds 10,000. Then, the viscosity of the resin composition may increase, and the permeability of the resin composition to wood may decrease, resulting in poor surface hardness.

The above (meth) in the above vinyl ester
The chemical equivalent of the acryloyl group, that is, the average molecular weight per (meth) acryloyl group is not particularly limited, but is preferably 300 to 2,000. 300
If it is less than 3, since the crosslink density between the vinyl ester and the polymerizable unsaturated monomer increases, the flexibility of the composite wood obtained by impregnating the resin composition for the composite wood is inferior, and the resin composition Is inferior in flexibility, the cured resin composition cannot sufficiently follow shrinkage and swelling of wood, and there is a possibility that the occurrence of cracks cannot be sufficiently suppressed.
There is a possibility that the viscosity of the resin composition is increased and impregnating property to wood is deteriorated.

The above-mentioned vinyl ester has 1 carbon atom.
The two or more non-aromatic hydrocarbon chains are those having at least one atom group of an aliphatic hydrocarbon chain and an alicyclic hydrocarbon chain and having 12 or more carbon atoms. As the carbon atoms constituting the non-aromatic hydrocarbon chain, those constituting one group of carbon atoms constituting the main chain and carbon atoms constituting the side chains are shown. The non-aromatic hydrocarbon chain having 12 or more carbon atoms has flexibility and flexibility in vinyl ester,
Provides basic performance such as mechanical strength, 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 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. In the vinyl ester, the non-aromatic hydrocarbon chain having 12 or more carbon atoms may be incorporated in the middle of the molecular chain of the vinyl ester or at any of the molecular chain terminals, but the vinyl ester has sufficient flexibility. In order to have, it is preferable to be incorporated in the middle of the molecular chain.

The above-mentioned vinyl ester having 1 carbon atom
The two or more non-aromatic hydrocarbon chains are not particularly limited,
For example, an atomic group having 12 or more carbon atoms obtained by removing a carboxyl group from a polybasic acid having a non-aromatic hydrocarbon chain having an average carbon number of 12 or more (hereinafter, referred to as polybasic acid (I)) is exemplified. These may be used alone or in combination of two or more. Among the polybasic acids (I), 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.

The polybasic acid (I) is not particularly limited as long as it is a compound having the non-aromatic hydrocarbon chain having 12 or more carbon atoms and at least two carboxyl groups. For example, dodecane diacid, Tetradecandioic acid, hexadecandioic acid, eicosandioic acid, 1,16- (6-ethylhexadecane) dicarboxylic acid, 1,18- (7,1
2-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, trimer acid, hydrogenated dimer acid (hydrogenated dimer acid) obtained from unsaturated fatty acids such as linoleic acid; SLB-12, ULB-20, SL -2
0, SB-20 (both trade names, manufactured by Okamura Oil Co., Ltd.); ENPOL 1022, ENPOL 1024 (both trade names, manufactured by Emery Co.); Acid); Hararidimer # 200 (trade name, dimer acid manufactured by Harima Chemical Industry Co., Ltd.) and the like. Among these,
Since the vinyl ester has a flexible structure, and the occurrence of cracks in the composite wood is further improved and the surface hardness is excellent, 1,16- (6-ethylhexadecane) dicarboxylic acid, Preferred are 12- (6-ethyldodecane) dicarboxylic acid, dimer acid and hydrogenated dimer acid.

In the vinyl ester of the present invention, the non-aromatic hydrocarbon chain having 12 or more carbon atoms has a carbon content of 35% or more of the total carbon content of the vinyl ester. The present inventors have studied various resin compositions for composite wood, and when the resin composition was composed using the above vinyl ester, when combined with wood, heat resistance, excellent water resistance and the like were obtained. The inventors have discovered that durability can be obtained, and have completed the present invention. Here, there is a gist of the present invention. When the carbon content of the non-aromatic hydrocarbon chain having 12 or more carbon atoms is less than 35% of the total carbon content of the vinyl ester, the flexibility of the resin composition is poor, and the occurrence of cracks in the composite wood is sufficiently suppressed. In this case, the density of ester bonds in the resin composition becomes too high, and heat resistance, water resistance and the like decrease.

