JP2009172919A - Plate-shaped molded article and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a plate-shaped molded article superior in accuracy of the plate thickness, bending modulus, having a small dimension shrinkage factor, scarcely having thin spots, remaining voids and sag in plate thickness and small in curve and twist and excellent in production efficacy, and its manufacturing method. <P>SOLUTION: A plurality of fibrous threads are impregnated with a thermosetting resin composition and cured in a heating die to give a plurality of draw-molded articles, and then the articles are adhered to one another by one of an adhesive agent, an adhesive sheet and a pre-preg to give the desired plate-shaped molded article. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a plate-shaped molded article and a method for producing the same, and in particular, is a plate-shaped molded article that is excellent in sheet thickness accuracy and bending elastic modulus and has no curling, void residue, etc. It relates to a manufacturing method.

Plate-shaped molded products are widely used for electrical insulation spacers, partition walls, semiconductor transfer devices, reaction vessel outer walls, structural materials, fixing plates for electronic components, transfer plates, and the like. In particular, plate-shaped molded products used for electrical insulating spacers, various partition walls, semiconductor transfer devices, and the like are required to have high thickness accuracy and little warpage, twisting, and dimensional change.
Conventionally, a plate-shaped molded product is manufactured as a laminated plate (primary molded product) having a thickness of about 1 to 3 mm by stacking a plurality of prepregs in which a woven fabric or a nonwoven fabric is impregnated with a resin and then heating and pressing. ing. Further, a thick molded product (secondary molded product) having a thickness of about 10 to 100 mm is manufactured by further stacking a plurality of the laminated plates and heating and press-molding each layer through a prepreg or an adhesive sheet. ing. When manufacturing a thick molded product, the molding pressure (4 to 8 MPa) is the same as that for a thin molded product. However, there is a problem that air bubbles (voids) and voids (scratch) are likely to be generated between the layers, and sufficient attention must be paid to the prepreg used and the molding conditions.

  A laminate in which a plurality of prepregs are laminated is pressed at a resin flow temperature in a vacuum state to form a composite sheet, and a laminate in which a predetermined number of the composite sheets are laminated is heated and pressurized in a vacuum state to be cured and thickened. Proposals such as making a laminate have been made (see, for example, Patent Document 1). However, a thick laminate that can be said to be sufficient with respect to plate thickness accuracy, dimensional change, blurring, voids, warpage, and the like has not been obtained.

JP-A-2-162017

In the conventional method for manufacturing a thick molded article, a large number of laminated plates, prepregs, and laminated sheets are overlapped, so that there is a lot of material loss and much time is required for the overlapping. In particular, for molded articles with a thickness of 10 mm or more, the molding pressure must be low in order to prevent misalignment, resulting in the occurrence of scraping, void residue, plate thickness sagging, etc., and obtaining a highly accurate product. It was difficult.
In view of the above-mentioned problems, the present invention is excellent in sheet thickness accuracy and bending elastic modulus, has a small dimensional shrinkage ratio, no sag, void residue, and sheet thickness sagging, and has less warping and twisting, and has good productivity. An object of the present invention is to provide a molded product, particularly a thick plate-shaped molded product.

  As a result of intensive studies, the present inventors have used a pultruded product obtained by impregnating a thermosetting resin composition into a plurality of fiber yarns and then curing while passing through a heating mold, The inventors have found that the above object can be achieved and completed the present invention.

That is, the present invention
1. A plurality of pultruded products obtained by impregnating a thermosetting resin composition into a plurality of fiber yarns and then curing with a heating die are bonded with one or more of an adhesive, an adhesive sheet, and a prepreg. Plate-shaped molded products manufactured by
2. A plate-shaped product manufactured by further bonding a pair of prepregs or reinforcing plates to the front and back surfaces of the plate-shaped molded product according to 1 above,
3. The plate-shaped molded product according to 1 or 2, wherein the pultruded molded product has a hollow structure,
4). The plate-shaped molded product according to any one of the above 1 to 3, which is manufactured by superimposing so that the fiber direction of the pultruded molded product is one direction,
5. The plate-shaped molded product according to any one of the above 1 to 3, which is produced by superimposing so that the fiber directions of the pultruded molded product are different,
6). 6. The plate-shaped molded article according to any one of 1 to 5 above, which has a thickness of 10 to 150 mm, and A plurality of pultruded products obtained by impregnating a thermosetting resin composition into a plurality of fiber yarns and then curing with a heating die are bonded with one or more of an adhesive, an adhesive sheet, and a prepreg. A method for producing a plate-shaped molded article,
Is to provide.

