JP6774807B2 - Fiber reinforced resin molded product and its manufacturing method - Google Patents

Description

The present invention relates to a resin molded product made of fiber reinforced plastic (FRP) and a method for producing the same.

In recent years, it has been studied to use fiber reinforced plastic (FRP), which is lightweight and does not have to worry about rust, as an alternative material to metal. Among them, fiber-reinforced resin molded bodies using carbon fiber, glass fiber, etc. as reinforcing fibers have particularly high strength, and are OA (office auto) for components of transportation equipment, building materials, electrophotographic copying machines, printers, facsimiles, etc. Mation: Office Automation) It is expected to be effectively used as a housing for equipment, a support member or a shaft of a roll (charged roll, developing roll, etc.) (see, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2016-79376

However, since the fiber-reinforced resin molded body has low rigidity (flexural modulus), it is necessary to review the design such as increasing the wall thickness of the fiber-reinforced resin molded body in order to exhibit the same level of rigidity as metal. It becomes. Further, when the wall thickness of the fiber-reinforced resin molded body is increased, the weight is increased accordingly. Therefore, there is a problem that the advantage of the fiber-reinforced resin molded body is not obtained as compared with, for example, an aluminum alloy member.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide a fiber-reinforced resin molded product and a method for producing the same, which are lightweight, have high strength, and exhibit high rigidity.

In order to achieve the above object, the present invention is a fiber reinforced resin molded body in which continuous fiber bundles are embedded in parallel, wherein the continuous fiber bundle is composed of at least one of carbon fibers and glass fibers, and the fiber reinforced. The matrix resin of the resin molded body comprises a resin composition containing the following (A) as a main component and the following components (B) and (C), and the component (B) constitutes the continuous fiber bundle. The first gist is a fiber-reinforced resin molded body that is distributed in an oriented state along continuous fibers.
(A) A thermosetting resin which is at least one selected from the group consisting of vinyl ester resin, epoxy resin and phenol resin.
(B) An alumina fiber and potassium titanate which are needle-shaped inorganic fillers having a Mohs hardness of 4 or more and whose outer diameter satisfies the relationship shown in the following formula (1) with respect to the outer diameter of the continuous fiber . At least one needle-like inorganic filler.
Outer diameter of needle-shaped inorganic filler ÷ Outer diameter of continuous fiber = 0.01 to 0.71 …… (1)
(C) A curing agent for the components (A).

Further, the present invention is a method for producing the above-mentioned fiber-reinforced resin molded body, in which continuous fibers composed of at least one of carbon fibers and glass fibers are bundled, and the following component (A) is used as a main component as described below. A step of drawing into a tank containing a resin composition containing the components (B) and (C) and impregnating the resin composition with continuous fibers, and a step of pulling out the continuous fibers impregnated with the resin composition and heat-curing them. The second gist is a method for producing a fiber-reinforced resin molded body provided with.
(A) A thermosetting resin which is at least one selected from the group consisting of vinyl ester resin, epoxy resin and phenol resin.
(B) An alumina fiber and potassium titanate which are needle-shaped inorganic fillers having a Mohs hardness of 4 or more and whose outer diameter satisfies the relationship shown in the following formula (1) with respect to the outer diameter of the continuous fiber . At least one needle-like inorganic filler.
Outer diameter of needle-shaped inorganic filler ÷ Outer diameter of continuous fiber = 0.01 to 0.71 …… (1)
(C) A curing agent for the components (A).

That is, the present inventors have conducted intensive studies to solve the above problems. In the process of the research, the present inventors used a continuous fiber bundle composed of at least one of carbon fiber (CF) and glass fiber (GF) as a fiber to be a reinforcing material of a fiber reinforced resin molded body, and used a fiber reinforced resin. It was examined to include a filler in the matrix resin in order to embed the continuous fiber bundle parallel to the molded body and further enhance the reinforcing property and the dispersibility of the force. Then, as a result of repeating various experiments, it is a needle-like inorganic filler having a Morse hardness of 4 or more, and the outer diameter thereof is based on the above formula (1) with respect to the outer diameter of the continuous fibers constituting the continuous fiber bundle. The needle-shaped inorganic filler (B) satisfying the relationship shown is contained as the filler, and the specific needle-shaped inorganic filler (B) is further oriented along the continuous fibers constituting the continuous fiber bundle. As a result, it was found that the reinforcing property and the dispersibility of the force of the fiber-reinforced resin molded body were enhanced, and as a result, an extremely high bending elasticity (rigidity) was exhibited instead of the reaction force. Reached.