In order to improve the basic performance and durability of the composite wood and to sufficiently suppress the occurrence of cracks, the vinyl ester of the present invention has 12 carbon atoms.
The carbon content of the non-aromatic hydrocarbon chain described above is preferably in the range of 45 to 80%, more preferably in the range of 50 to 70% of the total carbon content of the vinyl ester.

The above-mentioned vinyl ester has the above carbon number 1
The ratio of the number of carbon atoms of the two or more non-aromatic hydrocarbon chains can be appropriately set within the above-described range depending on the use of the obtained composite wood, the physical properties required for the composite wood, and the like.

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 in 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.

The method for producing the vinyl ester in the present invention is not particularly limited. For example, a method of subjecting the polybasic acid (I) to an esterification reaction with a (meth) acrylate having an epoxy group (hereinafter referred to as a production method);
A method of subjecting the polybasic acid (I), (meth) acrylate having an epoxy group, and if necessary, an unsaturated monobasic acid and a polyfunctional epoxy compound to an esterification reaction (hereinafter referred to as a production method); ), An unsaturated monobasic acid and a polyfunctional epoxy compound in an esterification reaction (hereinafter referred to as a production method); a carboxyl group at a molecular chain terminal which is a condensate of polybasic acid (I) and a polyhydric alcohol And a method of causing an esterification reaction of a polyester having an epoxy group with a (meth) acrylate having an epoxy group (hereinafter referred to as a production method).

The (meth) acrylate having an epoxy group is not particularly limited as long as it is a compound having at least one epoxy group and / or glycidyl group and at least one (meth) acryloyl group in a molecule. Glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, methacrylic acid-4,5
-Epoxypentyl, acrylate-6,7-epoxypentyl and the like. These may be used alone,
Two or more kinds may be used in combination. Among these, glycidyl (meth) acrylate is preferred because it is easily available.

The ratio of the polybasic acid (I) and the epoxy group-containing (meth) acrylate in the above production method is not particularly limited, but is based on 1 equivalent of the carboxyl group of the polybasic acid (I). The ratio of the reaction raw materials is preferably set so that the epoxy group and the glycidyl group of the (meth) acrylate having an epoxy group are 0.9 equivalent to 1.1 equivalent.
In addition, in this specification, a reaction raw material means all the raw materials which will constitute the product by the reaction.

In the above production method, the polybasic acid (I)
The ratio of the (meth) acrylate having an epoxy group, the unsaturated monobasic acid if necessary, and the polyfunctional epoxy compound is not particularly limited, but the polybasic acid (I)
And the total amount of the epoxy group-containing (meth) acrylate having an epoxy group and the epoxy group and / or glycidyl group of the polyfunctional epoxy compound is 0 with respect to 1 equivalent of the total amount of the carboxyl group of the unsaturated monobasic acid used as required. It is preferable to set so as to be in the range of 0.9 to 1.1 equivalents. The ratio of the (meth) acrylate having an epoxy group to the polyfunctional epoxy compound is set as follows: the epoxy group and / or the glycidyl group of the (meth) acrylate having an epoxy group and the epoxy group and / or
Alternatively, it is preferable to set the equivalent ratio of the glycidyl group to be in the range of 1: 4 to 4: 1.

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.

In the above manufacturing method, (meth) acrylic acid or the like may be used, if necessary, in consideration of the basic properties such as the viscosity of the resin composition, flexibility and mechanical strength required for the composite wood, and the like. Can be used. The amount of the unsaturated monobasic acid used is not particularly limited, but may be appropriately set according to the molecular weight distribution of the vinyl ester, the crosslinking density when the resin composition is cured, and, for example, the carboxyl groups of all the raw materials. 2 to 30% based on equivalent
May be set to fall within the range.

The polybasic acid (I) and the polyfunctional epoxy compound in the above production method are not particularly limited, and examples thereof include the same ones as described above. These may be used alone or in combination of two or more.