  The plate-shaped molded article of the present invention is excellent in plate thickness accuracy, has a small dimensional shrinkage rate, is free from sag, void residue and plate thickness sagging, and has almost no warpage or twist. Moreover, since the manufacturing method of this invention becomes a simple thing by using a pultruded molded product, it is excellent in productivity. In particular, the present invention can provide a thick plate-like molded product having a high plate thickness of 100 mm or more, which has been difficult to manufacture.

Hereinafter, the present invention will be described in detail.
The plate-shaped molded article of the present invention is produced by adhering a plurality of pultruded molded articles produced in advance with any one or more of an adhesive, an adhesive sheet, and a prepreg.

[Pull-molded product]
The pultruded product in the present invention can be performed in the same manner as the production of a general pultruded product in which a plurality of fiber yarns are impregnated with a thermosetting resin composition and then cured while passing through a heating mold. it can.
Hereinafter, the production of the pultruded product will be described in detail.

(Fiber yarn)
The fiber yarn is obtained by converging the fibers, and is not particularly limited as long as it is a fiber yarn conventionally used for producing a pultruded product. Examples of the fibers include glass fibers, carbon fibers, aramid fibers, xylon fibers, wholly aromatic polyester fibers, chemical-resistant organic fibers, and the like, and commercially available fibers can be used.

Examples of the glass fiber include E-glass fiber, T-glass fiber, and D-glass fiber. Examples of the carbon fiber include PAN-based and pitch-based, and examples of the aramid fiber include Para-type and meta-type fibers such as poly-p-phenylene terephthalamide and poly-m-phenylene isophthalamide are listed.
The fibers used in the fiber yarn of the present invention, particularly glass fibers and carbon fibers, are preferably those whose surface is subjected to sizing treatment to maintain chemical resistance. Examples of the sizing agent that performs this sizing treatment include agents that have low reactivity with the alkali component and good wettability to the matrix resin. Specifically, silane coupling agents such as methacryl silane and ureido silane, or these A mixed product or the like is preferable.
In addition, the above fibers may be used alone or a plurality of types may be mixed. In particular, it is preferable to use glass fibers and carbon fibers each alone or a composite system of glass fibers and carbon fibers as fiber yarns.
The content of the fiber yarn is preferably an average volume content (volume ratio) of the fiber base material in the pultruded product, and is usually preferably 50 to 80% by volume. If it is 50% by volume or more, the rigidity of the molded product can be made sufficient, and if it is 80% by volume or less, the entire fiber base material can be impregnated with the thermosetting resin composition. The physical properties can be improved.

(Thermosetting resin composition)
The thermosetting resin composition impregnated into the fiber yarn can use a thermosetting resin such as a vinyl ester resin, an epoxy resin, or an unsaturated polyester resin as a base resin.
For example, when used as a thermosetting resin composition for impregnating a fiber yarn with a vinyl ester resin composition, (A) a vinyl ester resin, (B) a crosslinking agent, (C) a low shrinkage agent, (D) an inorganic filler, It is preferable to use (E) a mold release agent and (F) an organic peroxide as an essential component.

(A) The vinyl ester resin is not particularly limited as long as it is generally used as a molding material. For example, D-953 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) Can be mentioned. Such (A) vinyl ester resin is obtained by reacting (a-1) an acid component and (a-2) an epoxy resin component.
(A-1) Examples of the acid component include unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, and sorbic acid, and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, A mixture of two or more dibasic acids and acid anhydrides such as tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, and adipic acid can also be used.
(A-2) As an epoxy resin component, as long as it has two or more epoxy groups in one molecule, it can be widely used without being limited by molecular structure, molecular weight, etc. Specifically, Examples thereof include an epoxy resin having a bisphenol type, novolak type or biphenyl type aromatic group, an epoxy resin in which a polycarboxylic acid is glycidyl etherified, and an epoxy resin having an alicyclic group in which an epoxy group is condensed to a cyclohexane derivative. These epoxy resins can be used in combination with a liquid monoepoxy resin as necessary.
(A) It is preferable that the compounding quantity of vinyl ester resin is the range of 70-90 mass% normally in a thermosetting resin composition.