It is difficult to distribute the needle-shaped inorganic filler (B) as described above in an oriented state along the continuous fibers constituting the continuous fiber bundle by conventional injection molding. Therefore, the continuous fibers are drawn into a tank containing a resin composition containing a thermosetting resin, the needle-like inorganic filler (B), and a curing agent in a bundled state, and the continuous fibers are impregnated into the resin composition. After that, when a special manufacturing method such as drawing out the continuous fiber impregnated with the above resin composition and thermosetting it was applied, the above problem was solved and the special fiber reinforced resin molded product as described above was solved. The present inventors have found that the above-mentioned plastic can be produced satisfactorily.

As described above, the fiber-reinforced resin molded body of the present invention is a fiber-reinforced resin molded body in which continuous fiber bundles are embedded in parallel, and the continuous fiber bundle is composed of at least one of carbon fibers and glass fibers. The matrix resin of the fiber-reinforced resin comprises a resin composition containing a thermosetting resin (A) as a main component and a specific needle-like inorganic filler (B) and a curing agent (C), and the specific needle. The state-inorganic filler (B) is distributed in a state of being oriented along the continuous fibers constituting the continuous fiber bundle. Therefore, it is possible to exhibit an extremely high flexural modulus (rigidity) and strength comparable to those of a metal member, and further, it is possible to achieve weight reduction as compared with a metal member. In addition, as the flexural modulus (rigidity) is high as described above, the characteristic of controlling vibration (vibration characteristic) is also improved. Therefore, it is preferably used for applications such as a support member for transportation equipment or a roll shaft for OA equipment. Can be done.

In particular, when the specific acicular inorganic filler (B) is at least one of alumina fiber and potassium titanate, higher bending elasticity (rigidity) and strength can be exhibited.

Further, when the ratio of the specific needle-like inorganic filler (B) in the resin composition is in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin (A), other performance is obtained. It is possible to exhibit a high flexural modulus (rigidity) without impairing it.

Further, when the thermosetting resin (A) is at least one selected from the group consisting of vinyl ester resin, unsaturated polyester resin, epoxy resin and phenol resin, it becomes excellent in processability and the like.

Further, when the ratio (Vf value) occupied by the continuous fiber bundle is in the range of 45 to 80%, the surface smoothness of the fiber-reinforced resin molded product becomes excellent.

Further, when the specific elastic coefficient of the fiber-reinforced resin molded body exceeds the specific elastic coefficient of the fiber-reinforced resin molded body containing the component (B), the resonance frequency shifts to the high frequency side and other vibration transmissibility. Will be better at.

Further, in a state where the continuous fibers are bundled, the resin composition is drawn into a tank containing the resin compositions containing the components (A) to (C), the continuous fibers are impregnated into the resin composition, and then the resin composition is impregnated. When a fiber-reinforced resin molded body is manufactured by a special manufacturing method such as drawing out the continuous fibers that have been made to be heat-cured, a specific needle-like inorganic filler (B) is continuously applied to form a continuous fiber bundle as described above. It can be distributed in an oriented state along the fibers, and the fiber-reinforced resin molded product of the present invention can be satisfactorily produced.

It is a schematic diagram which showed the cross-sectional state in the longitudinal direction of an example of the fiber-reinforced resin molded article of this invention.

Next, embodiments of the present invention will be described in detail.

As described above, the fiber-reinforced resin molded body of the present invention is a fiber-reinforced resin molded body in which continuous fiber bundles are embedded in parallel, and the continuous fiber bundles are formed from at least one of carbon fibers and glass fibers. The matrix resin of the fiber-reinforced resin is composed of a resin composition containing a thermosetting resin (A) as a main component and a specific needle-like inorganic filler (B) and a curing agent (C), and described above. The specific needle-like inorganic filler (B) is distributed in a state of being oriented along the continuous fibers constituting the continuous fiber bundle. The specific needle-like inorganic filler (B) has a Mohs hardness of 4 or more, and its outer diameter satisfies the relationship shown in the following formula (1) with respect to the outer diameter of the continuous fiber. ..

