JP2002113706A - Lumber cell reinforced composite material, prepreg therefor, and method for manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lumber cell reinforced composite material comprising a new composite structure, while a prepreg suitable for manufacture thereof and the manufacturing method are provided, which is equipped with mechanically physical properties equivalent to or exceeding those of high rigid natural lumber such as rosewood, ebony and the like, can be substituted for the ebony and the like and is equipped with mechanically physical properties for becoming parts of a machine, an apparatus and a structure. SOLUTION: A lumber cell reinforced composite material is a formed body of an elaborate structure wherein a thermosetting resin constitutes a continuous phase from a sheet-like lumber group in which a content in the lumber cell is a touch or none and the thermosetting resin. The prepreg is provided wherein its sheet-like lumber is impregnated with a thermosetting resin. The manufacturing method is a method wherein the prepreg is integrated by pressurizing and heating by a quantitative ratio of 50-400 pts.wt. (thermosetting resin)/100 pts.wt. (sheet-like lumber).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a wood cell reinforced composite material comprising a novel composite structure of a wood cell wall and a thermosetting resin. The present invention specifically relates to a wood-cell-reinforced composite material having mechanical properties that can be replaced with high-rigidity natural wood (for example, rosewood and ebony, etc.) and can also be a metal member. Another invention relates to prepregs which provide the wood cell reinforced composites of the invention. Further, the present invention relates to a method for facilitating industrial production of the wood cell-reinforced composite material of the present invention.

[0002]

2. Description of the Related Art Thermosetting resin-based composite materials (composite materials of a reinforcing material and a thermosetting resin matrix (base material)) are dispersion-type, fiber reinforcing materials in which a particle reinforcing material is dispersed in a matrix. And a lamination type in which a thermosetting resin is impregnated into a cloth (cotton cloth, asbestos, glass cloth, carbon cloth, etc.) and laminated.
Any type (such as a laminated type) is known by industrial practice.

A thermosetting resin-based composite material is a fiber-reinforced fiberglass-reinforced material (FRP).
The analysis of plastics (fiber reinforced plastic) is progressing, and a certain correlation has been found between the volume fraction of glass fiber and thermosetting resin and the physical strength (tensile strength, elasticity, etc.) of FRP. At a rate of 50%, it is known that 90% or more of the tensile strength and the like of FRP depends on glass fibers.

As reinforcing materials for thermosetting resin-based composite materials, glass fibers (short fibers and long fibers), carbon fibers, vinylon fibers, nylon fibers, tetron fibers, polyester fibers, rayon fibers, wholly aromatic polyamides Fibers, metal fibers, boron fibers, aluminum fibers, alumina whiskers, silicone whiskers, potassium titanate whiskers, graphite whiskers, metal whiskers, mica, asbestos, pulp and their cloths (woven, non-woven, etc.), etc. Is known. Known cloths include glass cloth, carbon fiber cloth, organic fiber cloth, fine ceramic fiber cloth, and cotton cloth. Reinforcing materials often have poor wetting, and it is generally difficult to disperse or fill the thermosetting resin in an amount required to make the composite material have high strength physical properties. For this reason, most proposals regarding thermosetting resin-based composite materials are directed to a high-strength reinforcing material, improvement in wettability of the reinforcing material, improvement in moldability of the reinforcing material, etc. -271689, Tokiohei 9-50
4319, JP-A-9-118821, JP-A-9-19-1
18829, JP-A-9-40727, etc.).

As the resin used for the thermosetting resin-based composite material, unsaturated polyester resin, epoxy resin, silicone resin, maleimide resin, vinyl ester resin, phenol resin, melamine resin and the like can be used. It has been known.

[0006] Proposals intended to use thermosetting resin-based composite materials for applications similar to wood include synthetic wood, which includes ceramic particles, silica powder, glass powder, glass micro balloon, wood powder and Synthetic wood formed by combining wood cuttings and the like into a resole type phenol resin and press-forming (Japanese Patent Application Laid-Open Nos. Hei 10-231581 and Hei 10-
166321, JP-A-9-137384) and synthetic wood (see JP-A-6-271689) in which an organic titanium compound, an organic zirconium compound, an organic zirconium aluminum compound and carbon fiber are filled in a thermosetting resin. Proposed. All of the synthetic woods according to the conventional proposals merely use a known thermosetting resin-based composite material for the synthetic wood.

[0007]

Conventional proposals regarding the dispersion type and the filling type mainly focus on improving the wettability of the reinforcing material and the combination of the reinforcing material and the thermosetting resin. No proposal has been made on the problem (for example, analysis of a composite structure), and the strength of the composite material is treated as depending on the additivity with the reinforcing material.

