JP3166967B2 - Wood sheet with carbon fiber prepreg for wood reinforcement, carbon fiber composite wood sheet for wood reinforcement, and carbon fiber reinforced wood - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon fiber-containing wood sheet for reinforcing wood and a carbon fiber reinforced wood, and more particularly to a carbon fiber prepreg- attached wood sheet excellent in adhesiveness, handleability and workability. The present invention relates to a carbon fiber reinforced wood sheet and a carbon fiber reinforced wood sheet which is integrated by attaching them to the surface of a single piece of wood, or to any of a plurality of boards or laminated boards made of a single board, or between or between the single boards. is there.

[0002]

2. Description of the Related Art Heretofore, a single piece of wood, a laminated board or a small squared lumber cut in a long direction in the fiber direction, and glued together with an adhesive with the fiber directions parallel to each other are mainly used in construction. It is used as a frame material such as columns and beams, and recently for wooden bridges and large domes.

[0003] In particular, glued laminated wood has high degree of freedom in dimensions and shape because it is used for gathering sawn boards and small squared wood, and has little variation in product strength, cracking, and irregularity, and can easily manufacture bent wood. Has excellent characteristics.

[0004] However, when these laminated materials are used for large buildings and structures, the rigidity and strength of the laminated materials need to be increased, so that the thickness of the laminated materials must be increased.
As a result, the ceiling of buildings and structures is lowered or unnecessarily high, so carbon fiber with high rigidity and strength is used.
It has been proposed to use reinforced single wood or reinforced glue glued through an adhesive.

[0005] In particular, such carbon fiber reinforced wood and carbon fiber reinforced laminated wood have sufficient water resistance, corrosion resistance, fire resistance, heat resistance, and adhesiveness required for wood buildings and structures. Considering this, a method of applying an adhesive such as a phenolic resin or a resorcinol-based resin to a wood surface, arranging carbon fibers thereon, impregnating the adhesive between the fibers, and adhering to the wood (Japanese Unexamined Patent Publication No. 3-230904 ) ) Or a method of bonding a prepreg in which carbon fiber is well impregnated with an adhesive (Japanese Patent Laid-Open No. 53-108182 ). Because it is difficult to secure a work place, carbon fiber prepregs are often used from the viewpoints of workability at other places and workability.

[0006]

However, when these carbon fiber prepregs are bonded to wood, there is a problem in that the adhesiveness varies because wood is a natural product having different properties depending on the growth environment. In addition, the state of the resin used for the prepreg in order to ensure adhesiveness, that is, frequent adjustments such as selecting and optimizing the state and amount of the solid, semi-solid, liquid, etc., are necessary, and economical and quality There were many challenges.

[0007] Further, since the carbon fiber prepreg is rolled up or rolled up in a sheet shape and transported or stored,
Release paper is placed on one or both sides of the prepreg so that they do not adhere to each other.However, when bonding with wood, it is necessary to perform a complicated and time-consuming processing operation such as removing the release paper. The paper pattern turned into waste, causing environmental pollution.

The inventors of the present invention have conducted intensive studies to solve the conventional problems, and as a result, have found that these problems can be solved by using a specific carbon fiber sheet and carbon fiber reinforced wood.

That is, an object of the present invention is to provide a carbon fiber prepreg-attached wood sheet in which a carbon fiber prepreg sheet or strand impregnated with a specific resin is arranged on a wood-based sheet, and a carbon fiber obtained by integrating the carbon fiber and the wood-based sheet. An object of the present invention is to provide a fiber composite wood sheet and a carbon fiber reinforced wood obtained by integrating these with wood.

[0010] That is, an object of the present invention is to apply a carbon fiber prepreg sheet and a strand to which a carbon fiber prepreg sheet and a strand, which are excellent in adhesiveness, handleability and workability and do not cause environmental pollution, are applied to wood and laminated wood. Woody sheet,
Another object of the present invention is to provide a carbon fiber composite wood sheet obtained by curing the same, and to provide a single wood and laminated wood having high rigidity and strength using the carbon fiber prepreg-attached wood sheet and the carbon fiber composite wood sheet. To provide.