The "main component" of the resin composition has a great influence on the characteristics of the entire composition, and in the present invention, means 50% by weight or more of the entire composition. Further, "the specific needle-like inorganic filler (B) is distributed in a state of being oriented along the continuous fibers constituting the continuous fiber bundle" means that the needle-like inorganic filler is aggregated. It means a state in which the longitudinal direction of the needle-like inorganic filler is dispersed in a state of being oriented along the continuous fibers. A schematic representation of this state is shown in FIG. FIG. 1 schematically shows a support member (or shaft) which is an example of a fiber-reinforced resin molded product of the present invention. In the figure, 1 is a support member (or shaft), and 2 is a continuous fiber bundle. Reference numeral 2a is continuous fibers constituting the continuous fiber bundle, 3 is a needle-like inorganic filler, and 4 is a matrix resin. The distribution state of the needle-shaped inorganic filler can be confirmed by observing the longitudinal cross section of the shaft with an electron microscope.

In the fiber-reinforced resin molded product of the present invention, the fibers embedded as the reinforcing material need to be continuous fibers from the viewpoint of strength and rigidity as described above, and they are bundled as described above. There is. As the continuous fiber, at least one of carbon fiber and glass fiber is used because it is excellent in reinforcing property.

When the fiber-reinforced resin molded body of the present invention is a conductive fiber-reinforced resin molded body, it is preferable to use carbon fiber as the continuous fiber from the viewpoint of enhancing conductivity, and more preferably, at least the fiber-reinforced resin. The continuous fibers of carbon fibers are embedded in the outer peripheral portion of the molded body. In the fiber-reinforced resin molded body having such a structure, the continuous fibers embedded therein are preferably carbon fibers from the viewpoint of reinforcing property, but from the viewpoint of cost reduction, glass fibers, polyester fibers and the like. It is preferable to use at least one selected from the group consisting of aramid fibers, and among them, glass fibers are more preferable because they have excellent reinforcing properties.

In the fiber-reinforced resin molded product of the present invention, the thermosetting resin (A) constituting the resin composition which is the material of the matrix resin is a vinyl ester resin, an unsaturated polyester resin, or an epoxy resin from the viewpoint of processability. , Phenolic resin is preferably used. These may be used alone or in combination of two or more. Of these, vinyl ester resin is more preferable because it has high adhesion to continuous fibers.

As the curing agent (C) of the thermosetting resin (A), for example, for vinyl ester resin and unsaturated polyester resin, methyl ethyl ketone peroxide, acetyl acetone peroxide, benzoyl peroxide, tertiary butyl peroxy-2-ethyl Organic peroxides such as hexanoate, benzoyl peroxide, tertiary butyl perbenzoate, and dicumyl peroxide are used. Epoxy resins include bisphenol A, tetrabromobisphenol A, bisphenol S, bisphenol F, bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ethane, 1,3,3-trimethyl-1-m-hydroxy. Phenylindan-5-ol, 1,3,3-trimethyl-1-m-hydroxyphenylindan-7-ol, 1,3,3-trimethyl-1-p-hydroxyphenylindan-6-ol, resorcin, hydroquinone , Catecol, nadic acid, maleic acid, phthalic acid, methyl-tetrahydrophthalic acid, methyl nadic acid and other polycarboxylic acids and their anhydrides, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, phenylenediamine, diaminodicyclohexylmethane, xylylene diamine , Toluenediamine, diaminodicyclocyclohexane, dichloro-diaminodiphenylmethane (including isomers), polyamine compounds such as ethylenediamine and hexamethylenediamine, dicyandiamide, tetramethylguanidine, active hydrogen-containing compounds capable of reacting with epoxy groups, etc. are used. .. Hexamethylenetetramine, methylolmelamine, methylolurea and the like are used as the phenol resin. These may be used alone or in combination of two or more. The ratio of the curing agent (C) in the resin composition is preferably in the range of 0.5 to 10 parts by weight, more preferably with respect to 100 parts by weight of the thermosetting resin (A), from the viewpoint of its curability. Is in the range of 1 to 5 parts by weight.

