JPH02217231A - Fiber reinforced synthetic resin molded form and production thereof - Google Patents

Abstract

PURPOSE:To obtain a fiber reinforced synthetic resin molded form which is excellent in shaping properties and melt-sticking properties to thermoplastic resin and durability by impregnating reinforced fiber with the mixed resin liquid of thermosetting resin and thermoplastic resin. CONSTITUTION:Reinforced fiber 11 such as glass roving is arranged to the lengthwise direction and introduced into an impregnation tank 30. The reinforced fiber 11 is impregnated with the mixed resin liquid 14 of thermosetting resin 12 and thermoplastic resin 13 in the impregnation tank 30. This reinforced fiber 11 impregnated with the mixed resin liquid 14 is defoamed and regulated in thickness by a pair of pinch rolls 31. Thereafter it is passed through a heating and drying furnace 40 and therein curing reaction of thermosetting resin 12 contained in the mixed resin 14 is performed to obtain the fiber reinforced synthetic resin molded form 10.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fiber-reinforced synthetic resin molded article and a method for producing the same.

(Prior Art) Building materials such as eaves gutters are molded into long lengths from thermoplastic resin such as vinyl chloride resin and are widely used. However, such molded bodies of thermoplastic resin have large thermal expansion and contraction and low rigidity, and therefore have the disadvantage that they deform due to seasonal changes and temperature changes between day and night, and are susceptible to cracking.

In order to improve such drawbacks, for example, Japanese Patent Application Laid-Open No. 1986-
Publication No. 209560 discloses that a fiber mantle such as a glass fiber mat is impregnated with a thermosetting resin liquid such as an unsaturated polyester resin and then molded to form a core material, and this core material is passed through the crosshead of an extruder. A method for producing a fiber-reinforced synthetic resin molded article such as an eave gutter by introducing it into a mold and melt-extruding a thermoplastic resin such as vinyl chloride resin is disclosed.

(Problem to be Solved by the Invention) However, in the manufacturing method of such a fiber-reinforced synthetic resin molded article, the heat impregnated into the fibers is heated when the core material is shaped into the shape of an eaves gutter, etc. As the curing of the curable resin progresses, it is difficult to accurately bend it into the desired shape, and its formability is insufficient.Also, when coating such a core material with a thermoplastic resin by melt extrusion, the thermosetting resin in the core material and It is difficult to sufficiently fuse the thermoplastic resin coated on the core material, and when used for a long period of time, there is a problem that the core material cracks or peels between the eyebrows due to impact.

The present invention is intended to solve the above-mentioned problems, and its purpose is to provide a fiber-reinforced synthetic resin molded article that has excellent shaping properties and fusion properties with thermoplastic resins.

Another object of the present invention is to provide a fiber-reinforced synthetic resin molded article with improved deformation due to heat expansion and contraction, impact resistance, and glabellar peeling, and excellent durability, and a method for manufacturing the same.

(Means for Solving the Problems) The fiber-reinforced synthetic resin molded article of the present invention is obtained by impregnating reinforcing fibers with a mixed resin liquid of a thermosetting resin and a thermoplastic resin, and then molding the same. Further, the fiber-reinforced synthetic resin molded article of the present invention is formed by integrally covering a core material with a thermoplastic resin by impregnating reinforcing fibers with a mixed resin liquid of a thermosetting resin and a thermoplastic resin and molding the core material.

Furthermore, the method for manufacturing a fiber-reinforced synthetic resin molded article of the present invention includes impregnating reinforcing fibers with a mixed resin liquid of a thermosetting resin and a thermoplastic resin and molding the same to form a core material. It is characterized in that it is introduced into a crosshead mold of an extruder to melt the thermoplastic resin, and the thermoplastic resin is melt-extruded and coated and integrated.

With the above configuration, the object of the present invention is achieved.

Hereinafter, the present invention will be explained with reference to the drawings.

FIG. 1 is a partially cutaway sectional view showing an example of the fiber-reinforced synthetic resin molded article of the present invention. In FIG. 1, 11 is a reinforcing fiber, and as the reinforcing fiber 11, rovings, nonwoven fabrics, mats, woven fabrics, nets, etc., such as glass fibers, carbon fibers, alumina fibers, and aramid fibers are used.

The molded product of the present invention is generally formed into a long length, and thermal expansion and contraction in the longitudinal direction is a major problem in such a long product. When disposed, the linear expansion coefficient of the obtained molded body closely matches the theoretical value, so it is preferable to dispose a large number of rovings in the longitudinal direction as shown in the figure.

The reinforcing fibers 11 are impregnated with a liquid mixed resin 14 of the thermosetting resin 12 and the thermoplastic resin 13, and the reinforcing fibers 1111 are made of the mixed resin 14 of the thermosetting resin 12 and the thermoplastic resin 13. 14 to form the fiber-reinforced synthetic resin molded article IO of the present invention.

The fiber-reinforced synthetic resin molded body 10 described above is manufactured by the method shown in FIG.

In FIG. 3, reinforcing fibers 11 such as glass rovings are first arranged in the longitudinal direction and introduced into an impregnating tank 30. The reinforcing fibers 11 are usually defibrated by a defibrating tool before being introduced into the impregnating tank 30 or within the impregnating tank 30.