Further, the present invention provides single wood and laminated wood reinforced with useful carbon fiber which not only expands the use of wood for large buildings and structures, but also reduces the amount of natural wood used. Is to do.

[0012]

The present invention relates to a carbon fiber prepreg sheet impregnated with a mixed resin of a thermosetting resin and a curing agent or a curing catalyst.
A carbon fiber prepreg-attached wood sheet on which a wood-based sheet of 01 to 0.3 mm is arranged. And a carbon fiber strand prepreg impregnated with the resin having a thickness of 0.01 to 0.3 mm.
Can be achieved by applying a carbon fiber strand prepreg-attached wood sheet in which the strands are arranged in parallel on the surface of a wood-based sheet.
This is achieved by a carbon fiber composite wood sheet integrated by pressing.

In particular, the resin used for the carbon fiber prepreg is at least one resin selected from the group consisting of resorcinol-based resins and resol-type phenol-based resins, and formaldehyde as a curing agent or an inorganic or organic acid as a curing catalyst. It is preferable to use a liquid mixed resin containing

Further, the object of the present invention is to provide the carbon fiber prepreg-attached wood sheet, the carbon fiber strand prepreg-attached wood sheet, and the carbon fiber composite wood sheet obtained by integrating them with a single wood surface or a plurality of boards or veneers. This is achieved by attaching to any of the boards or veneers or the surface of the laminated wood, interposing an adhesive if necessary, and further applying heat and pressure if necessary to form an integrated carbon fiber reinforced wood.

[0015]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described in detail.

The resin used in the present invention is a phenol or oligomer having one phenolic hydroxyl group such as phenol, cresol, xylenol, ethylphenol, chlorophenol and bromophenol, and a phenolic hydroxyl group such as resorcinol, hydroquinone, catechol and phloroglicinol. Phenols having two or more phenols and aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, furfural, benzaldehyde, trioxane and tetraoxane are phenols / aldehydes = 2/1 to 1/3, preferably 5
A known resol-type phenol resin (phenol-formaldehyde initial addition condensation resin) and resorcinol resin obtained by methylolation in the presence of an alkali catalyst such as potassium hydroxide or sodium hydroxide in a molar ratio of / 4 to 2/5. is there.

Further, a resin having a number average molecular weight in terms of polystyrene of preferably from 120 to 2,000 and particularly preferably from 150 to 500 by high performance liquid chromatography (HPLC), and a resin having a viscosity adjusted at 25 ° C. of 3 to 150 poise. Is preferred.

The curing agent is resorcinol resins, among known ones are found used as a curing agent such as resol-type based phenolic resin, paraformaldehyde, formaldehyde, acetaldehyde, furfural, trioxane, like mixed with the resin as paste or Those that are liquid are preferred.

Para-toluenesulfonic acid as a curing catalyst,
Those which are mixed with the resin, such as benzenesulfonic acid, xylenesulfonic acid, and phenolsulfonic acid, and dissolved in a liquid are preferable.

In order to uniformly cure the prepreg, a curing agent or a curing catalyst which becomes a uniform liquid at 35 ° C. or lower, which is a normal prepreg production temperature when a mixed resin is used, is particularly preferable.

The carbon fiber used in the present invention is not particularly limited, but the nitrogen content obtained from the polyacrylonitrile fiber is 0.1 to 15% by weight, and the tensile strength is 2500.
Carbon fibers having a modulus of 150 to 700 GPa and a modulus of 150 to 700 GPa are preferred.
Carbon fibers having an elastic modulus of 350 GPa and a diameter of 5 to 9 microns are preferred from the viewpoint of adhesiveness.

In the present invention, the oxygen / carbon on the surface of the carbon fiber measured by an ESCA surface analyzer (manufactured by Shimadzu Corporation) is 0.1 / 1 to 0.3 / 1, particularly 0.15.
/ 1 to 0.25 / 1 are preferable because the bonding strength can be increased.

In actual use, the carbon fiber has a fiber diameter of 5 to 9 microns and the number of carbon fibers is 1,000 to 300.
Fiber bundles (strands) composed of 000 fibers are used by being bundled in a desired amount or widened into a sheet shape.