In the above production method, the ratio of the polybasic acid (I), the unsaturated monobasic acid, and the polyfunctional epoxy compound is not particularly limited, but the polybasic acid (I) and the unsaturated monobasic acid are not limited. The total of the epoxy group and / or glycidyl group of the polyfunctional epoxy compound is 0.9 to 1 equivalent of the carboxyl group of the basic acid.
It is preferable to set the ratio of the reaction raw materials so as to be 1.1 equivalent. Further, the ratio of the reaction raw materials is such that the ratio of the carboxyl group of the polybasic acid (I) to the carboxyl group of the unsaturated monobasic acid is 2: 1 to 1: 2 in equivalent ratio. It is preferable to set. If the polybasic acid (I) is less than 1: 2, the resin composition may not have flexibility and flexibility, and the polybasic acid (I) may have a 2: 1 ratio. 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 production method, the polybasic acid (I)
Polyhydric alcohol in the case of obtaining a polyester having a carboxyl group at the molecular chain end which is a condensate of a polyhydric alcohol and the polyhydric alcohol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. , Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, hydrogenated bisphenol A, propylene oxide adduct of bisphenol A,
1,4-cyclohexanedimethanol, 3-methyl-
1,3-butanediol and the like. These may be used alone or in combination of two or more.

The proportion of the polybasic acid (I) and the polyhydric alcohol used is not particularly limited, but one of the hydroxyl groups contained in the polyhydric alcohol may be used in order to efficiently leave a carboxyl group at the molecular chain terminal. The carboxyl group of the polybasic acid (I) is 1.1 to 2.2 with respect to the equivalent.
It is preferable to set so as to be within the range of the equivalent. As the condensation reaction method for obtaining the polyester having a carboxyl group at the molecular chain terminal, a conventionally known method can be applied and is not particularly limited.

The (meth) acrylate having an epoxy group in the above production method is not particularly limited, and examples thereof include the same ones as described above. These may be used alone or in combination of two or more.

Further, when the polyester having a carboxyl group at the molecular chain terminal and the (meth) acrylate having an epoxy group are subjected to an esterification reaction, the use ratio of the polyester and the (meth) acrylate having an epoxy group is as follows: Although not particularly limited, the epoxy group of the (meth) acrylate having an epoxy group may be set to fall within the range of 0.9 to 1.1 equivalents with respect to 1 equivalent of the carboxyl group of the polyester. preferable.

In the esterification reaction, it is preferable to use a reaction catalyst because the esterification reaction can be promoted without causing gelation. Examples of the reaction catalyst include organic acid zincs 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. Among these, in the production method and in the production method, it is preferable to use organic acid zincs, and in the production method, it is preferable to use a catalyst such as an organic acid zinc and other amines in combination, and in the production method, , And other amines are preferably used.

The amount of the esterification catalyst to be used is not particularly limited. When the above-mentioned organic acid zincs are used, the amount of the above-mentioned organic acid zinc is determined by the amount of zinc atom based on the total weight of the reaction raw materials. The content is preferably set to be in the range of 0.005 to 3.0% by weight. When the above-mentioned other amines and the like are used, 0.005 to 3.0% by weight based on the total weight of the reaction raw materials. It is preferable to set so as to be within the range of 0% by weight.

In the esterification reaction, if necessary, a solvent inert to the reaction may be used, or a polymerizable unsaturated monomer may coexist. The solvent is not particularly limited, and includes, for example, toluene, xylene and the like. These may be used alone or in combination of two or more. In addition, because it sufficiently prevents gelation,
It is preferable to carry out the reaction in the presence of molecular oxygen such as a mixed gas of an inert gas such as air or nitrogen and air or oxygen, or a radical polymerization inhibitor such as hydroquinone or benzoquinone.

The order of mixing and the method of mixing the reaction raw materials, catalysts, solvents and the like used in the above-mentioned esterification reaction are not particularly limited, and the mixing can be carried out according to the usual mixing order or method of the esterification reaction. The reaction temperature of the esterification reaction is not particularly limited. The reaction time of the esterification reaction is not particularly limited, for example, a combination of raw materials, the amount of catalyst added, the presence or absence of a solvent,
What is necessary is just to set suitably according to reaction temperature etc.