[0008] Further, with respect to the laminated type, even if the laminating conditions and the laminating method are devised, there is a problem that the integration in the composite is insufficient and the interlayer densification and interlayer delamination occur frequently, and the mechanical properties are poor. There was a problem that it was enough. In the past, there was no idea that the physical properties of a thermosetting resin-based composite material would be at a level that did not depend on the reinforcing material. There was no idea to make the structure high. Therefore, the possibility of using a thermosetting resin-based composite material and having physical properties that do not exist in the reinforcing material, and properties that have not been realized conventionally, depends on the structure of the composite material and the properties of the reinforcing material. In this connection, the present inventors have examined in detail the experimental subject and found some new scientific facts, on which the present invention was invented.

[0009] The first object of the present invention is to provide a wood cell reinforced composite material having high mechanical strength and low water absorption. The first invention provides excellent gloss (for example,
It is another object of the present invention to provide a wood cell reinforced composite material capable of obtaining gloss equivalent to the surface of rosewood and ebony. A first aspect of the present invention provides a wood cell reinforced composite material having properties equivalent to or higher than high rigidity valuable materials (for example, rosewood, ebony, etc.), and which can be easily replaced with high rigidity valuable materials. It also aims at. A first object of the present invention is to provide a wood cell reinforced composite material having mechanical strength equivalent to that of a metal member. A first object of the present invention is to provide a wood cell-reinforced composite material that can easily give a wood grain pattern clearly.

A second object of the present invention is to provide a prepreg which enables efficient industrial production of the wood cell-reinforced composite material according to the first invention.

A third object of the present invention is to provide a method for producing the wood cell-reinforced composite material according to the first invention, which enables efficient industrial production.

[0012]

Means for Solving the Problems The first invention (claim 1)
The wood-cell-reinforced composite material according to the present invention described in (1) above is
It is a composite material of wood-like wood and thermosetting resin, characterized by having the features defined in the following (1) to (4). (1) The composite material is formed by integrating sheet-like wood, which contains a small amount or no content of components in the wood cells, with the thermosetting resin in an arrangement in which the surfaces facing each other are arranged in parallel. (2) In the molded article of the composite material, the thermosetting resin fills the gap between the parallel sheet-like woods and penetrates into the sheet-like woods. With the feature of being integrated, (3) the molded body of the composite material is:
It is characterized in that the sheet-like wood and the thermosetting resin have a quantitative ratio of 50 to 400 parts by weight (thermosetting resin) / 100 parts by weight (sheet-like wood). (4) In the case of a molded article of a composite material, when a sample having a thickness of 1 mm or less × area of 5 × 5 cm ² is sampled from an arbitrary place, the sample has only one micro void with a probability of one or less. The structure has a feature that the fine voids, if present, have a compactness under the condition that the maximum length does not exceed 30 microns and the maximum depth does not exceed 30 microns. ing.

Second invention (the invention according to claim 2)
Is characterized in that a thermosetting resin is impregnated in a sheet-like wood having a small or no content of components contained in the wood cells.

The third invention (the invention according to claim 3)
The method of manufacturing wood cell reinforced composites by
Prepreg preparation process and subsequent prepreg as defined below
The manufacturing method consists of an integrated process,
Gives the mold effective movement to make it a dense structure as defined in
And perform it.Prepreg preparation process  In the prepreg preparation process, the content of components in wood cells is small.
Or hardenable heat-hardened sheet-like wood
Impregnated with a curable resin.Prepreg integration process  In the prepreg integration process, place the prepreg in the mold
The sheet-like wood and the thermosetting resin are 50 to 400 weights.
Amount (thermosetting resin) / 100 parts by weight (sheet-like wood)
Laminate under the condition that the quantitative ratio of
It consists of becoming.Dense structure  The dense structure is a composite material obtained by integration.
1mm or less thickness × 5 × 5cm from any location^Two Body
When the product is sampled, there is a probability that there is less than one minute void
Therefore, even if there are fine voids, the maximum length is 30 mm.
The maximum depth exceeds 30 micron with a size not exceeding the cron
A dense structure that allows only small voids
is there.

[0015]

DETAILED DESCRIPTION OF THE INVENTION [ First Invention ] The first invention will be specifically described with reference to FIGS. Figures 1-5 are preferred embodiments of the first invention, but are a part of illustrations of many embodiments encompassed by the invention. In the respective drawings, the same reference numerals denote the same or equivalent components.

FIG. 1 is an explanatory view schematically showing one specific example of a molded article of a composite material according to the present invention. The cube 1 shown in FIG. 1 is a sheet-like wood 2, 2,... In parallel, the gaps between the sheet-like woods 2, 2,... 2 are filled with the thermosetting resin 3, and the insides of the sheet-like woods 2, 2,.
And the two materials are integrated to form a dense compact. In FIG. 1, the gaps between the sheet-like woods 2, 2,... 2 are uniformly expressed to facilitate visual recognition (the same applies to FIGS. 2 and 3).

