JP3115023B2 - Manufacturing method of fiber reinforced resin molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fiber-reinforced resin molded product by a filament winding method.

[0002]

2. Description of the Related Art In general, a fiber-reinforced resin molded product by a filament winding method is formed by winding a roving fiber material impregnated with a thermosetting resin liquid around an outer periphery of a mandrel and laminating the same at room temperature or by heating the resin. Manufactured by curing.

[0003] In such a manufacturing method, the resin liquid in the roving fiber material wound around the mandrel moves to the outside, and the resin in the inner roving fiber material decreases, so-called resin withering occurs. . Therefore, cracks and voids are generated in the inner part of the product, and delamination occurs, resulting in a decrease in mechanical strength. Also, in applications where internal pressure is applied by a fluid flowing therethrough, such as piping, there is a drawback that weeping (perspiration) occurs.

Japanese Patent Application Laid-Open No. 64-45625 discloses that a half-piece core member of a pipe joint is formed by a hand lay-up method, and the half-piece core members are joined to each other in a pipe joint shape. A method of manufacturing a fiber reinforced resin pipe joint by winding and laminating a roving fiber material impregnated with a thermosetting resin liquid and curing the resin has been proposed.

According to this method, generation of cracks and voids in the inner portion of the product is prevented, and in applications where internal pressure is applied, generation of weeping is also prevented.
However, since the hand lay-up method is used, the molding is troublesome and time-consuming, and the productivity is low, and the interlayer adhesion between the core member and the roving fiber material laminated thereon is not sufficient. In addition, weeping may occur from the joint between the half-shaped core members, and the reliability of quality is lacking.

[0006]

In order to remedy such a drawback, the present inventor applied a thermosetting resin liquid to the surface of a mandrel and heated it to gel the resin liquid. A method of winding and laminating a roving fiber material impregnated with a thermosetting resin liquid and heating the resin to cure all the resins was attempted. In this case, it was found that the generation of cracks and voids in the inner part of the product was prevented, the delamination did not occur, and the occurrence of weeping was well prevented in applications in which the internal pressure was applied by a fluid.

However, in this method, it takes a considerable time (for example, several tens of minutes) to heat and gel the thermosetting resin liquid applied to the surface of the mandrel. Speed balance is poor, and there is still a problem in product productivity. Further, it has been found that there is a problem that the gelation state varies and the quality of the product is not stable.

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems. It is an object of the present invention to provide a method for producing a fiber-reinforced resin molded product by a filament winding method, in which no cracks or voids are generated on the inner part of the product. ,
An object of the present invention is to provide a method for stably producing a product free of weeping with high productivity in applications where internal pressure is applied by a fluid.

[0009]

According to the present invention, a curable resin solution containing a photo-curing agent and a thermo-curing agent is applied to the surface of a mandrel and irradiated with light. The curable resin liquid is gelled, and the outer periphery is wound around a roving fiber material impregnated with a thermosetting resin liquid and laminated.
This is cured at room temperature or by heating all the resin to produce a fiber-reinforced resin molded product.

In the present invention, first, a curable resin liquid containing a photocuring agent and a thermosetting agent is applied to the surface of the mandrel. Application methods include brush coating, roll coating,
Spraying or the like is adopted. The coating thickness is generally 0.5 to 2 mm
And particularly preferably about 1 mm.

The curable resin liquid is a conventional unsaturated polyester resin liquid in which a crosslinking monomer such as styrene is dissolved in unsaturated polyester, and a curable unsaturated resin obtained by adding both a photocuring agent and a thermosetting agent. Saturated polyester resin liquids are preferred. In this case, it is desirable to use a resin that forms a soft cured layer rather than a resin that forms a hard cured layer. In addition, a curable vinyl ester resin liquid to which both a light curing agent and a heat curing agent are added is also preferable.

As a photo-curing agent, 2,2-dimethoxy-2
Acetophenones such as phenylacetophenone and methoxyacetophenone; benzoin ethers such as benzoin ethyl ether and benzoin isopropyl ether; ketals such as benzyl dimethyl ketal; and disulfides such as diphenyl disulfide. Such a photocuring agent is generally used in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the above-mentioned unsaturated polyester resin liquid or vinyl ester resin liquid.