The polymerizable unsaturated monomer in the present invention is not particularly limited as long as it is a monomer having a polymerizable unsaturated bond which can be cross-linked by polymerizing with the (meth) acryloyl group of the vinyl ester. For example, aromatic vinyl compounds such as styrene, vinyltoluene, and chlorostyrene; methyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, diethylene glycol di (meth) acrylate, 2-hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, methyl (α-hydroxymethyl) acrylate, ethyl (α-hydroxymethyl) acrylate,
(Meth) acrylic acid esters such as butyl (α-hydroxymethyl) acrylate; These may be used alone or in combination of two or more.

Among the polymerizable unsaturated monomers in the present invention, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methyl (α-hydroxymethyl) acrylate, ethyl (α-hydroxymethyl) acrylate, Since those having a hydroxyl group such as butyl (α-hydroxymethyl) acrylate are well compatible with wood, the resin composition can be sufficiently impregnated into the interior of a wood conduit, and when used for composite wood. Further, it is preferable because the surface hardness is excellent.

The ratio between the vinyl ester and the polymerizable unsaturated monomer is not particularly limited, but the total amount of the vinyl ester and the polymerizable unsaturated monomer is 30 to 8 parts by weight.
0 parts by weight, and preferably 70 to 20 parts by weight of the polymerizable unsaturated monomer. When the vinyl ester is less than 30 parts by weight and the polymerizable unsaturated monomer exceeds 70 parts by weight, the basic performance of the composite wood is poor, and the generation of cracks due to the influence of heat, water, etc. is sufficiently suppressed. When the amount of the vinyl ester exceeds 80 parts by weight and the amount of the polymerizable unsaturated monomer is less than 20 parts by weight, the viscosity of the resin composition increases, and the impregnation property to wood becomes poor. May be inferior.

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 the composite wood for various uses and the permeability to wood. Additives, solvents and the like can be blended. In order to harden the resin composition by polymerizing the vinyl ester and the polymerizable unsaturated monomer, a polymerization initiator may be added to the resin composition for composite wood of the present invention, or an active energy ray may be added. When irradiating to polymerize, 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 resin composition for composite wood in advance, or may be added when impregnating wood with the resin composition. However, the time 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 and the like. 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 irradiating it 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 a composite wood of the present invention, it is possible to obtain a composite wood by impregnating the resin composition into a completely dried wood, for example, by impregnating the resin composition. 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, pressurized), 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 115 ° C., or active energy rays such as ultraviolet rays, electron beams, and radiation may be irradiated.

By using the resin composition for composite wood of the present invention, the cured resin composition has basic properties such as flexibility, mechanical strength, heat resistance, water resistance, etc. Since it has the flexibility enough to follow the shrinkage and swelling of the wood due to the influence, it is possible to obtain a composite wood excellent in durability by sufficiently suppressing the occurrence of cracks.
In addition, since the resin composition has a high permeability that can sufficiently impregnate the interior of the wood conduit, it is integrated with the wood, and is excellent against mechanical impact on the surface of the composite wood, so that the conduit is not collapsed. Thus, a uniform and high-performance composite wood having excellent surface hardness can be obtained.

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

[0046]

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 reaction vessel, and 490 parts of glycidyl methacrylate as an epoxy group-containing (meth) acrylate, polybasic As the acid (I), dimer acid (trade name “Versa Dime 228”, manufactured by Henkel, acid number 19)
4 mg KOH / g, number average molecular weight 619) 2000 parts,
Zinc octylate (Zinc content 1
5 parts by weight) and 0.9 part of hydroquinone as a polymerization inhibitor were charged. Subsequently, the mixture was stirred in an air stream and reacted at 115 ° C. for 2 hours. The acid value of this product was 78 mg KOH / g. Furthermore, bisphenol A type epoxy compounds (trade name “Araldide GY-250”, Ciba.
640 parts of Geigy's average epoxy equivalent 185)
14 parts of triethylamine were charged as an esterification catalyst. The mixture was stirred in an air stream and reacted at 115 ° C. for 3 hours. This gives an acid value of 4.0 mg KOH
/ G, a vinyl ester having a number average molecular weight of 2,200 as a reaction product. The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain to the total number of carbon atoms of the vinyl ester (hereinafter referred to as the ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain) is about 62%. Met. By mixing 3130 parts of hydroxyethyl methacrylate as a polymerizable unsaturated monomer with this vinyl ester, 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, 980 parts of glycidyl methacrylate, 2,000 parts of dimer acid, 14 parts of zinc octylate, and 0.9 part of hydroquinone were charged into a reaction vessel.
Subsequently, the mixture was stirred in an air stream at 115 ° C.
For 4 hours. This results in an acid value of 6.0 mg KO.
H / g vinyl ester was obtained as the reaction product. The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain of the vinyl ester was about 68%. By mixing 1490 parts of hydroxyethyl methacrylate and 1490 parts of styrene monomer with this vinyl ester, a resin composition (2) for composite wood according to the present invention was obtained.