As described above, the specific needle-like inorganic filler (B) used together with the thermosetting resin (A) has a Mohs hardness of 4 or more, and its outer diameter is the outer diameter of the continuous fiber. On the other hand, those satisfying the relationship shown in the following equation (1) are used.

When the continuous fiber is a carbon fiber, the value of "outer diameter of needle-shaped inorganic filler / outer diameter of continuous fiber" is preferably in the range of 0.071 to 0.71. When the continuous fiber is glass fiber, the value of "outer diameter of needle-shaped inorganic filler ÷ outer diameter of continuous fiber" is preferably in the range of 0.025 to 0.5, more preferably 0.25. It is in the range of ~ 0.5. In this way, the reason why the preferable range of "outer diameter of needle-shaped inorganic filler ÷ outer diameter of continuous fiber" differs depending on the type of continuous fiber is that each fiber (filament) diameter is different, so that an external force is applied. This is because the filler diameters that can be supported are different. The outer diameter of the needle-shaped inorganic filler in the fiber-reinforced resin molded body and the outer diameter of the continuous fiber are determined by microtome, cross-section polisher (CP) processing, focused ion beam (FIB) processing, etc. on the fiber-reinforced resin molded body. It can be measured by cutting out and observing the cross section with a magnifying mirror, SEM (electron microscope) or the like. Before producing the fiber-reinforced resin molded product, the needle-shaped inorganic filler and continuous fibers may be observed as they are using a magnifying glass, SEM, or the like. The outer diameter of the needle-shaped inorganic filler and the outer diameter of the continuous fibers are the outer diameter (minor diameter) of 50 or more needle-shaped inorganic fillers and 50 or more fibers observed by the above method. The average value of the outer diameters (fiber diameters) of continuous fibers is used as the value. The Mohs hardness is based on the old Mohs hardness, and its upper limit is 10, which is a value measured by a Mohs hardness meter (manufactured by Tokyo Science Co., Ltd.). Then, by using a needle-shaped inorganic filler that satisfies each of the above-mentioned regulations, the reinforcing property and the dispersibility of the force of the fiber-reinforced resin molded product are enhanced, and as a result, a high flexural modulus (rigidity) is exhibited. Become. Further, as the bending elastic modulus (rigidity) is exhibited as described above, the characteristic of controlling vibration (vibration characteristic) is also improved. The definition of whether or not the inorganic filler is needle-shaped is defined as "needle-shaped" when the aspect ratio of the particles of the inorganic filler is measured by SEM observation or the like and the value is 20 to 40. The average length of the major axis of the specific needle-shaped inorganic filler (B) particles, which can also be measured by SEM observation or the like, is 10 to 50 μm, which is the mixing property with the resin and the reinforcing property. From the point of view, it is preferable.

It should be noted that generally known inorganic fillers such as silica, carbon black, talc, mica, etc. do not exhibit the high hardness as described above, and may be needle-shaped as defined above. Absent. That is, the needle-like inorganic filler (B) is a special one, for example, potassium titanate, alumina fiber, zinc oxide, titanium oxide, boron fiber, zirconia fiber, or at least one of titanium and zirconium, and silicon. , Carbon and oxygen ceramic fibers, carbon nanotubes, glass milled fibers and the like correspond to this needle-like inorganic filler (B). These needle-like inorganic fillers may be used alone or in combination of two or more. Among them, at least one of alumina fiber and potassium titanate is preferable as the needle-like inorganic filler (B) because the fiber-reinforced resin molded product of the present invention exhibits higher rigidity and strength. Further, the needle-like inorganic filler may be surface-treated with a silane coupling agent in advance, and examples of the types of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltri. Ethoxysilane, 3-aminopropyltriethoxysilane, vinyltricrolsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxy Propyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyl Trimethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyandiapropyltriethoxysilane, vinyltrimethoxysilane , Vinyl triethoxysilane, p-styryltrimethoxysilane and the like. These may be used alone or in combination of two or more. As the surface treatment method, spraying or the like is convenient and preferable.