Examples of the thermosetting agent include methyl ethyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate and the like, which can be cured at 60 to 80 ° C. for medium temperature curing, or Room temperature curing, to which an accelerator such as cobalt naphthenate or dimethylaniline is added, is used. Such a thermosetting agent is generally used in an amount of 0.5 to 2 parts by weight based on the above-mentioned unsaturated polyester resin liquid or curable vinyl ester resin liquid.

As described above, a curable resin solution containing a photo-curing agent and a thermo-curing agent is applied to the surface of the mandrel, and thereafter, this is irradiated with light. As the light to be irradiated, active rays such as ultraviolet rays and visible rays, in particular, ultraviolet lamps having a wavelength of 300 to 410 nm, high-pressure mercury lamps, metal halogen lamps and the like are used. Irradiation varies depending on the shape and size of the product, but is generally performed at an output of 40 to 1000 W from a distance of 10 to 100 cm so as to uniformly gel the curable resin liquid. The irradiation time required for gelation is a few minutes. Here, the gelation means a semi-cured state in which the viscosity of the resin liquid rapidly rises and solidifies in an agar state.

Next, a roving fiber material impregnated with a thermosetting resin solution is wound around the outer periphery of the gelling layer and laminated. The resin-impregnated roving fiber material is wound in a predetermined pattern by a filament winding device, for example, in a helical shape and laminated to a desired thickness. The resin-impregnated roving fiber material is generally laminated so as to have a thickness of 1 to 30 mm.

The thermosetting resin liquid used herein is generally an unsaturated polyester resin liquid for forming a hard cured layer or a thermosetting unsaturated polyester resin obtained by adding the same thermosetting agent to a vinyl ester resin liquid. Liquid or thermosetting vinyl ester resin liquid. As the roving fiber, a fiber bundle composed of hundreds to thousands of continuous monofilaments, for example, an inorganic fiber such as glass fiber or carbon fiber, or an organic fiber such as polyester fiber or aramid fiber is preferably used. . The diameter of the monofilament is preferably 1 to 50 μm. The content of roving fiber material is
Generally, it is 30 to 70% by volume.

Thereafter, it is placed in a heating furnace or the like, heated and cured at an appropriate temperature, and finally removed from the mandrel. The mandrel is set in various shapes, and according to this shape, for example, it is possible to manufacture fiber-reinforced resin molded bodies of various shapes such as a cheese type, an elbow type, a socket type pipe joint or a long pipe, a container, and the like. it can. The heating temperature is generally 60
The temperature is in the range of -100 ° C, but in some cases, thermosetting is possible even at a heating temperature of normal temperature. In this way, the lower layer gelled resin and the upper layer fiber-impregnated resin are thermally cured.
The heat setting time is generally between 60 and 120 minutes.

In the present invention, a filler (particularly, an inorganic filler) such as calcium carbonate, talc, clay or aluminum hydroxide or a short glass fiber is added to a curable resin solution containing a photocuring agent and a thermosetting agent. It is preferable to include them.
Generally, the length of the short glass fiber is preferably 5 to 50 mm. The filler is generally contained in an amount of 10 to 200 parts by weight based on 100 parts by weight of the above-mentioned unsaturated polyester resin liquid or vinyl ester resin liquid. In addition, glass short fibers are generally used in the unsaturated polyester resin liquid or vinyl ester resin liquid described above.
It is contained in the range of 1 to 10 parts by weight based on 100 parts by weight.

[0019]

[Function] A roving fiber material impregnated with a thermosetting resin liquid is wound around the outer periphery of the mandrel and laminated, and when the resin is cured at room temperature or by heating, a light curing agent is previously applied to the surface of the mandrel. When a curable resin liquid containing a thermosetting agent is applied and irradiated with light to gel the curable resin liquid, the gelled layer has a reduced fluidity, so that the gelled layer is directed outward. It is difficult to move, the inner resin does not wither, and cracks and voids are prevented from occurring in the inner part of the product.