The woody sheet used in the present invention is Dao,
Oak, perch, beach, cypress, cedar, cherry, maple, teak and other known natural woods made by known means using a slicer and known paper using wood-based pulp, thin plates such as nonwoven fabrics, Alternatively, it is a fiber sheet, and the thickness is preferably 0.01 to 0.3 mm. Thickness 0.01
If it is less than 0.3 mm , the sheet properties in the width direction of the prepreg will be poor and handling will be difficult. On the other hand, if it is more than 0.3 mm , the flexibility will decrease and the post-processability will deteriorate, which is not preferable.

The carbon fiber prepreg-attached wood sheet according to the present invention in which a wood-based sheet is attached to one surface of the carbon fiber prepreg is obtained by mixing one or more of the resin, a curing agent or a curing catalyst, and, if necessary, an inorganic filler. A strand of carbon fiber is continuously dipped in a liquid mixed resin to impregnate the carbon fiber so that the mixed resin is 30 to 80% by weight, and if necessary, after drying the volatile matter, a drum is formed beforehand. On a wrapped wood-based sheet, the fibers are wound so as to be parallel to each other, then dried if necessary, and then cut in the width direction of the drum, or
Alternatively, it is prepared by a method in which a carbon fiber strand is placed in parallel while being pressed by a roll on a wood-based sheet on which the resin is applied on the surface, and the resin is allowed to penetrate the fiber.

FIG . 1 shows the present invention using a prepreg sheet.
Of wood sheets with carbon fiber prepreg for wood reinforcement
Shows the state, especially on both sides of the carbon fiber prepreg sheet 2.
Attaching carbon fiber prepreg to which wood-based sheets 1 and 3 are attached
It is a wooden sheet. The carbon fiber prepreg-attached wooden sheet
The carbon fiber prepreg sheet 2 has a wood-based
Wood sheet with carbon fiber prepreg attached with sheet 1 attached
In the manufacturing process or after manufacturing, separate the side without wood-based sheet 1
Is produced by sticking a wood-based sheet 3 of the above.

FIG . 2 shows a book using a strand prepreg.
Of carbon fiber prepreg affixed wood sheet for wood reinforcement of the invention
This shows a stacked state. In the present invention, the carbon fiber strand prepreg-attached wood sheet is prepared by winding the carbon fibers in parallel with each other or arranging them in such a manner that the fibers are spaced apart from each other. After impregnating to 30 to 80% by weight, the volatile matter is dried, and if necessary, a powdered inorganic substance such as talc is adhered to the surface to form a carbon fiber strand prepreg 4 , which is previously wrapped around a drum. 1 , the fibers are wound so as to be parallel to each other, or the carbon fiber strand prepregs 4 are arranged on the wood-based sheet 1 while being pressed in parallel with rolls, and if necessary, As shown in FIG.
In, having a wood-based sheets 1 and 3 on both sides by further sticking another wood-based sheet 3 on the side that is not adhered wood based sheet 1
Wood sheet with carbon fiber prepreg for wood reinforcement
I do.

It is preferable that the mixed resin is a uniform solution in order to uniformly impregnate the carbon fibers and perform uniform curing. If the prepreg is not uniform, the resulting prepreg will be unsatisfactory in curing and will have poor adhesion, which is not preferable.

When the amount of the mixed resin of the prepreg impregnated with the mixed resin is 30% by weight or less, the adhesiveness to wood is poor. When the amount of the mixed resin is 80% by weight or more, the handleability such as the resin falling from the prepreg is reduced. Is not preferable because it becomes difficult. In particular, 40 to 60% by weight is preferable from the viewpoint of adhesiveness and handleability of the prepreg.

Further, the mixed resin preferably has a viscosity at 25 ° C. of 3 to 150 poise. When the viscosity is 3 poise or less, the resin easily falls from the prepreg. Is not preferred because Adjustment of the viscosity can also be performed by adding water.