The ratio of the needle-like inorganic filler (B) in the resin composition which is the material of the matrix resin is in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin (A). It is preferable because it can exhibit a high flexural modulus (rigidity) without impairing other performance. The more preferable range of the content of the needle-like inorganic filler (B) with respect to 100 parts by weight of the thermosetting resin (A) is 5 to 15 parts by weight when the continuous fiber is a carbon fiber, and the continuous fiber is In the case of glass fiber, it is in the range of 2 to 10 parts by weight. In this way, the reason why the preferable range of the needle-like inorganic filler content differs depending on the type of continuous fiber is that the diameter of each fiber (filament) is different and the diameter of the filler that can be supported when an external force is applied is different. Is. If the amount of the needle-like inorganic filler (B) is too small, sufficient rigidity cannot be obtained, and conversely, if the amount of the needle-like inorganic filler (B) is too large, the resin composition The viscosity becomes high, the resin composition is not completely impregnated in the fiber bundle, and problems such as deterioration of moldability are observed.

Further, the resin composition may contain, if necessary, a curing accelerator, a coupling agent, a dispersant, an inorganic filler such as talc, carbon black and mica, a shrinkage inhibitor such as calcium carbonate and magnesium oxide, and a flame retardant. A mold release agent or the like may be added as appropriate.

Next, the fiber-reinforced resin molded product of the present invention is produced, for example, as follows.

That is, in a bundled state of continuous fibers, the main component is a thermosetting resin (A), and the curing agent (C), a specific needle-like inorganic filler (B), and other additives as necessary are contained. The resin composition is drawn into a tank containing the resin composition to be used, and the resin composition is impregnated with the continuous fibers. Then, the continuous fibers impregnated with the resin composition are drawn out and heat-cured by press molding or drawing into a mold. If the fiber-reinforced resin molded product obtained by the above heat curing is a long one, it is cut to a predetermined length. In addition, when the resin composition is impregnated with continuous fibers and then pressed into a mold or pressed into a mold, a non-woven fabric (materials include polyester, glass, and aramid) is used to suppress exposure of the continuous fibers to the surface. There is) may be set. By such a special manufacturing method, the target fiber-reinforced resin molded product can be satisfactorily manufactured.

By using a kneader such as a triple roll or a bead mill to prepare the resin composition used for the impregnation treatment, the agglomeration of the needle-like inorganic filler (B) is further eliminated, and the resulting fiber-reinforced resin molding is obtained. The flexural modulus (rigidity) of the body can be further increased. In particular, it is preferable to use a three-roll as the kneader because the gap between the rolls can be easily adjusted for processing in order to break the aggregation of the filler. The kneading treatment is performed before the curing agent (C) is added, and the kneading is performed again after the curing agent (C) is added. In the kneading at this time, the curing agent (C) is contained in the resin composition. Since it may be mixed, any of manual stirring, feather stirring and kneading by roll may be used. Of these, kneading by stirring the blades is preferable because it is simple.

Further, it is preferable that the viscosity of the resin composition used for the impregnation treatment is 25 Pa · s or less from the viewpoint of satisfactorily performing the above special production method. That is, if the viscosity is too high, the resin composition is not sufficiently impregnated in the continuous fiber bundle, and problems such as deterioration of the moldability of the fiber-reinforced resin molded product are observed. The viscosity was measured before the addition of the curing agent (C), and was measured at a temperature of room temperature (28 ° C. to 35 ° C.) using a B-type viscometer in accordance with JIS K 7117. The value.

The thermosetting of the impregnated resin composition is carried out by heat treatment at 100 to 160 ° C. for about 1 to 60 minutes.

The long fiber-reinforced resin molded product obtained by the above heat curing is cut to a predetermined length by a cutting machine or the like to obtain a target fiber-reinforced resin molded product.

The above series of manufacturing methods can also be performed using a general pultrusion molding machine.

The continuous fiber content (Vf value) in the fiber-reinforced resin molded product of the present invention thus obtained is preferably 45 to 80%, more preferably 55 to 70%. The continuous fiber content (Vf value) is a value calculated by the following formula (2). If the Vf value is too small, the molding shrinkage may be severe and the dimensionality may not be ensured. On the contrary, if the Vf value is too large, the amount of resin may be small and the surface smoothness may not be ensured.