(B) The crosslinking agent can be used as long as it has a double bond polymerizable with (A) vinyl ester resin. For example, styrene, divinylbenzene, diallyl phthalate, methyl methacrylate, triallyl isocyanurate. Etc.
(B) It is preferable that the compounding quantity of a crosslinking agent is the range of 1-2 mass% normally in a thermosetting resin composition.

(C) As the low shrinkage material, polyethylene resin, saturated polyester resin, rubber or the like which is a thermoplastic resin can be used, but polyethylene resin is preferable from the viewpoint of chemical resistance, light weight, and low shrinkage. . Of these, the use of polyethylene resin powder having a glass transition point of 70 to 120 ° C. satisfies chemical resistance, light weight, and molding shrinkage, and can satisfy long-term reliability as a support product. This is particularly preferable because an inexpensive pultruded product can be produced. The same applies to the case where an unsaturated polyester resin other than the vinyl ester resin is used as the base resin.
(C) It is preferable that the compounding quantity of a low shrinkage material is 0.5-1.5 mass% normally in a thermosetting resin composition.

Examples of the (D) inorganic filler include, but are not particularly limited to, commonly used materials such as barium sulfate, calcium carbonate, aluminum hydroxide, silica, and glass balloon.
(D) It is preferable that the compounding quantity of an inorganic filler is the range of 10-28 mass% normally in a thermosetting resin composition.

(E) The release agent may be any release agent that is usually used as a molding material, and examples thereof include commercially available silicone oils. Among them, epoxy-modified silicone oils are preferable.
(E) It is preferable that the compounding quantity of a mold release agent is the range of 0.01-2 mass% normally in a thermosetting resin composition.

(F) The organic peroxide is not particularly limited as long as it is a compound usually used as a curing agent for a vinyl ester resin, and examples thereof include benzoyl peroxide, di-t-butyl peroxide, and isobutyryl peroxide. Etc.
(F) It is preferable that the compounding quantity of an organic peroxide is 0.1-2 mass% normally in a thermosetting resin composition.

(Manufacture of pultruded products)
As a method for producing a pultruded product, first, a plurality of fiber yarns, for example, about 50 to 500 fiber yarns were impregnated with a thermosetting resin composition, and the thermosetting resin composition adhered to the fiber yarns. State. At this time, since it is necessary for the fiber yarn to be able to withstand the pulling force at the time of pultrusion molding, it is preferable to use the fiber yarn oriented in the pulling direction.
Next, the fiber yarn impregnated with the above-mentioned thermosetting resin composition is passed through a heating mold, and the thermosetting resin composition is heat-cured and the outer shape is adjusted to a predetermined shape and then drawn to form a molded product. To do.

The mold used at this time is not particularly limited as long as it is a mold used for pultrusion molding, and any mold can be used as long as it can be controlled by a heater or the like in order to obtain a pultrusion molded product by curing the resin. Although the temperature of a metal mold | die can be suitably selected according to the resin composition to be used, it is preferable that it is 70-170 degreeC normally. When the mold temperature is 70 ° C. or higher, the fiber yarn impregnated with the thermosetting resin composition can be completely cured and pulled out. When the mold temperature is 170 ° C. or lower, the curing reaction rate is moderate. The molded product is free from cracks and warping.
The drawing time (time for passing through the mold) can be appropriately selected according to the resin composition to be used, but it is usually preferable to be within the range of 0.5 to 3 minutes. The drawing speed that provides such drawing time is usually preferably in the range of 10 to 120 cm / min, and more preferably 20 to 35 cm / min. When the drawing speed is 10 cm / min or more, curing in the molding die can be completed in an appropriate time, and stable continuous molding can be performed without resistance when drawing. Moreover, if the drawing speed is 120 cm / min or less, the cured state of the fiber yarn impregnated with the thermosetting resin composition can be made sufficient.
That is, in pultrusion molding, a fiber yarn impregnated with a thermosetting resin composition is continuously drawn into a heated mold, and the resin is subjected to a predetermined temperature and cured while passing through the mold. It is important to withdraw from the mold outlet at a predetermined time.

The apparatus used in the pultrusion molding may be the same as that of a generally used pultrusion product manufacturing apparatus, and can be used without particular limitation. The mold part is preferably at the temperature described above.
Thereby, the thermosetting resin composition can be efficiently cured, and the pultruded product can be molded with good operability.
The cross-sectional shape of the cut surface of the pultruded product of the present invention manufactured by the above-described manufacturing method is, for example, that having a square cross section as shown in FIG. 1, or having a hollow cross section as shown in FIG. It can be.