Preparation Example 3 In the same manner as in Preparation Example 1, 490 parts of glycidyl methacrylate, 2,000 parts of dimer acid, 14 parts of zinc octylate, and 0.9 part of hydroquinone were charged into a reaction vessel.
Subsequently, the mixture was stirred in an air stream at 115 ° C.
For 2 hours. The acid value of this product is 78 mg KO
H / g. Further, 1020 parts of a bisphenol A type epoxy compound, 180 parts of methacrylic acid, and 14 parts of triethylamine were added. The mixture was stirred in an air stream and reacted at 115 ° C. for 3 hours. This gave an acid value of 3.4 mg KOH / g and a number average molecular weight of 147.
A vinyl ester of 0 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 53%. By mixing 3690 parts of hydroxyethyl methacrylate with the vinyl ester, the resin composition for composite wood according to the present invention (3)
I got

Preparation Example 4 In the same manner as in Preparation Example 1, 284 parts of glycidyl methacrylate, a mixture of 1,12- (6-ethyldodecane) dicarboxylic acid and 1,16- (6-ethylhexadecane) dicarboxylic acid were placed in a reaction vessel. 685 parts (trade name “SB-20”, manufactured by Okamura Oil Co., Ltd., acid value: 328 mg KOH / g), 4 parts of zinc octylate, and 0.4 part of hydroquinone were charged. Subsequently, the mixture was stirred in an air stream to obtain 11
The reaction was performed at 5 ° C. for 2 hours. The acid value of this product is 115 m
gKOH / g. Further, 374 parts of a bisphenol A type epoxy compound and 1.4 parts of triethylamine were added. The mixture is stirred in a stream of air,
The reaction was performed at 5 ° C. for 3 hours. This gives an acid value of 5.0 mg.
KOH / g vinyl ester was obtained as the reaction product.
The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain of the vinyl ester was about 47%. By mixing 1343 parts of hydroxyethyl acrylate with this vinyl ester, a resin composition (4) for composite wood according to the present invention was obtained.

Preparation Example 5 In the same manner as in Preparation Example 1, 2531 parts of a bisphenol A type epoxy compound, 1976 parts of dimer acid, 589 parts of methacrylic acid, 15 parts of triethylamine, and
0.75 parts of hydroquinone was 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 4.8 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 of the vinyl ester was about 38%. By mixing 5096 parts of hydroxyethyl methacrylate with this vinyl ester, a resin composition (5) for composite wood according to the present invention was obtained.

Comparative Preparation Example 1 In the same manner as in Preparation Example 1, 284 parts of glycidyl methacrylate, 308 parts of hexahydrophthalic anhydride were placed in a reaction vessel.
4 parts of zinc octylate and 0.4 part of hydroquinone were charged. Subsequently, the mixture was stirred in an air stream and reacted at 115 ° C. for 2 hours. The acid value of this product was 95 mgKOH / g. Further, 374 parts of a bisphenol A type epoxy compound and triethylamine 1.
And 4 parts. The mixture was stirred in an air stream and reacted at 115 ° C. for 3 hours. This gave a comparative vinyl ester with an acid value of 5.0 mg KOH / g as a reaction product. By mixing 966 parts of hydroxyethyl acrylate with this comparative vinyl ester,
A comparative resin composition (1) was obtained.