The fiber-reinforced resin molded product of the present invention thus obtained preferably has a flexural modulus of 65 GPa or more, more preferably in the range of 70 to 100 GPa. The flexural modulus of the fiber-reinforced resin molded product having a length of 100 mm was determined in accordance with JIS K 7074 at room temperature (28 ° C. to 35 ° C.) at a test speed of 2 mm / min and a distance between spans. The elastic modulus calculated by performing a three-point bending test at 100 mm.

When the specific elastic modulus of the fiber-reinforced resin molded product exceeds the specific elastic modulus of the fiber-reinforced resin molded product that does not contain the specific needle-like inorganic filler (B), the resonance frequency is on the high frequency side. It is preferable because it becomes more excellent in vibration transmissibility such as shifting to. The specific elastic modulus is the value obtained by measuring the specific gravity of the sample of the fiber-reinforced resin molded product in accordance with JIS K 0061 (balance method) and the value of the bending elastic modulus measured as described above. Based on this, it can be calculated according to the following formula (3).

Further, the fiber-reinforced resin molded product of the present invention obtained by the above manufacturing method is not limited to a columnar one such as a shaft in a long one, but has a square pipe shape, a round pipe shape, a channel shape, and an angle shape. , Flat bar shape, sheet shape, etc., which can be drawn out. Further, as an example of a non-long one, a continuous fiber impregnated with the resin composition is wound on a metal plate or the like and press-molded.

The fiber-reinforced resin molded product of the present invention can be preferably used for a support member for transportation equipment and a roll shaft for OA equipment, depending on its shape. Specific examples of the support members for transportation equipment include automobile tower bars, automobile performance dampers, automobile arm parts, automobile side door beams, automobile cross members (member frames), automobile bracket stays, and automobiles. Subframes for use can be mentioned. Specific examples of the roll shaft for OA equipment include a charging roll shaft, a developing roll shaft, a toner supply roll shaft, a transfer roll shaft, a paper feed roll shaft, and a cleaning roll shaft. can give. These are useful because they are lighter in weight, less likely to rust, and have higher strength, rigidity, and vibration characteristics than conventional products. In addition, the roll shaft for OA equipment is blurred or uneven or printed due to the roll floating between the printing paper and the roll, as in the case of using a conventional non-rigid FRP shaft. This is particularly useful because problems such as uneven paper transport can be eliminated and the roll printing / printing paper transport performance can be improved.

Next, Examples will be described together with Comparative Examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

First, the materials shown below were prepared prior to Examples and Comparative Examples. The outer diameter (minor diameter) and length (major diameter) of the following needle-shaped fillers (B1) to (B6) are the outer diameter (minor diameter) and length (major diameter) of 50 or more needle-shaped fillers according to SEM observation. ) Is the measured average value. The outer diameter (fiber diameter) of the following continuous glass fibers and continuous carbon fibers is an average value obtained by measuring the outer diameter (fiber diameter) of 50 or more continuous fibers by SEM observation. The Mohs hardness of the following needle-shaped fillers (B1) to (B6) is a value measured by a Mohs hardness meter (manufactured by Tokyo Science Co., Ltd.).

[Thermosetting resin (A1)]
Vinyl ester resin (main agent) (CBZ-500LM-AS, manufactured by Japan U-Pica Company)

[Needle-shaped filler (B1)]
Potassium titanate (Morse hardness: 4, outer diameter 0.5 μm, length: 15 μm) (Tismo D102, manufactured by Otsuka Chemical Co., Ltd.)

[Needle-shaped filler (B2)]
Alumina fiber (Mohs hardness: 9, outer diameter 5 μm, length: about 5000 μm) (Arsen B97NK4, manufactured by Denka)

[Needle-shaped filler (B3)]
Glass milled fiber (Mohs hardness: 5, outer diameter 10 μm, length: 100 μm) (SS 05C-404, manufactured by Nitto Boseki Co., Ltd.)

[Needle-shaped filler (B4)]
Glass milled fiber (Mohs hardness: 5, outer diameter 25 μm, length: 80 μm)

[Needle-shaped filler (B5)]
Carbon nanotubes (Mohs hardness: 5, outer diameter 0.1 μm, length: about 10 μm) (AMC, manufactured by Ube Industries, Ltd.)