[Adhesion of pultruded products]
The plate-shaped molded product in the present invention can be produced by bonding a plurality of pultruded molded products.
Adhesion may use any of an adhesive, an adhesive sheet, or a prepreg, and may be used alone or in combination of two or more. In particular, a thick plate-like molded product obtained by laminating plate-like molded products to an appropriate thickness is preferably bonded using a prepreg in order to increase the strength such as the flexural modulus. Further, a pair of adhesive sheets, prepregs, or reinforcing plates can be bonded to the front and back surfaces of the plate-shaped molded product, and in particular, the strength can be increased by bonding the reinforcing plates.

(Adhesive and adhesive sheet)
The adhesive composition used in the present invention and the adhesive composition of the adhesive sheet can use an epoxy resin, an acrylic resin, an unsaturated polyester resin, a silicone resin, a phenol resin, a polyimide resin, or the like as a base resin.
For example, as an epoxy resin, as long as it has two or more epoxy groups in one molecule like the epoxy resin used in a resin for a pultruded product, it is widely used without being limited by molecular structure, molecular weight, etc. Can be used. Specifically, an epoxy resin having a bisphenol type, novolak type or biphenyl type aromatic group, an epoxy resin obtained by glycidyl esterification of a polycarboxylic acid, or an epoxy resin having an alicyclic group obtained by condensing an epoxy group to a cyclohexane derivative Etc. These epoxy resins can be used individually or in mixture of 2 or more types. Furthermore, in addition to the above epoxy resin, a liquid monoepoxy resin can be used in combination as required.

Examples of the curing agent that can be used when curing the epoxy resin include amine-based curing agents, phenol-based curing agents, and acid anhydride-based curing agents.
Examples of the amine curing agent include aromatic diamines such as dicyandiamide, m-phenylenediamine, 4,4′-diaminodiphenylsulfone, and m-xylylenediamine. Examples of the phenolic curing agent include phenol novolak resin, cresol novolak resin, bisphenol A type novolak resin, triazine-modified phenol novolak resin, and the like. Examples of the acid anhydride curing agent include phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride. Examples include acid, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like.
These curing agents may be used alone or in admixture of two or more.
The amount of the curing agent used is usually preferably 0.4 to 1.5% by mass, more preferably 0.5 to 0.5% by mass with respect to the epoxy resin from the viewpoint of balance between curable properties and curable resin physical properties. The range is 1.3% by mass.

When using an acid anhydride, you may mix | blend a hardening accelerator in order to accelerate | stimulate the hardening. There is no restriction | limiting in particular as a hardening accelerator, From what is used as a conventional hardening accelerator, arbitrary things can be selected suitably and can be used. For example, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, etc. Examples include imidazole compounds, boron trifluoride complexes, tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, and triphenylphosphine. These curing accelerators may be used alone or in combination of two or more.
The amount of the curing accelerator used is usually preferably 0.05 to 10% by mass, more preferably 0.1 to 3% by mass with respect to the epoxy resin, from the viewpoint of the balance between the curing accelerator and the cured resin properties. % Range.

In order to impart flexibility to the cured adhesive layer, an elastomer can be added to the adhesive composition, if necessary, in addition to the above resin. Examples of the elastomer include various synthetic rubbers such as acrylic rubber, acrylonitrile butadiene rubber, carboxyl group-containing acrylonitrile butadiene rubber and vinyl group-containing acrylonitrile butadiene rubber, rubber-modified high molecular weight compounds, polymer epoxy resins, phenoxy resins, modified polyimides, and the like. Examples thereof include modified polyamide. These elastomers may be used alone or in combination of two or more.
Moreover, a well-known phenolic anti-aging agent, a filler, etc. can be added to an adhesive composition suitably.

(Prepreg)
The prepreg used in the present invention can be produced by impregnating a fiber base material into a resin composition, drying and curing in accordance with a conventional method. The impregnation apparatus may be either a horizontal drying tower or a vertical drying tower. Moreover, you may manufacture a prepreg by crimping | bonding a fiber base material to a resin sheet.
The fiber used for a fiber base material will not be specifically limited if it is manufactured in sheet form, such as a woven fabric, a nonwoven fabric, and a unidirectional fiber (roving). Examples of the fibers include fiber yarns made of glass fibers, carbon fibers, xylon fibers, wholly aromatic polyester fibers, chemical-resistant organic fibers, and the like. Specifically, it is the same as the fiber exemplified in the production of the pultruded product.