Comparative Preparation Example 2 In the same manner as in Preparation Example 1, 2531 parts of a bisphenol A type epoxy compound, 988 parts of dimer acid, 1178 parts of methacrylic acid, 10 parts of triethylamine, and
0.5 part of hydroquinone was charged. Subsequently, the mixture was stirred in an air stream and reacted at 115 ° C. for 6 hours. This gave a comparative vinyl ester with an acid value of 4.9 mg KOH / g as reaction product. The ratio of the number of carbon atoms constituting the non-aromatic hydrocarbon chain of the vinyl ester was about 21%. By mixing 3647 parts of hydroxyethyl methacrylate with this comparative vinyl ester, a comparative resin composition (2) was obtained.

Comparative Preparation Example 3 In the same manner as in Preparation Example 1, a reaction vessel was charged with 1850 parts of a bisphenol A type epoxy compound, 860 parts of methacrylic acid, 10 parts of triethylamine, and 0.5 part of hydroquinone. Subsequently, the mixture was stirred in an air stream and reacted at 115 ° C. for 6 hours. This gave a comparative vinyl ester with an acid value of 4.0 mg KOH / g as reaction product. The comparative vinyl ester was mixed with 2710 parts of hydroxyethyl methacrylate to obtain a comparative resin composition (3).

Comparative Preparation Example 4 A styrene monomer 271 as a polymerizable unsaturated monomer was added to a comparative vinyl ester obtained in the same manner as in Comparative Preparation Example 3.
By mixing 0 parts, a comparative resin composition (4) was obtained.

Example 1 Resin composition for composite wood obtained in Preparation Examples 1 to 5 (1)
To (5) 1 part of Percure O (trade name, manufactured by NOF Corporation) was added as a polymerization initiator to 100 parts of each. Next, after drying a 0.2 mm thick oak veneer veneer at 80 ° C. for 3 hours, it is placed in a decompression vessel and subjected to 30 Torr under a reduced pressure of 15 Torr.
Degassed for a minute. Further, each of the oak veneers was impregnated with each of the composite wood resin compositions (1) to (5) to which a polymerization initiator had been added, and the pressure was returned to normal pressure and allowed to stand for 6 hours. afterwards,
After draining the oak veneer veneer impregnated with the resin composition, the veneer veneer is drained, and then placed on a 15 mm-thick plywood to which a urethane-based adhesive has been applied in advance, and a PET film is further placed on the plywood. 5C at 10 Kgf / cm ²
The composite woods (1) to (5) were obtained by curing for minutes. The obtained composite woods (1) to (5) were each cut into a test piece of 15 cm × 15 cm. The obtained test pieces were evaluated by the following method. The results are shown in Table 1.

[0057]Evaluation method  (1) Heat resistance test The obtained test piece was left in a thermostat at 80 ° C. ± 3 ° C.
Take out every 4 hours and check for cracks on the surface of the test piece
The condition was visually evaluated according to the following criteria. A: No crack is observed. ：: Observation of minute cracks that are difficult to confirm visually
Is done. Δ: Generation of small cracks is observed. X: Generation of a large crack is observed.

(2) Water Resistance Test The obtained test piece was immersed in water at a water temperature of 25 ° C. ± 3 ° C. for 24 hours, and then dried in a thermostat at 60 ° C. ± 3 ° C. for 20 hours.
This was one cycle. At each cycle, the occurrence of cracks on the surface of the test piece was visually evaluated based on the same criteria as in the heat resistance test.

(3) Surface Hardness Test According to the pencil scratch test specified in 8.4.1 of JIS K 5400 (1995), a test piece obtained using a pencil lead with a load of 1 kg was applied. When the surface was scratched five times, the density symbol of the hardest pencil among the pencils in which scratches on the surface were recognized less than two times was defined as the surface hardness.

Comparative Example 1 In place of the composite resin compositions (1) to (5), the comparative composite resin compositions (1) to (4) obtained in Comparative Preparation Examples 1 to 4 were used. The same operation as in Example 1 was carried out except that each was used, to obtain composite woods (1) to (4) for comparison. The obtained composite woods (1) to (4) for comparison were cut into test pieces of 15 cm × 15 cm, respectively. The test piece obtained was evaluated by the method shown in Example 1.
The results are shown in Table 1.