The single wood and the glued laminated lumber in the present invention are not particularly limited as long as they are conventionally used woods, and are generally known wood used for buildings such as cedar, hinoki, larch, pine, spruce and the like. Wood, oak, drill, zelkova, maple, tochi, ho, cherry, teak, lauan,
Known wood used for plywood such as spinal can be used.

FIG . 3 shows for single wood 5 and glulam 6
Reinforced with a carbon fiber prepreg-attached wood sheet,
It is sectional drawing of the carbon fiber reinforced wood of this invention. The bonding of the carbon fiber prepreg-attached wood sheet of the present invention to a single piece of wood and a laminated wood is performed as follows and integrated. That is, a single wood, a surface of a laminated wood and a surface of a laminated wood sheet, if necessary, a resin used in the present invention and a resin mixed with an inorganic acid or an organic acid as a curing agent or a curing catalyst, particularly preferably a carbon fiber. After applying the mixed resin used for the prepreg to the wood surface, the carbon fiber prepreg-attached wood sheet is attached so that the direction of the carbon fibers is parallel to the fiber direction of the wood to be coated. 1-15 After the carbon fiber pre-flop leg sticking wood sheets and other thin for several sheets of laminated wood are laminated through an adhesive by a known method
5 kg / cm ² at normal temperature to 120 ° C.
Heat for 24 hours.

The carbon fiber reinforced wood and laminated wood of the present invention can be applied to applications used as ordinary wood and laminated wood. Particularly, large buildings such as schools, gymnasiums, auditoriums, various indoor ballparks and domes, It is suitable as aggregate for houses on three or more floors and wooden bridges.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which should not be construed as limiting the scope of the invention. The bending properties and the interlaminar shear strength of the carbon fiber resin composite material are respectively JIS K707
4. The viscosity was measured according to JIS K7078, and the viscosity was measured using a rheometer (manufactured by Rheometrics). Further, the flexural modulus and flexural strength of wood and glulam and carbon fiber reinforced wood and glulam are JASZ21.
01 was measured.

[0035]

Example 1 Carbon fiber "Vesfite (registered trademark) HTA12K" (manufactured by Toho Rayon Co., Ltd.) having a fiber characteristic of 7 μm in single fiber diameter, 12,000 fibers, tensile strength of 3890 MPa and tensile modulus of elasticity of 236 GPa.
Of the strand is resol type phenolic resin “AH-3”
82 "of 43" (manufactured by Lignite) and 18 parts of an organic curing catalyst "D-5" (manufactured by Lignite) based on paratoluenesulfonic acid are uniformly mixed and dissolved at room temperature. The resin was passed through a resin bath containing the mixed resin (having a viscosity of 35 poise at 20 ° C. of 35 poise) at a rate of 5 m / min and immersion time of 0.5 minute, and the content of the resin was reduced to 55% by weight with a squeeze roll.
The strands were wound up to a width of 100 cm so as to be parallel to a drum having a diameter of 90 cm, and a sheet of 0.1 mm in thickness was previously wound from a cedar, and dried at 60 ° C. for 1 hour. The obtained carbon fiber prepreg and the wood sheet were integrally cut off from the drum to obtain a prepreg-attached wood sheet having a carbon fiber weight of 300 g / m ^{2 and} a width of 100 cm and a length of about 2.8 m. This wood sheet with carbon fiber prepreg is
0mm, cut into strips with a length of 100mm, carbon fiber prepreg surface is aligned with the lower side, depth 3mm, width 100m
m, 100mm long mold, pressure 10k
The resultant was cured by heating at 60 ° C. for 2 hours under g / cm ² to obtain a flat plate of a composite material composed of a carbon fiber, a resin and a woody sheet having a thickness of 3 mm. The carbon fiber content in the cured product of the carbon fiber prepreg in this plate was 55% by volume. The plate was cut out from this plate, and the bending characteristics were measured as a strip-shaped test piece having a width of 10 mm and a length of 100 mm. The elastic modulus was 130 GPa and the interlaminar shear strength was 70 MPa, which was an extremely excellent value of 92% of a value (referred to as a theoretical value) obtained by proportional calculation from the strength and elastic modulus of the carbon fiber itself. Here, the theoretical value is a value obtained by the following Expressions 1 and 2.