In the present invention, the thermosetting resin is inserted into the gaps between the sheet-like woods and into the sheet-like woods to integrate them, thereby forming a group of closely parallel sheet-like woods. The first requirement to enjoy the effects of the present invention for a molded article of a composite material is to form a molded article arranged in the continuous phase of the thermosetting resin (for the sheet-like wood and the thermosetting resin). Details will be described later).

In the present invention, the thermosetting resin and the sheet wood are used in an amount of 50 to 400 parts by weight (preferably 100 to 400 parts by weight).
By setting the quantitative ratio of (-300 parts by weight) (thermosetting resin) / 100 parts by weight (sheet-like wood), the molded article of the composite material has excellent mechanical properties (particularly high mechanical strength). This is the second requirement for a dense structure having chemical properties (particularly, water absorption). 400 thermosetting resin
In the region exceeding the weight part, the mechanical strength of the composite material is close to that of the thermosetting resin, and in the region where the thermosetting resin is less than 50 parts by weight, the thermosetting resin and the sheet wood are integrated. The tendency to become insufficient becomes remarkable. In addition, in a region where the thermosetting resin exceeds 300 parts by weight and in a region where the amount of the thermosetting resin is less than 100 parts by weight, such phenomena are likely to occur, and it is difficult to enjoy the effects of the present invention.

In the present invention, when a sample having a thickness of 1 mm or less, an area of 5 × 5 cm ² is collected from an arbitrary place of a molded article made of a composite material, there is only one micro void at a probability of one or less. The complex structure is such that the microvoids, if present, have a dense structure whose maximum length does not exceed 30 microns and whose maximum depth does not exceed 30 microns. This is the third requirement for enjoying the effects of the invention with respect to the molded body of the material.

A sample can be technically collected when its volume is large, and it is substantially difficult to enjoy the effects of the present invention for a molded article of a composite material if microvoids exist with a higher probability. Become. The phrase “the microvoids exist with a probability of not more than one” in the present invention means that even if the microvoids exist in the sample, there is one.
The maximum size of the fine voids allowed in the molded article of the composite material is a size that can be recognized by the naked eye when an optical microscope sample having a magnification of 2 × 5 is observed.
According to the observation results of many prototypes, the largest thing confirmed as a fine void is about 5 microns long and about 5 microns deep.

When the molded article of the composite material of the present invention is observed with an optical microscope at a magnification of 2 × 5 times, it has been found in the present invention that substantially no fine voids are present (see Examples described later). ). When the conditions are satisfied for the microvoids in which the molded body of the composite material is present (that is, when the composite body has denseness), the molded body of the composite material has excellent mechanical properties (hardness, flexural strength, flexural modulus, Impact strength, etc.) and physical properties (water absorption), and have vivid gloss, so that the effects of the present invention can be maximized.
In addition, a laminated composite material made of a general thermosetting resin and cloth has a large number of fine voids that can be sufficiently distinguished with the naked eye when observed with an optical microscope at a magnification of 2 × 5 times, and There are also many microvoids having a maximum length exceeding 30 microns.

The composite material of the present invention has remarkably superior mechanical and chemical properties as compared with a laminated thermosetting resin-based composite material using a natural material such as cotton cloth, and has high mechanical properties such as rosewood and ebony. It has physical properties equivalent to rigid precious materials. Table 1
9 shows mechanical properties of a laminated resin composite material using a cotton cloth (see Comparative Example 1 described later).

[0023]

[Table 1]

Table 2 shows the mechanical properties of ebony, one of the high rigidity valuable materials. Ebony is a timber belonging to the southern timber oyster family (Ebenaceae) and has higher mechanical strength than ordinary timber, and is approximately 0.85 to 1.08.
It is a Nanyo lumber that has a characteristic of air-dry specific gravity, glossy black (which is said to be derived from the color of the heartwood), etc. (Shoji Sudo: "Shinsei Supplement, Nanyang Lumber") Earth Co., Ltd. (Published in 1998, p. 152-155).

It is known that there are several dozen ebony tree species. Depending on the species, the color of the sapwood becomes white, blue-gray, pink or light red, and the heartwood varies from pure black to various black. Up to those having stripes. In Japan, ebony is classified into real ebony, striped ebony, blue ebony, and garbage ebony, and this ebony is the highest grade in terms of color and gloss. The mechanical property values shown in Table 2 are excellent in the mechanical property values of ebony and belong to the region (Shoji Sudo: “Newly revised and supplemented, Nanyo Zaiku”, Earth Co., Ltd., 1998)
Year, p155).