Next, the resin composition used for the prepreg used in the present invention can use, for example, an epoxy resin, a phenol resin, a polyimide resin, a bismaleimide resin, an unsaturated polyester resin, or the like as a base resin.
For example, the epoxy resin can be widely used without being limited by the molecular structure, molecular weight, etc., as long as it has two or more epoxy groups in one molecule as in the adhesive composition. Specifically, it is the same as the epoxy resin exemplified in the adhesive composition. Furthermore, the epoxy resin can be used in combination with a polyimide resin, a bismaleimide resin, and a liquid monoepoxy resin as necessary.

As the curing agent for curing the epoxy resin, an amine curing agent, a phenol curing agent, an acid anhydride curing agent, or the like can be used, and specifically, it is the same as the curing agent exemplified in the adhesive composition. .
The amount of the curing agent used is usually preferably 0.4 to 1.5% by mass, more preferably 0.5 to 1 with respect to the epoxy resin from the viewpoint of balance between curability and physical properties of the curable resin. The range is 3 mass%.
Moreover, when using an acid anhydride, you may mix | blend a hardening accelerator in order to accelerate | stimulate the hardening. The curing accelerator is not particularly limited, and can be appropriately selected and used from those conventionally used as a curing accelerator for epoxy resins. Specifically, the adhesive composition described above is used. It is the same as the curing accelerator exemplified in the product.
The use amount of the curing accelerator is usually preferably 0.05 to 10% by mass, more preferably 0.1 to 3% by mass with respect to the epoxy resin, from the viewpoint of the balance between the curing accelerator and the cured resin properties. Range.

[Manufacture of plate-shaped products]
The plate-shaped molded product in the present invention can be obtained by bonding the pultruded molded product using any one or more of the adhesive, the adhesive sheet, and the prepreg manufactured as described above.
First, after aligning the length and width of a predetermined number of pultruded products, the upper and lower surfaces and side surfaces thereof are bonded using one or more of an adhesive, an adhesive sheet, and a prepreg. At this time, a prepreg, a reinforcing plate, and the like can be superimposed on the front and back surfaces of a plurality of pultruded products bonded with an adhesive or the like, if necessary. Next, a plurality of pultruded products bonded with an adhesive or the like are heat-molded under a pressure of about 0 to 10 MPa with a molding press. At this time, by performing pressure reduction at the same time, a molded plate without voids can be obtained.
In addition, when bonding a pultruded product with an adhesive or the like, by shifting the fiber direction of the pultruded product and superimposing it vertically, a molded product having high bending strength in both the short and long directions of the plate-shaped molded product is obtained. be able to. When shifting the fiber direction, it is preferable to overlap so that the upper and lower fiber directions are different by an angle of 90 degrees from the viewpoint of further increasing the strength of the plate-shaped molded product.

  Furthermore, by stacking a plurality of pultruded molded products and performing adhesion and heat molding in the same manner as described above, a thick plate-shaped molded product having a thickness of about 10 to 150 mm can be obtained. If the thickness is 150 mm or less, it can be produced without causing deviation or sagging. The number of pultruded products to be overlapped at this time may be appropriately determined depending on the thickness of the target thick plate-shaped product. The thick plate-shaped molded product is preferably 10 to 150 mm in thickness and more preferably 10 to 100 mm in thickness from the viewpoints of displacement and plate thickness prevention, ease of manufacture, and strength of the molded product. preferable. Moreover, when manufacturing a thick plate-shaped molded article, it is preferable to bond using a prepreg in order to strengthen strengths, such as a bending elastic modulus.

  The present invention also provides a plurality of pultruded products obtained by impregnating a plurality of fiber yarns with a thermosetting resin composition and then curing with a heating mold, and are any of an adhesive, an adhesive sheet, and a prepreg. There is also provided a method for producing a plate-shaped molded article bonded with one or more kinds.