[0036]

(Equation 1)

[0037]

(Equation 2)

Further, lamination on the mold is easy and requires no labor, and the required time is about one minute.

[0039]

Comparative Example A carbon fiber prepreg sheet was prepared in the same manner as in Example 1 except that a release paper was used instead of the woody sheet used in Example 1. This and the wood sheet used in Example 1 were cut into strips, and the carbon fiber sheet and the wood sheet from which the release paper had been removed were alternately laminated on the mold of Example 1 and heated and cured to form a composite material. Flat plate. The carbon fiber content in this plate was 54% by volume, and cut out from this plate to a width of 10 mm and a length of 100 mm.
When the bending characteristics were measured as a strip-shaped test piece, the bending strength was 1401 MPa, the bending elastic modulus was 129 GPa, and the interlaminar shear strength was 70 MPa. The value 92 (the theoretical value) obtained by proportionally calculating the strength and elastic modulus of the carbon fiber itself was used. %, And the same value as in Example 1 was obtained, but it took 11 minutes to remove the release paper when laminating on the mold, and the removed release paper became waste. Since some resin adhered, gloves for preparation and handling of a disposal bag were required, which was complicated.

[0040]

Example 2 Strand of carbon fiber "Vesfite (registered trademark) HTA6K" ( manufactured by Toho Rayon Co., Ltd.) having a fiber characteristic of a single fiber diameter of 7 microns, a number of fibers of 6000, a tensile strength of 3990 MPa, and a tensile elasticity of 238 GPa. Is a resol type phenol resin “AH-343”
(Lignite Co., Ltd. ) 80 parts and organic curing agent "D-5" (Lignite
And 20 parts of a mixed resin (having a viscosity of 35 poise at 20 ° C.) uniformly mixed and dissolved at room temperature.
150g on a 0.25mm thick sheet made from cedar
/ M ² on a resin film applied using a coater so as to have a thickness of
While continuously arranging at equal intervals in the mm width,
After drying 20 minutes at ° C., further continuously sticking a wood sheet on both taken up at its over a whole while placing a sheet of work made by the thickness 0.25mm from cedar by applying a roll 3m / min A 200 mm wide carbon fiber prepreg-attached wood sheet was obtained. This carbon fiber prepreg-attached wood sheet is cut into strips having a width of 200 mm and a length of 2000 mm, and this one sheet is 25 mm thick, 200 mm wide and 20 mm long.
The same resin as above was applied at 150 g / m ^{2 on} both surfaces of a glued laminated lumber obtained by laminating 6 pieces of 00 mm cedar wood, and then adhered, and then heated and cured at 60 ° C. for 2 hours under a pressure of 10 kg / cm ^2. To obtain a carbon fiber reinforced laminated wood. This carbon fiber reinforced laminated wood has an improved bending strength of 28% and a flexural modulus of 30% as compared with the laminated wood before being reinforced with the carbon fiber prepreg-attached wood sheet, exhibiting excellent values. No waste and excellent workability. Furthermore, the adhesion between the carbon fiber prepreg and the wood sheet and the adhesion between the wood sheet and the laminated wood were good.

[0041]

Example 3 instead of the cedar sheet used in Example 1,
Used paper and paper a natural cellulose having a thickness of 0.03 mm, and a flat plate of the composite material in the same manner as in Example 1. The carbon fiber content in the cured product of the carbon fiber prepreg in this plate was 50% by volume.
When the bending characteristics were measured as a rectangular test piece having a length of 0 mm and a length of 100 mm, the bending strength was 1410 MPa, the bending elastic modulus was 132 GPa, and the interlaminar shear strength was 70 MPa. Value of 92.4%).

[0042]

The carbon fiber prepreg-attached wood sheet obtained by the practice of the present invention not only eliminates the waste problem caused by release paper in the conventional carbon fiber prepreg, but also
It has high strength and rigidity and excellent adhesiveness.It also has sufficient water resistance, corrosion resistance, fire resistance, heat resistance, and long-term storage, so it can efficiently reduce the weight and length of wood and laminated wood. it is possible that arrive. In addition, the carbon fiber reinforced wood and laminated wood of the present invention can be used to make various large buildings, wooden bridges and domes, etc. Resources can be used effectively and the environment is also beneficial.