[0026]

[Table 2]

On the other hand, Table 3 shows the mechanical properties of one example of a molded article of the composite material according to the present invention (see Examples described later).

[0028]

[Table 3]

The molded product of the present invention shown in Table 3 is superior to the laminated resin composite material and ebony in all of hardness, bending strength, flexural modulus, impact strength and water absorption. The bending strength and the water absorption are remarkably improved. The water absorption shows a numerical value of 1.0% or more also in the dispersion-type and filling-type resin-based composite materials. Therefore,
The molded article of the composite material according to the present invention shows a water absorption rate in a region where the conventional resin-based composite material and the woody material did not have.

The molded article of the composite material according to the present invention not only can be replaced with a high-rigidity valuable material due to the characteristics derived from physical properties, but also has the same appearance as the high-rigidity valuable material and has physical properties higher than the high-rigidity valuable material. It becomes possible to be a body. Also,
The molded article of the composite material according to the present invention can also be used for applications requiring higher mechanical properties (ie, applications equivalent to metal members) due to the characteristics derived from the properties.

FIG. 2 is an explanatory view schematically showing an arc-shaped cross section of a molded article of a composite material according to the present invention. 2 are integrated with thermosetting resins 22, 22... 22 in parallel with sheet-like wood 21, 21.

FIG. 3 is an explanatory view schematically showing a cross section of a cylinder of the composite material according to the present invention. The circular cross section 30 shown in FIG. 3 also has the sheet-like woods 31, 31,.
2 ... 32 are integrated. The composite material of the present invention can be formed into an arbitrary shape by forming a molded body according to the molding conditions, and can also be processed into an arbitrary shape by subsequent cutting or the like.

< Sheet-like wood > The sheet-like wood is a sheet-like material collected from wood. Although "sheet" is a polysemous word, it is generally a plastic meaning whose thickness is extremely small compared to its length and width ("JIS industrial terminology encyclopedia": Japanese standard). Association, 1987) and a piece of paper or sheet (Daijibayashi:
Sanseido Bookstore). The term "sheet-like wood" of the present invention is used in the meaning of wood whose thickness is extremely small as compared with its length and width.

In the present invention, a sheet-like wood containing a small amount or no wood cell-containing components is used.
This is because the location where the wood cell-containing component is present is made a void and filled with a thermosetting resin to form a composite material molded article to form a dense structure having a continuous phase of the thermosetting resin. In the sheet-like wood containing a small amount or no component contained in the wood cells, the sheet-like wood may be in a state where the components contained therein are originally removed by volatilization or the like. It is suitable to extract and remove with an extraction solvent such as water, water and an organic solvent (ether, alcohol, benzene, etc.).

Wood can be roughly divided into constituent components. The constituent components (major component) of the wood cell wall are composed of complex macromolecules (mainly composed of lignin and carbohydrate), and the components contained in the cells contained in the wood cells (extraction). Component))
The content of the intracellular component varies depending on the type of wood, but is about 5 to 30% by weight. In the present invention,
Using a sheet-like wood having a small amount or no intracellular component (extracting component), the thermosetting resin is allowed to penetrate into the voids derived from the intracellular component in the sheet-like wood. The compact of the composite material is a dense structure.

Accordingly, the “small amount” of the “small amount of components contained in the cell” of the present invention means that the amount of the thermosetting resin penetrating into wood which is effective for making the compact into a dense structure. This is the amount that can be secured. The “small amount of the intracellular component” in the present invention means, for example, that the main content of the intracellular component of the sheet-like wood is 50% by weight or less. In addition, the phrase “the wood cell-containing component is not contained” in the present invention means that a region corresponding to the main content of the cell-containing component in the sheet-like wood is void. . When using sheet-like wood containing a small amount or no intracellular components, natural wood under such conditions may be converted into a sheet. It is suitable to extract and remove the contained components. In addition, vibration can be applied during the extraction and removal processing to increase the extraction and removal effect. Vibration, extraction removal effect can be obtained is used the number of vibrations, for example vibration frequency of the 0.01～2KH _Z is applied.

The sheet-like wood is obtained by cutting and collecting the longitudinal section, the transverse section or the peripheral surface of the wood in the form of a sheet. According to the dispensing method (the same method as for cooking wigs), endless thin sheet-like wood can be obtained. Sheet-like wood collected from wood exhibits various changes derived from natural products (for example, perforations at nodes, breaks, etc.). It has been found that in the composite materials of the present invention, they do not cause a decrease in mechanical properties.