The gelled layer is formed by light irradiation, and the light irradiation can be performed in a very short time and can be controlled freely by stopping the irradiation. As a whole, it is possible to accurately set the desired degree of gelation in a relatively short time.

Moreover, since the roving fiber material impregnated with the thermosetting resin liquid is wound around the gelled layer in the semi-cured state, the gelled layer and the resin-impregnated roving fiber material thereon are well bonded. Then, it is firmly integrated at a normal temperature or by thermal curing by heating, and delamination is prevented.

In particular, when a filler or short glass fiber is contained in a curable resin liquid containing a light curing agent and a heat curing agent,
Thereby, the water repellency of the resin liquid with respect to the mandrel is improved, and the viscosity is increased so that no residual coating occurs, and the coating workability is improved.

[0023]

EXAMPLES Examples and comparative examples of the present invention will be described below. Example 1 A T-shaped mandrel that can be assembled and disassembled was prepared, and a curable unsaturated polyester resin solution containing a photocuring agent and a thermosetting agent was applied to the surface of the mandrel with a brush to a thickness of about 1 mm. The curable unsaturated polyester resin liquid is 100 parts by weight of unsaturated polyester (Polymer 6320F: manufactured by Takeda Pharmaceutical Co., Ltd.) and a photo-curing agent (Irgacure 651: manufactured by Ciba Geigy)
0.5 parts by weight and 1 part by weight of a thermosetting agent (Percadox 16: manufactured by Kayaku Akzo). To this, a 365nm ultraviolet lamp (1KW x 2) is applied over almost the entire circumference from a distance of 100cm to 3
The resin solution was uniformly gelled by irradiation for minutes.

On the other hand, as shown in FIG. 1, ten glass fiber rovings (fiber diameter: about 16 μm, count: 2230 g / km) and a large number of roving fibers 11, 12, and 13 are aligned and the fiber feeding rolls 31 and The resin-impregnated roll 40 and the fiber feed roll 32 were passed to form ten resin-impregnated fiber rovings impregnated with a thermosetting unsaturated polyester resin liquid.

The above-mentioned thermosetting unsaturated polyester resin liquid is composed of 100 parts by weight of unsaturated polyester (Ester R235: manufactured by Mitsui Toatsu) and 0.7 part by weight of a thermosetting agent (Kayamec M: manufactured by Kayaku Akzo). . Further, the content of the glass fiber roving was about 60% by volume.

Next, the resin-impregnated fiber roving 11 '
, 12 ', 13', etc., were passed through the traverse eye 50 in a state of being aligned, and converged into a tape shape having a width of about 45 mm. This converged tape-shaped resin impregnated fiber roving 60,
A helical coil was wound around and laminated in a predetermined pattern on the outer periphery of the mandrel 70 on which the gel layer was formed, and this was heated and cured at 80 ° C. for 1 hour to produce a cheese-type pipe joint. The length of the main pipe was set to 700, the length of the branch pipe was set to 400 mm, and the inner diameter of the pipe was set to 165 mm.

The thickness of the main pipe part and the branch pipe part of the obtained cheese type pipe joint is about 5 mm, and the thickness of the junction part of the main pipe part and the branch pipe part is 10 mm. (Specification: 13 tons or more), no destruction occurred, and no delamination occurred. Also, even when a strong water pressure (breaking water pressure 40 kg / cm ² ) was applied to the inside, no weeping (water seepage) occurred at all.

Example 2 In Example 1, a glass roving (fiber diameter: about 16 μm, count: 1150 g / km) was added to a curable unsaturated polyester resin solution containing a photocuring agent and a thermosetting agent by a rotary chopper to about 1 /. 3 parts by weight of chopped short fibers cut to a length of 4 inches were mixed. Other than that, it carried out similarly to Example 1.

In this case, no destruction occurred at a tensile stress of 13 tons, and no delamination occurred. Also, no weeping (bleeding of water) occurred at a breaking water pressure (42 kg / cm ² ).

Example 3 In Example 1, 100 parts by weight of calcium carbonate was mixed with a curable unsaturated polyester resin solution containing a photocuring agent and a thermosetting agent. The irradiation of the ultraviolet lamp was changed to 10 minutes to gel the above resin solution. Other than that, it carried out similarly to Example 1.