Hereinafter, the present invention will be specifically described by way of examples.
Example 1
As a thermosetting resin component, vinyl ester resin (manufactured by Dainippon Ink Chemical Co., Ltd., trade name: UE3505) 22 parts by mass, styrene monomer (manufactured by Nippon Yupica Co., Ltd., trade name: styrene monomer) 0.35 parts by mass, 0.25 parts by mass of polyethylene (manufactured by Sumitomo Seika Co., Ltd., trade name: Frocene UF-1.5), barium sulfate (trade name: precipitated barium sulfate-100, manufactured by Sakai Chemical Industry Co., Ltd.) 3.7 Part by mass, release agent (manufactured by Kozakura Shokai Co., Ltd., trade name: INT-1850HT [organic acid, glyceride, synthetic resin condensate]) 0.35 parts by weight, organic peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name) : Perhexa HC) 0.35 parts by mass was placed in a kneader (disper) and kneaded for about 20 minutes to obtain a thermosetting resin composition.
Next, 60 carbon fibers (trade name: UT-500-24K, manufactured by Toho Tenax Co., Ltd.) as a fiber base material are impregnated in a resin tank containing the obtained thermosetting resin composition, and the carbon fibers After passing through an extrusion molding jig, it is continuously heated to 160 ° C., sent to a molding die (length: 800 mm, internal dimensions: 19 mm × 50.3 mm), and sufficiently cured, and a speed of 20 cm / min. Was drawn to obtain a pultruded product. The cross-sectional dimension was 18.8 mm x 50 mm.
Next, as shown in FIG. 3, the obtained pultruded products are arranged in two stages so that each stage has 10 pieces, and an epoxy resin / anhydride two-component adhesive (manufactured by KYOCERA Chemical Corporation, trade name: TVB2620 / TVB2625) is applied, and a glass epoxy reinforcing plate (trade name: TLB551, manufactured by Kyocera Chemical Co., Ltd.) having a thickness of 1 mm is overlapped on the front and back surfaces and charged into a molding press at a molding pressure of 0.5 MPa. A plate-shaped molded product having a length of 1010 mm, a width of 1008 mm, and a thickness of 41.3-41.8 mm was obtained by heating at 60 ° C. for 60 minutes.

Example 2
As shown in FIG. 4, a 0.1 mm thick epoxy resin adhesive sheet (manufactured by Kyocera Chemical Co., Ltd., trade name: TFA-880) was used for interlayer adhesion of the pultruded product obtained in Example 1. Was molded in the same manner as in Example 1 to obtain a plate-shaped molded product having a length of 1010 mm, a width of 1008 mm, and a thickness of 40-41.7 mm.

Example 3
As shown in FIG. 5, a glass epoxy prepreg having a thickness of 0.19 mm (manufactured by Kyocera Chemical Co., Ltd.) was used for adhesion between the front and back surfaces of the pultruded molded product obtained in Example 1 and the interlayer without using a reinforcing plate. Except for using name: TLP-551), molding was carried out in the same manner as in Example 1 to obtain a plate-like molded product having a length of 1010 mm, a width of 1008 mm, and a thickness of 39.9-40.7 mm.

Example 4
The carbon fiber impregnated with the thermosetting resin composition of Example 1 is fed into a cored mold (length: 800 mm, inner dimension: 8.8 mm × 40 mm), sufficiently cured, and 20 cm / min. The hollow pultruded molded product was continuously obtained by drawing at a speed. At this time, the core jig (length: 500 mm, outer shape: 10 mm, set temperature: 140 ° C.) was installed so as to come into contact with the fiber from 10 cm before the mold.
The obtained hollow pultruded product was cut into a length of 1010 mm with a cutting device to obtain a hollow pultruded product having a volume ratio of carbon fibers of 70%. The cross-sectional dimension was 18.8 mm x 50 mm.
Next, as shown in FIG. 6, the obtained hollow pultruded molded products are arranged in two stages so that each stage has 10 pieces, and epoxy resin / anhydride two-component adhesive (trade name, manufactured by Kyocera Chemical Co., Ltd.). : TVB2620 / TVB2625), charged in a molding press, heated at a molding pressure of 0.5 MPa, 180 ° C. for 60 minutes, and formed into a hollow plate having a length of 1010 mm, a width of 1008 mm, and a thickness of 38.6-39.8 mm. I got a product.

Comparative Example 1
21 sheets of glass epoxy prepreg (product name: TLP551, manufactured by Kyocera Chemical Co., Ltd.) having a length of 1020 mm, a width of 1020 mm, and a thickness of 0.19 mm are superposed and charged into a forming press through an OPP film as a release film. Heating was performed at 4 ° C. and 180 ° C. for 90 minutes to obtain a glass epoxy laminate having a thickness of 3.9 mm. Furthermore, 10 laminates and 9 glass epoxy prepregs were alternately superposed and heated at 2 MPa and 180 ° C. for 60 minutes to obtain a molded product. The cured resin product protruding from the end face of the molded product was cut into a plate-shaped molded product having a length of 1010 mm, a width of 1008 mm, and a thickness of 37-39.2 mm.