[0061]

[Table 1]

Example 2 The resin compositions (1), (3) and (4) for composite wood obtained in Preparation Examples 1, 3 and 5 were each 0.2 m thick.
m was applied onto a composite plywood obtained by adhering a 5 m thick veneer veneer to a 15-mm-thick plywood, and the mixture was allowed to stand at 1 g / scale ² for 1 hour. Then, using an area beam type electron beam irradiation device,
Composite woods (6) to (8) were obtained by curing the resin composition by irradiating one-pass electron beam under a nitrogen atmosphere at an acceleration voltage of 350 kV, an irradiation dose of 200 kGy, and a conveyor speed of 5 m / min. Each of the obtained composite woods (6) to (8) is 15 cm × 15 cm.
Was cut into test pieces. The test piece obtained was evaluated by the method shown in Example 1. The results are shown in Table 2.

Comparative Example 2 In place of the composite resin compositions (1), (3) and (4), the comparative composite resin compositions (2) to (2) obtained in Comparative Preparation Examples 2 to 4 were prepared. The same operation as in Example 2 was carried out except that each of (4) was used, and the comparative composite woods (5) to (5)
(7) was obtained respectively. The obtained composite woods (5) to (7) for comparison were each cut into a test piece of 15 cm × 15 cm. The test piece obtained was evaluated by the method shown in Example 1. The results are shown in Table 2.

[0064]

[Table 2]

As can be seen from Table 1, the composite wood resin compositions (1) to (5) were each impregnated into a veneer veneer by a vacuum injection method and cured by pressing and heating. Woods (1) to (5) were excellent in heat resistance and water resistance, suppressed generation of cracks, and were excellent in durability. Furthermore, it was hard to be damaged and had excellent surface hardness. Also,
As is clear from Table 2, the composite wood resin compositions (1), (3) and (4) were used to impregnate the oak veneer by a coating impregnation method, and then cured by irradiating with active energy rays. The same results were obtained for the composite woods (6) to (8).

On the other hand, using the comparative composite wood resin compositions (1) to (4), the oak veneer veneer was impregnated by a reduced pressure injection method, and was hardened by pressurizing and heating. (1) to (4) were inferior in heat resistance and water resistance, could not suppress generation of cracks, and were inferior in durability. In addition, the comparative composite wood (5) obtained by impregnating a oak veneer with a coating impregnation method using the comparative composite resin compositions (2) to (4) and irradiating with active energy rays to cure the composite wood was used. )-(7)
Was easily damaged and had poor surface hardness.

[0067]

As described above, the resin composition for composite wood of the present invention has the above-mentioned structure, and therefore has high permeability to wood, and the composite wood impregnated with it and cured has flexibility. It is excellent in basic performance such as mechanical strength, heat resistance, water resistance and the like, and is excellent in durability by sufficiently suppressing generation of cracks due to the influence of heat, water and the like, and excellent in surface hardness.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 2B230 AA07 AA08 AA13 AA16 AA30 BA01 BA03 CB01 CB06 CB08 CB25 CC02 DA02 EA20 EB01 EB04 EB05 EB12 EB13 EB28 EB29 EC02 4J027 AB33 AE02 AE03 AE07 BA05 BA08

Claims (2)

[Claims] 1. A composite wood resin composition comprising a vinyl ester having a (meth) acryloyl group and a non-aromatic hydrocarbon chain having 12 or more carbon atoms, and a polymerizable unsaturated monomer. The vinyl ester has at least two (meth) acryloyl groups per molecule on average, and a non-aromatic hydrocarbon chain having 12 or more carbon atoms has a carbon content of the hydrocarbon chain of not less than the total amount of the vinyl ester. A resin composition for composite wood, wherein the carbon content is 35% or more of the carbon content. 2. The resin composition for a composite wood according to claim 1, wherein the polymerizable unsaturated monomer has a hydroxyl group.