[Brief description of the drawings]

FIG. 1 is a view showing a laminated state of a carbon fiber prepreg-attached wooden sheet of the present invention using a prepreg sheet.

FIG. 2 is a view showing a laminated state of a carbon fiber prepreg-attached wooden sheet of the present invention using a strand prepreg.

FIG. 3 is a sectional view of the carbon fiber reinforced wood of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Wood-based sheet 2 Carbon fiber prepreg sheet 3 Wood-based sheet 4 Carbon fiber strand prepreg 5 Single wood 6 Glulam

──────────────────────────────────────────────────続 き Continuing on the front page (73) Patent holder 391004207 Saito Wood Industry Co., Ltd. 561, Wada-mura, Oguni-gun, Nagano Prefecture (72) Inventor Shigehisa Ishihara 3-23-12 Tenjin, Nagaokakyo-shi, Kyoto (72) Invention Person Hiroyasu Ogawa 3-3-9, Nihonbashi, Chuo-ku, Tokyo Inside Toho Rayon Co., Ltd. (72) Inventor Yoshihiro Endo 234 Takaishi, Kamitsukari, Nagaizumi-cho, Sunto-gun, Shizuoka Prefecture Toho Rayon Co., Ltd. 72) Inventor Isamu 2-5, Chikko Shinmachi, Sakai City, Osaka (72) Inventor Hideo Tsukihito 24, Fukami, Sugatsu, Jinmeji-cho, Kaifu-gun, Aichi Prefecture (72) Inventor Satoshi Saito 561, Wadamura, Oguni-gun, Nagano Prefecture Address (56) References JP-A-4-286323 (JP, A) JP-A-6-122178 (JP, A) JP-A-6-23912 (JP, A) JP-A-4-279332 (JP, A) JP-A-60-984 90 (JP, A) JP-A-60-107336 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 C08J 5/24 EPAT (QUESTEL) WPI / L (QUESTEL)

Claims (6)

(57) [Claims] A carbon fiber for wood reinforcement comprising a carbon fiber prepreg sheet impregnated with a thermosetting resin and a mixed resin of a curing agent or a curing catalyst, and a wood-based sheet having a thickness of 0.01 to 0.3 mm disposed on one or both sides of the carbon fiber prepreg sheet. Wood sheet with fiber prepreg attached. 2. A carbon fiber strand prepreg impregnated with a mixed resin of a thermosetting resin and a curing agent or a curing catalyst, wherein the strands are arranged in parallel on the surface of a wood-based sheet having a thickness of 0.01 to 0.3 mm, Alternatively, a wood sheet to which a carbon fiber prepreg for wood reinforcement is further attached, on which a wood-based sheet is further arranged. 3. The resorcinol-based resin according to claim 1, wherein
A liquid mixed resin containing at least one resin selected from resole type phenolic resins and formaldehyde as a curing agent or an inorganic acid or an organic acid as a curing catalyst. 2. Wood sheet with carbon fiber prepreg for wood reinforcement 4. The wood sheet to which the carbon fiber prepreg for wood reinforcement according to claim 1 or claim 2 or 3 is attached ,
Pressurized heat pressurized, integrated wood reinforcing carbon fiber composite wood sheets. 5. The wood sheet to which the carbon fiber prepreg for wood reinforcement according to claim 1 or claim 2 or 3 is attached, wherein the wood sheet is a single wood surface or a board made of a plurality of boards or a single board. Alternatively, carbon fiber reinforced wood that is affixed between veneers or on the surface and integrated by heating and pressing. 6. The carbon fiber composite wood sheet for reinforcing wood according to claim 4, which is applied to the surface of a single piece of wood, or to any one of a plurality of boards or laminated boards composed of veneers, or between or between veneers. Affixed and integrated carbon fiber reinforced wood.