[Needle-shaped filler (B6)]
Carbon milled fiber (Mohs hardness: 5, outer diameter 7 μm, length: 100 μm) (CFMP-150X, manufactured by Nippon Polymer Co., Ltd.)

[Coupling agent]
3-Aminopropyltrimethoxysilane (KBM903, manufactured by Shin-Etsu Polymer Co., Ltd.)

[Curing accelerator]
PR-CBZ-02, manufactured by Japan U-Pica Company

[Curing agent (C1)]
Kayaester O-50E, manufactured by NOF CORPORATION

[Continuous glass fiber]
Continuous glass fiber with an outer diameter of 20 μm (RS440 RR-520, manufactured by Nitto Boseki)

[Continuous carbon fiber]
Continuous carbon fiber with an outer diameter of 7 μm (Trading Card T-700, manufactured by Toray Industries, Inc.)

[Examples 1 to 16, Comparative Examples 1 to 4]
The above thermosetting resin and the like (excluding the curing agent) were blended and kneaded with three rolls. Then, a curing agent was added and the blades were stirred to prepare a resin composition. The blending ratio of each of the above components was as shown in Tables 1 and 2 below.
Then, the viscosity of the resin composition after kneading with three rolls (viscosity before adding the curing agent) was measured under the following conditions.
・ Equipment: TOKI SANGYO, VISCOMETER TVB-10 (TVR) ・ Rotor type: H7
・ Number of revolutions: 60 rpm
-Measurement environment: Room temperature (28 ° C to 35 ° C)

Subsequently, the continuous fibers are bundled and drawn into a tank containing the resin composition prepared above, the continuous fibers are impregnated with the resin composition, and then wound on a metal plate of 100 mm × 150 mm × 3 mm and wound at 5 MPa. A plate-shaped sample was prepared by pressing at 150 ° C. for 30 minutes under pressure.

In addition to the above sample, a rod-shaped sample was also prepared. That is, in a state where the continuous fibers are bundled, they are drawn into a tank containing the resin composition prepared above, the continuous fibers are impregnated with the resin composition, and then drawn into a mold and thermoset, and the resulting long length is obtained. The fiber-reinforced resin molded product of No. 1 was cut to prepare a rod-shaped (cylindrical) sample having a diameter of 8 mm and a length of 100 mm.

As the continuous fibers, only continuous glass fibers (RS440 RR-520, manufactured by Nitto Boseki Co., Ltd.) were used in Examples 1 to 8 and Comparative Examples 1 and 2, and in Examples 9 to 16 and Comparative Examples 3 and 4. , Only continuous carbon fiber (Trading Card T-700, manufactured by Toray Industries, Inc.) was used.

Further, in the samples of Examples 1 to 16 and Comparative Examples 1 to 4 prepared above, the continuous fiber content (Vf value) obtained according to the following calculation formula (2) is 59% in each case. did.

With respect to the samples of Examples and Comparative Examples thus obtained and the sample made of SPCC-91, which is a general steel material, prepared as a reference example, each characteristic was measured according to the following criteria. The results are shown in Tables 1 and 2 below together with the viscosity of the resin composition (viscosity before adding the curing agent).

≪Bending elastic modulus≫
A three-point bending test was performed on a rod-shaped sample at room temperature (28 ° C to 35 ° C) at a test speed of 2 mm / min and a span distance of 100 mm in accordance with JIS K 7074, and the flexural modulus (GPa) was obtained. Was calculated.

≪Specific elastic modulus≫
The specific gravity of the rod-shaped sample was measured according to JIS K 0061 (balance method). Then, the specific elastic modulus was calculated according to the following formula (3) based on the measured value of the flexural modulus obtained by the above measuring method and the measured value of the specific gravity. As for the specific elastic modulus in Table 1, the value of the specific elastic modulus in the sample of Comparative Example 1 was set to 1.000, and the value of the specific elastic modulus in each example and the sample of the comparative example was index-converted to this value. It is a thing. Further, for the specific elastic modulus in Table 2, the value of the specific elastic modulus in the sample of Comparative Example 3 was set to 1.000, and the value of the specific elastic modulus in the samples of each Example and the Comparative Example was index-converted to this value. It is a thing.