One sheet of wood may be cut from a piece of wood into a single sheet, a plurality of sheets may be laminated into one piece, or one piece of wood cell wall piece may be used. It may be formed in a sheet shape. The thickness of one sheet of wood is such that the thickness of the wood can be maintained in the shape of a sheet and has a minimum thickness, is capable of being integrated with the thermosetting resin, and is dense. The thickness that can be made into a structure is the largest. When a single sheet of wood has a minimum thickness exceeding the limit and is too thin, or a maximum thickness exceeding the limit and is too thick, effective mechanical properties of the composite material cannot be obtained. The thickness of one sheet of wood is, for example, about 0.05 to 2.5 mm (preferably about 0.1 to 1.0 mm).

< Thermosetting Resin > The type and curing mechanism of the thermosetting resin are not particularly limited as long as a three-dimensional cured product capable of enjoying the effects of the present invention is formed. The thermosetting resin is generally cured by a curing agent, but may be cured by physical energy such as light and heat or radicals of a radical polymer.

The thermosetting resin is, for example, a phenol resin, a modified phenol resin, an unsaturated polyester resin, an epoxy resin, a polyimide resin, a maleimide resin, a vinyl ester resin, a phenol co-condensation resin, a melamine resin or Use of a silicone resin is effective. From the viewpoint of physical properties, if a phenol resin, an epoxy resin, an unsaturated polyester resin, a polyimide resin, or the like is used, the composite material can easily enjoy the effects of the present invention.

As the phenol resin, a resin of a resole type (typically, a resin obtained by condensing phenols and aldehydes with an alkali) is suitable. Phenol as a condensation raw material includes, for example, phenol orthophenol, metaphenol, paraphenol, isopropylphenol, para-tert-butylphenol, paraisopropenylphenol, nonylphenol, and bisphenol. A or the like is used. As the aldehydes, formaldehyde is generally used, but acetaldehyde and furfuraldehyde can also be used. There are no particular restrictions on the catalyst for resolving, but for example, ammonia, various amines and metal hydroxides are used. Examples of the phenol co-condensation resin include a co-condensation resin of melamine and phenol.

The epoxy resin has various bonding modes (reactivity), for example, glycidyl ether type, glycidyl ester type, glycidylamine type and allied type, etc. Is possible.
Raw materials include, for example, bisphenol A, hydrogenated bisphenol
A, bisphenol F, tetrabromobisphenol A, tetraphenyl ethane, propylene glycol
, Hexahydrophthalic anhydride, dimer acid, diaminodiphenylmethane, isocyanuric acid, hidaiton, p-
Aminophenol, p-oxybenzoic acid and the like can be generally used, and the same applies to the present invention. As the curing agent, any compound having a functional group capable of reacting with the epoxy resin can be used. For example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, isophorodiamine , Bis (4-amino-3
Aliphatic amines such as -methylcyclohexyl) methane and menthanediamine, m-phenylenediamine, 4,4,-
Aromatic amines such as diaminodiphenylmethane, 4,4, -diaminodiphenylsulfone, m-xylenediamine, amidoamine, polyamide, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, Acid anhydrides such as benzophenone tetracarboxylic anhydride, chlorendic anhydride, dodecynyl succinic anhydride, methyl tetrahydro phthalic anhydride and methyl endmethylene tetrahydro phthalic anhydride, and those having a recognized catalytic effect such as Lewis acids and Lewis bases can also be used. It is.

The maleimide resin is generally a resin composition in which a compound having two or more polyfunctional maleimide groups in a molecule accounts for 30% by weight. Compounds having a polyfunctional maleimide group include, for example, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 1,1
2-bismaleimide decane, 1,6-bismaleimide-
(2,2,4-trimethyl) hexane, 1,3-bismaleimidebenzene, 1,4-bismaleimidebenzene, and the like. The maleimide resin may contain a monofunctional maleimide group and other functional groups as needed.

The unsaturated polyester resin is typically a thermosetting resin obtained by copolymerization and crosslinking of a polycondensation reaction product of an unsaturated dicarboxylic acid and glulicol with a monomer having a reactive unsaturated group. Yes, but other types are available.

The second requirement of the present invention is 50 to 400 parts by weight (thermosetting resin) / 100 parts by weight (sheet-like wood).
The weight part of the thermosetting resin in the case of is based on the weight part of the cured thermosetting resin. Therefore, the weight part of the thermosetting resin is the total weight part of the resin constituting the cured thermosetting resin and the compound involved in the curing, and the curing is performed by a radical reaction with the monomer. In such a case, it is a part by weight including a monomer.

In the present invention, in order to more efficiently satisfy the third requirement of the molded article of the composite material and to improve weak points (for example, brittleness) of the thermosetting resin, the inorganic component may be used. Can be blended.