Also in this case, no destruction occurred at a tensile stress of 13 tons, and no delamination occurred. Also, no weeping (bleeding of water) occurred at a breaking water pressure (40 kg / cm ² ).

Comparative Example 1 A half mandrel having the same dimensions as the T-shaped mandrel used in Example 1 was prepared, and a glass fiber mat impregnated with a thermosetting resin solution was placed on the surface of the mandrel. A thermosetting resin liquid was impregnated by a lay-up method to produce a pipe-shaped half-core type core member.

The thermosetting resin liquid is composed of 100 parts by weight of an unsaturated polyester (Ester R235: manufactured by Mitsui Toatsu Co., Ltd.) and 0.7 part by weight of a thermosetting agent (Kayamec M: manufactured by Kayaku Akzo). The content of glass fiber roving was about 40% by volume. The thickness of the core member was 10 mm.

The half-shaped core members were joined to each other, and a resin-impregnated fiber roving was wound and laminated on the outer periphery thereof under the same conditions as in Example 1, and this was thermally cured to produce a cheese-type pipe joint.

In this case, no destruction occurred at a tensile stress of 13 tons, but delamination occurred. At the breaking water pressure (35 kg / cm ² ), weeping (water seepage) was observed from the joint portion of the half-shaped core member.

Comparative Example 2 A T-shaped mandrel which can be assembled and disassembled in the same manner as in Example 1 was prepared, and a thermosetting resin solution was applied to the surface of the mandrel with a brush to a thickness of about 1 mm. The thermosetting resin liquid is composed of 100 parts by weight of an unsaturated polyester (Ester R235: manufactured by Mitsui Toatsu) and 0.7 part by weight of a thermosetting agent (Kayamec M: manufactured by Kayaku Akzo). This was heated at 80 ° C. for 7 minutes and then allowed to stand for 20 minutes to gel the resin solution. Other than that, it carried out similarly to Example 1.

In this case, no breaking occurred at a tensile stress of 13 tons, and no delamination occurred. Also, no weeping (bleeding of water) occurred at a breaking water pressure (40 kg / cm ² ). However, it takes 27 minutes in total for heating and standing to gel the thermosetting resin liquid on the surface of the mandrel, which is lower in productivity as compared with the first embodiment. In addition, the degree of gelation was different for each product and was not stable.

[0038]

As described above, the method for producing a fiber-reinforced resin molded article of the present invention comprises applying a curable resin liquid containing a photo-curing agent and a thermo-curing agent to the surface of a mandrel and irradiating it with light. The curable resin liquid is gelled, and a roving fiber material impregnated with a thermosetting resin liquid is wound around the outer periphery and laminated,
This is a product that cures all the resin by heating it at room temperature or at room temperature, so that there is no generation of cracks or voids on the inner part of the molded product and no weeping in applications where internal pressure is applied by fluid. It can be manufactured stably with high productivity.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an embodiment of the present invention.

[Explanation of symbols]

 11 Roving fiber 12 Roving fiber 13 Roving fiber 11 'Resin impregnated roving fiber 12' Resin impregnated roving fiber 13 'Resin impregnated roving fiber 40 Resin impregnated roll 41 Impregnation tank 50 Traverse eye 60 Tape-shaped resin impregnated roving fiber 70 T-shaped mandrel .

Claims (3)

(57) [Claims] 1. A curable resin solution containing a photo-curing agent and a thermo-curing agent is applied to the surface of a mandrel, and the curable resin liquid is gelled by irradiating light onto the curable resin solution. A method for producing a fiber-reinforced resin molded product, comprising winding and laminating a roving fiber material impregnated with a liquid, and curing the resin at room temperature or by heating all the resin. 2. The method for producing a fiber-reinforced resin molded article according to claim 1, wherein a filler is contained in a curable resin liquid containing a photocuring agent and a thermosetting agent. 3. The method for producing a fiber-reinforced resin molded product according to claim 1, wherein the short glass fiber is contained in a curable resin liquid containing a photocuring agent and a thermosetting agent.