The thicknesses of the plate-like molded products obtained in Examples 1 to 4 and Comparative Example 1, the occurrence of scum and voids, and the warpage were measured, and the results are shown in Table 1.
In addition, the blur was measured on the whitened portion from the corner. As for the occurrence state of voids, the case where no voids were visually observed was “None”, and the case where voids were generated was “Yes”. The warpage was measured by a height gate while standing on a surface plate.

  From Table 1, it can be seen that the plate-like molded products obtained in Examples 1 to 4 are free from scumming and voids and have almost no warpage as compared with Comparative Example 1.

Example 5
As shown in FIG. 7, the fibers of the pultruded molded product were laminated in three stages through an adhesive so as to be in one direction in the longitudinal direction, thereby obtaining a thick plate-shaped molded product.
Example 6
As shown in FIG. 8, the center of the pultruded product was combined with the upper and lower ones by changing the direction at an angle of 90 degrees and laminated in three stages via an adhesive to obtain a thick plate-like molded product.

The bending elastic moduli (GPa) in the short side direction 8 and the long side direction 9 of the thick plate-like molded products obtained in Examples 5 and 6 were measured. The results are shown in Table 2.
The flexural modulus was measured according to JIS K 6911.

  From Table 2, it can be seen that the thick plate-like molded product obtained in Example 5 is excellent in the bending elastic modulus in the longitudinal direction because the fibers of the pultruded molded product are aligned in one direction. Further, the thick plate-like molded product obtained in Example 6 is overlapped so that the fiber directions of the upper and lower pultruded molded products are different at an angle of 90 degrees. It turns out that it is excellent in rate.

  The plate-like molded product of the present invention is excellent in plate thickness accuracy and bending elastic modulus, has a small dimensional shrinkage rate, no sag, void residue, and plate thickness sagging, less warpage and twist, and a thick plate-like molded product Even in such a case, since it is excellent in strength such as flexural modulus, it can be used for products that require these characteristics.

It is sectional drawing of a pultrusion molded product. It is sectional drawing of an air drawing product. 3 is a cross-sectional view illustrating a configuration of a plate-shaped molded product of Example 1. FIG. FIG. 5 is a cross-sectional view illustrating a configuration of a plate-shaped molded product of Example 2. 6 is a cross-sectional view illustrating a configuration of a plate-shaped molded product of Example 3. FIG. FIG. 6 is a cross-sectional view showing a configuration of a hollow plate-shaped molded product of Example 4. It is the figure which showed the structure of the thick plate-shaped molded product of Example 5. FIG. It is the figure which showed the structure of the thick plate-shaped molded product of Example 6. FIG.

Explanation of symbols

1: Pull-out molded product 2: Adhesive 3: Reinforcing plate 4: Adhesive sheet 5: Prepreg 6: Hollow pultruded molded product 7: Fiber direction 8: Short direction 9: Longitudinal direction

Claims (7)

  A plurality of pultruded products obtained by impregnating a thermosetting resin composition into a plurality of fiber yarns and then curing with a heating die are bonded with one or more of an adhesive, an adhesive sheet, and a prepreg. A plate-shaped molded product manufactured in the same manner.   A plate-shaped product produced by further bonding a pair of prepregs or reinforcing plates to the front and back surfaces of the plate-shaped product according to claim 1.   The plate-shaped molded product according to claim 1 or 2, wherein the pultruded molded product has a hollow structure.   The plate-shaped molded product according to any one of claims 1 to 3, which is manufactured by being overlapped so that the fiber direction of the pultruded molded product is one direction.   The plate-shaped molded product according to any one of claims 1 to 3, which is manufactured by being piled up so that the fiber directions of the pultruded molded product are different.   The plate-shaped molded product according to any one of claims 1 to 5, which has a thickness of 10 to 150 mm.   A plurality of pultruded products obtained by impregnating a thermosetting resin composition into a plurality of fiber yarns and then curing with a heating die are bonded with one or more of an adhesive, an adhesive sheet, and a prepreg. The manufacturing method of the plate-shaped molded article to do.

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