The inorganic component includes, for example, glass fiber, carbon fiber, metal fiber, boron fiber, aluminum fiber, alumina whisker, silicon kerbite whisker, potassium titanate whisker, graphite whisker, metal whisker,
Mica, asbestos, ceramic particles, silica powder, glass powder, glass micro balloon, alumina, boron oxide, zinc oxide, graphite, silicic acid, polyphosphoric acid, kaolin powder, crow powder, ground mineral, dolomite, gypsum, One or more kinds of talc, asbestos, rock wool, metal powder and the like are blended. The compounding amount of the inorganic component is within a range where the densification of the composite material molded article and the improvement of the physical properties of the thermosetting resin are effective, and varies depending on the type of the thermosetting resin. %, Preferably 0.1 to 10% by weight (based on the weight of the thermosetting resin)
It is. When blending the inorganic component, a coupling agent or the like is used if necessary.

< Composite Material > From the mechanical and chemical properties (see Table 3) of the molded article of the composite material according to the present invention, the field of wood (especially the field of valuable materials such as rosewood and ebony) And in the field of metal products. Further, there is no limitation on the form, and it is possible to form an arbitrary shape by appropriately selecting a manufacturing apparatus.

The molded article of the composite material according to the present invention can be used, for example, for daily necessities (for example, interior decorations), housing equipment (for example, furniture and other equipment), hobby goods (for example, musical instruments), office equipment, and the like. Supplies (for example, product display tools),
Transportation machinery (e.g., ship and vehicle equipment, etc.), general machinery (e.g., office machinery, etc.), industrial machinery (e.g., tools, accessories for industrial equipment, etc.), and civil engineering and construction supplies (e.g.,
Building materials, building structures, building components, fittings, interior and exterior materials for buildings, etc.).

[ Second Invention ] The wood cell-reinforced composite material of the present invention is optional in the production method as long as a composite material satisfying the requirements can be obtained. However, when the prepreg according to the second aspect of the present invention is used for the production according to the third aspect of the present invention, the wood cell-reinforced composite material of the present invention can be obtained industrially easily and efficiently. become.
The prepreg according to the second aspect of the present invention is obtained by impregnating a sheet-like wood having a small amount or no containing components in wood cells with a thermosetting resin. The sheet-like wood containing a small amount or no component in the wood cells is the same as described for the sheet-like wood of the first present invention. Further, various kinds of fillers may be impregnated with the thermosetting resin. The kind and amount of the filler are the same as those described in the first invention. The prepreg is in a state in which the prepreg can be cured by pressurizing and heating in the mold, and there is no restriction on the state of the prepreg. (A state in which the fluid flows partially by heating and pressurizing).

[ Third Invention ] The manufacturing method according to the third invention is performed in a prepreg preparation step and a subsequent prepreg integration step, and the integration step forms a compact into a dense structure. This is done by giving the mold an effective movement. The prepreg preparation step is performed by the method of the second prepreg preparation step according to the present invention. In the prepreg integration step, the sheet-like wood and the thermosetting resin are mixed with the prepreg in a mold at 50 to 50%. 400 parts by weight (thermosetting resin) /
The lamination is performed under the condition of a quantitative ratio of 100 parts by weight (sheet-like wood), and the heating and pressurization are performed to cure and integrate. The integration is performed, for example, at 50 to 200 kg / cm ² under pressure, at 120 to 250 ° C. under heating, and at a molding time of 30 to 240 minutes. _ In the process of performing the curing integration, the molding is performed by giving the mold an effective motion to satisfy the third requirement of the present invention. The motion imparted to the mold may be any type of motion as long as it is effective for forming the compact into a dense structure, and for example, motion such as vibration is also effective.

In the present invention, modifications or partial changes and additions of the present invention are optional as long as the objects of the present invention are met and the effects of the present invention are not particularly impaired. All are within the scope of the present invention. The present invention will be specifically described based on examples, but the examples are illustrative and do not restrict the present invention.

[0053]

[Example] <Example 1>Preparation of prepreg  Cedar wood is 0.25mm thick, 150mm wide and 1000 long
mm into thin sheet-like cedar wood, with a temperature of 95
Hot water treatment in hot water at ~ 100 ° C for 24 hours
And then 1: 1 methyl alcohol / acetone.
Organic solvent (50 ° C.) for 2 hours
Processing to remove wood cell components contained in the sheet-like wood.
Was. Note that the hot water treatment and the organic solvent treatment
A stainless steel container containing each solvent is inserted through an insulating plate
Attach ultrasonic vibrator and apply 1KHz vibration
Was. Sheet cedar is treated with hot water and organic solvent.
Wood cell of 14.5g / 100g (sheet-like cedar wood)
The components were removed. Next, the components contained in wood cells are removed.
The epoxy resin (trade name: Epico-
828) and a curing agent (triethylenetetramine 10 weight
%) In a solvent and impregnated with the solution at 60 ° C.
The prepreg was volatilized into a B-stage prepreg. Prep
The leg is a ratio of 80 g of resin / 100 g of sheet cedar.
Was.