≪Vibration characteristics≫
The plate-shaped sample was tested by the one-end fixed striking method according to JIS G 0602 "Vibration damping characteristic test method for vibration damping steel sheet", and the primary resonance frequency was determined by using the Hilbert transform. The higher the primary resonance frequency, the better the vibration characteristics.

From the above results, it can be seen that the sample of the example has a higher flexural modulus, a higher specific elastic modulus, and is also excellent in vibration characteristics as compared with the sample of the comparative example using the same continuous fibers as the example.

Since the fiber-reinforced resin molded body of the present invention is lightweight and has high strength, rigidity, and vibration characteristics, it is suitable for an automobile tower bar, an automobile performance damper, an automobile arm part, an automobile side door beam, and an automobile. Support members for transportation equipment such as cross members (member frames), automobile bracket stays, and automobile subframes, charging roll shafts, development roll shafts, toner supply roll shafts, transfer roll shafts, and paper feed rolls. It can be used for roll shafts for OA equipment such as shafts for cleaning rolls and shafts for cleaning rolls.

1 Support member (or shaft)
2 Continuous fiber bundle 2a Continuous fiber 3 Needle-shaped inorganic filler 4 Matrix resin

Claims (6)

A fiber-reinforced resin molded body in which continuous fiber bundles are embedded in parallel, the continuous fiber bundle is composed of at least one of carbon fibers and glass fibers, and the matrix resin of the fiber-reinforced resin molded body is the following (A). ) Is the main component, and the resin composition contains the following components (B) and (C), and the component (B) is distributed in a state of being oriented along the continuous fibers constituting the continuous fiber bundle. A fiber-reinforced resin molded body characterized by being present.
(A) A thermosetting resin which is at least one selected from the group consisting of vinyl ester resin, epoxy resin and phenol resin.
(B) An alumina fiber and potassium titanate which are needle-shaped inorganic fillers having a Mohs hardness of 4 or more and whose outer diameter satisfies the relationship shown in the following formula (1) with respect to the outer diameter of the continuous fiber . At least one needle-like inorganic filler.
Outer diameter of needle-shaped inorganic filler ÷ Outer diameter of continuous fiber = 0.01 to 0.71 …… (1)
(C) A curing agent for the components (A). The proportion of needle-shaped inorganic fillers in the resin composition (B) is a thermosetting resin (A) is in the range of 0.5 to 15 parts by weight of claim 1 Symbol placement of the fiber-reinforced resin molding 100 parts by weight body. The fiber-reinforced resin molded product according to claim 1 or 2 , wherein the ratio (Vf value) occupied by the continuous fiber bundle is in the range of 45 to 80%. The fiber-reinforced resin according to any one of claims 1 to 3 , wherein the specific elastic modulus of the fiber-reinforced resin molded product exceeds the specific elastic modulus of the fiber-reinforced resin molded product containing the component (B). Molded body. The fiber-reinforced resin molded product according to any one of claims 1 to 4 , which is a support member for transportation equipment or a shaft for rolls for OA equipment. The method for producing a fiber-reinforced resin molded product according to any one of claims 1 to 5 , wherein continuous fibers composed of at least one of carbon fibers and glass fibers are bundled and the following component (A) is present. The step of impregnating the resin composition with continuous fibers by drawing the resin composition into a tank containing the following components (B) and (C) as the main component, and the continuous fibers impregnated with the resin composition. A method for producing a fiber-reinforced resin molded body, which comprises a process of drawing and heat-curing.
(A) A thermosetting resin which is at least one selected from the group consisting of vinyl ester resin, epoxy resin and phenol resin.
(B) An alumina fiber and potassium titanate which are needle-shaped inorganic fillers having a Mohs hardness of 4 or more and whose outer diameter satisfies the relationship shown in the following formula (1) with respect to the outer diameter of the continuous fiber . At least one needle-like inorganic filler.
Outer diameter of needle-shaped inorganic filler ÷ Outer diameter of continuous fiber = 0.01 to 0.71 …… (1)
(C) A curing agent for the components (A).

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