<Embodiment 2>Preparation of prepreg  Rawan material is 0.25mm thick, 150mm wide, 10long
Sliced into 00mm to make thin sheet wood,
48 hours in hot water of 95-100 ° C, then methyl
Organic solvent consisting of 1: 1 alcohol / acetone (50 ° C)
In wood cells in sheet-like lauan wood after treatment for 3 hours
The contained components were removed. In addition, hot water treatment and organic solvent treatment
Was performed in the same manner as in Example 1. Sheet-like raw
13.5 g by hot water treatment and organic solvent treatment
/ 100g (sheet-like rawan) of wood cell content
Has been removed. Next, the wood from which the components contained in the wood cells were removed
-Caustic sodium with a molar ratio of 2.0 (P / F)
-Impregnated with a catalyst-resol type liquid phenol resin
The prepreg was dried at 0 ° C. to give a B-stage prepreg.
The prepreg has a resin content of 100 g / sheet-like cedar material of 100 g.
Ratio.

<Embodiment 3>Prepreg integration  Cut the prepreg prepared in Example 1 to a length of 150 mm
Cut 25 pieces and stack them in a mold under a pressure of 100k.
g / cm^Two At a molding temperature of 130 ° C. for 60 minutes.
Vibration motor (output: 25W, rotation)
(Number of rotations: 1600 rpm)
The mold was vibrated until the end of the shape. The obtained molded product is 150
mm × 150mm (flat) × 10mm (thickness), bright color
It has a beautiful grain pattern and looks like natural rosewood
there were. Molded product has hardness (JISK7202) 120H
_R , Bending strength (measured according to JIS K7203) 150M
Pa, flexural modulus (measured according to JIS K7203) 20
GPa, impact strength (JISK7110) 12Kgfcm
/ Cm and water absorption (measured according to JIS K7209)
It was 01% by weight. By optical microscope with 2x5x magnification
Observation revealed that there were no fine voids.

<Embodiment 4>Prepreg integration  Cut the prepreg prepared in Example 2 to a length of 150 mm.
, 80 sheets are piled on each other and the pressure is 100k
g / cm2 at a molding temperature of 160 ° C for 120 minutes
Was. The mold is used from the start of molding to the end of molding as in Example 1.
Vibrated. The obtained molded product is 150 mm x 150 m
m (flat) x 10mm (thickness), beautiful dark wood grain
Appearance, the cross-section is dense,
Dark brown rosewood, even with close observation
Or it was the same as ebony. Molded products have hardness (JIS
K7202) 120H_R , Bending strength (JISK7203
200 MPa, flexural modulus (JISK72
03 GPa) and water absorption (JIS K72)
09) (0.02% by weight). 2x5x
Even when observed with an optical microscope at a magnification of
Did not.

<Example 5> Under the same conditions as in Example 1, prepregs were prepared in the same ratio as in Example 4 except that the resin amount was changed from 50 to 400 g with respect to 100 g of the sheet cedar. The product was molded. The mechanical properties of the molded product were maintained at values close to those of Example 4, and the water absorption was 0.01 to 0.1.
It was maintained in the range of 02% by weight.

<Comparative Example 1> No. 11 cotton canvas was placed in hot water for 24 hours.
After degreasing over time, the molar ratio was 2.0 (P /
The phenol resin impregnated with the caustic soda catalyst of the type F) was impregnated with the resin and dried at 60 ° C. to prepare a prepreg in a B-stage state in a ratio of 100 g of resin / 100 g of canvas. The prepreg was integrated under the same conditions as in Example 4. The obtained molded product is 150 mm x 150 mm
(Plane) x 10 mm (thickness), with clear lamination, hardness (JIS K7202) 95H _R , bending strength (J
ISK7203) 160 MPa, flexural modulus (JISK
7203) 10 GPa, impact strength (JISK7110)
It was 8 kgfcm / cm and the water absorption (measured according to JIS K7209) 1.0% by weight.

[0059]

According to the first composite material for reinforcing wood cells of the present invention, various effects represented by the following (a) to (c) can be obtained. (A) Excellent mechanical strength such as bending strength and bending rigidity,
Further, a wood cell reinforced composite material having low water absorption is provided. (B) A wood cell reinforced composite material having a gloss equal to or higher than the surface of rosewood and ebony is provided. (C) A wood cell reinforced composite material that can be easily provided with a clear grain pattern is provided. (D) A wood cell reinforced composite material that can be substituted for a metal member in terms of mechanical strength is provided. (E) From the standpoint of mechanical strength and appearance, a wood cell reinforced composite material which can be replaced with valuable materials such as rosewood and ebony is provided.
A second present invention aims to provide a prepreg that enables efficient industrial production of the wood cell-reinforced composite material according to the first present invention. A third aspect of the present invention aims to provide a production method that enables efficient industrial production of the wood cell-reinforced composite material according to the first aspect of the present invention. According to the prepreg according to the second aspect of the present invention, there is an effect that the wood-cell-reinforced composite material of the first aspect of the present invention is molded under industrially easy molding conditions for molding a laminated thermosetting resin-based composite material. can get. According to the third production method of the present invention,
The wood cell reinforced composite material of the first invention is obtained efficiently and easily.

[Brief description of the drawings]

FIG. 1 is an explanatory view schematically showing a specific example of the present invention.

FIG. 2 is an explanatory view schematically showing another specific example of the present invention.

FIG. 3 is an explanatory view schematically showing another specific example of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cube 2 Wood cell wall 3 Thermosetting resin 20 Arc-shaped cross section 21 Sheet wood 22 Thermosetting resin 30 Circular cross section 31 Sheet wood 32 Thermosetting resin

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[Procedure amendment]

[Submission date] October 18, 2000 (2000.10.
18)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction contents]

[0028]

[Table 3]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

In the present invention, an inorganic component is blended in order to more efficiently satisfy the third requirement of the molded article of the composite material and to improve weak points (eg, brittleness) of the thermosetting resin. It is possible to

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 B29K 101: 10 // B29K 101: 10 105: 06 105: 06 B29L 9:00 B29L 9: 00 B29C 67/14 G (72) Inventor Shigeru Kanai 6-4-3 Nomura, Kusatsu-shi, Shiga Pref. 404 F-term (reference) No. 404 Granchario Kusatsu 2B250 BA04 DA01 FA41 HA01 4F072 AA01 AA07 AB03 AB27 AD13 AD27 AD28 AD31 AD38 AE02 AF02 AG17 AH21 AK14 AL01 AL09 4F100 AK01A AK01B AK01C AK01D AK33 AK53 AP01A AP01C BA03 BA04 BA05 BA08 BA10A BA10B BA10C BA10D DH01A DH01C EH012 EJ202 EJ252 HAEJJ EJ422 EJ821 HB01 JB13B13 JB13J03 JB13J03A13 4J002 AH002 BH021 CC041 CD051 CD101 CD131 CF221 FD010 FD140 GC00 GL00 GN00

Claims (3)

[Claims] 1. A composite material of a sheet-like wood and a thermosetting resin, wherein the composite material has the characteristics defined in the following (1) to (4). (1) The composite material is formed by integrating sheet-like wood, which contains a small amount or no content of components in the wood cells, with the thermosetting resin in an arrangement in which the surfaces facing each other are arranged in parallel. (2) In the molded article of the composite material, the thermosetting resin fills the gap between the parallel sheet-like woods and penetrates into the sheet-like woods. With the feature of being integrated, (3) the molded body of the composite material is:
The structure is characterized in that the sheet-like wood and the thermosetting resin have a quantitative ratio of 50 to 400 parts by weight (thermosetting resin) / 100 parts by weight (sheet-like wood). (4) When a sample having a thickness of 1 mm or less × an area of 5 × 5 cm ² is collected from an arbitrary place in the molded article of the composite material, the sample has only one microvoid with a probability of one or less, The structure is characterized in that the microvoids, if present, have a compactness under conditions that the maximum length does not exceed 30 microns and the maximum depth does not exceed 30 microns. I have. 2. A prepreg for a wood-cell-reinforced composite material, characterized in that the thermosetting resin is impregnated in a sheet-like wood having a small or no content in wood cells. 3. A process for preparing a prepreg as defined below and
Manufacturing method consisting of the subsequent prepreg integration process as defined in
And the integration process produces a dense structure as defined below
Giving effective movement to the mold.
Manufacturing method of wood cell reinforced composite material.Prepreg preparation process  In the prepreg preparation process, the content of components in wood cells is small.
Or hardenable heat-hardened sheet-like wood
Impregnating with a reactive resin.Prepreg integration process  In the prepreg integration process, place the prepreg in the mold
The sheet-like wood and the thermosetting resin are 50 to 400 weights.
Amount (thermosetting resin) / 100 parts by weight (sheet-like wood)
Laminate under the condition that the quantitative ratio of
It consists of becoming.Dense structure  The dense structure is a composite material obtained by integration.
1mm or less thickness × 5 × 5cm from any location^Two Body
When the product is sampled, there is a probability that there is less than one minute void
Therefore, even if there are fine voids, the maximum length is 30 mm.
The maximum depth exceeds 30 micron with a size not exceeding the cron
A dense structure that allows only small voids
is there.