The reinforcing fibers 11 are impregnated with a mixed resin liquid 14 of a thermosetting resin 12 and a thermoplastic resin 13 in an impregnating bath 30 .

The mixed resin liquid 14 may include a thermoplastic resin 13 dissolved in a liquid thermosetting resin 12 (or a powder of the thermoplastic resin 13 dispersed in a liquid thermosetting resin 12). You can.

The reinforcing fiber 11 impregnated with the mixed resin liquid 14 is defoamed and its thickness adjusted by a pair of pinch rolls 31, and then passed through a heating drying oven 40, where the thermosetting resin 12 in the mixed resin 14 is cured. A reaction takes place.

The curing reaction of the thermosetting resin 12 may be carried out to obtain a semi-cured prepreg molded body, or may be carried out to obtain a completely cured molded body.

Moreover, the shape can be formed into a desired shape such as a sheet, eaves gutter, corrugated plate, decking material, etc.

In this way, a fiber-reinforced synthetic resin molded body 10 as shown in FIG. 1 is obtained.

The reinforcing fiber 11 is made of thermosetting resin 12 and thermoplastic resin 13.
Theoretically, it can be contained up to 90% by volume with respect to the mixed resin 14, but it is usually preferably used in a range of 60% by volume or less. The reinforcing fiber 11 is 60% of the mixed resin 14.
If the capacity percentage is exceeded, cracks are likely to occur due to impact.

Further, it is preferable that the thermoplastic resin 13 is included in the mixed resin 14 in a range of 2 to 50% by weight. Thermoplastic resin 1
If the content of 3 is less than 2% by weight, the shaping properties and the fusion properties with the thermoplastic resin coated thereon will deteriorate. on the other hand,
When the content of the thermoplastic resin 13 exceeds 50% by weight, the viscosity of the mixed resin liquid 14 increases significantly, making impregnation difficult.

As the thermosetting resin 12, unsaturated polyester resin,
Diaryl phthalate resin, epoxy resin, etc. are used. Such a thermosetting resin 12 usually contains a thermosetting agent such as an organic peroxide, a photocuring agent such as a benzoin derivative, and other accelerators.

Examples of the thermoplastic resin 13 include vinyl chloride resin, vinylidene chloride resin, olefin resin such as polyethylene and polypropylene, acrylic resin, ethylene-vinyl acetate copolymer resin, vinyl chloride-ethylene copolymer resin, and vinyl chloride-vinyl acetate copolymer resin. Polymer resin, vinyl chloride-vinyl acetate-maleic acid copolymer resin, vinyl chloride-acrylic copolymer resin, vinyl chloride-urethane copolymer resin, ethylene-
Graft resins in which vinyl chloride is grafted onto vinyl acetate copolymer resins, engineering resins such as polyamide resins, polyphenylene sulfide resins, and polyether sulfone resins are used.

FIG. 2 is a partially cutaway sectional view showing another example of the fiber-reinforced synthetic resin molded article of the present invention. In FIG. 2, 10 is a core material, and this core material 10 has the same structure as the fiber-reinforced synthetic resin molded body 10 shown in FIG. 1, and is indicated by the same reference numerals. Moreover, this core material 10 is manufactured by the method shown in FIG.

The core material 10 is integrally coated with a thermoplastic resin 21,
A fiber-reinforced synthetic resin molded body 20 of the present invention is formed. As the thermoplastic resin 21 coated on the core material 10, a resin similar to the thermoplastic resin 13 used for the mixed resin 14 described above, and a combination that can be thermally fused with the thermoplastic resin 13, is used. . For example, when the fiber-reinforced synthetic resin molded body 20 is an eaves gutter, both thermoplastic resin 13
．． As 21, a vinyl chloride resin having good weather resistance is preferably used.

Note that if the thermoplastic resin 21 to be coated contains fillers with a small coefficient of linear expansion such as inorganic salts such as calcium carbonate, metal powders such as aluminum, short glass fibers, and wood powder, the line with the core material 10 will be reduced. This is preferable because the difference in expansion coefficients is small.

The fiber-reinforced synthetic resin molded body 20 described above is manufactured by the method shown in FIG. 4.

In FIG. 4, first, a semi-cured prepreg molded body manufactured by the method shown in FIG. By the heating forming device 50,
It is heated and softened to a temperature higher than the softening temperature of the thermoplastic resin 13 in the mixed resin 14, and shaped into a desired shape such as an eaves gutter, a corrugated plate, or a deck material. If the curing is not completed, the curing reaction is completed in the curing furnace 60.

Subsequently, the shaped core material 10'' is introduced into a crosshead mold 70 of an extruder 71, where the thermoplastic resin 21 melted and extruded from the crosshead mold 70 is applied to the core material 10''.
coated on the outer surface of the At this time, the thermoplastic resin 13 in the core material 10° is melted in the crosshead mold 70, and the thermoplastic resin 21 to be melt-extruded and coated is fused and integrated.

The length of the land portion of the crosshead mold 70 is determined by the extrusion temperature,
The gap is appropriately determined depending on the extrusion speed, the resin used, etc., and the gap is designed to have a desired shape, and is formed into a desired shape such as eaves troughs, corrugated plates, decking materials, etc.

Thereafter, a sizing device 80 consisting of a cooling mold or the like performs surface finishing, is cooled, and is taken out by a tensioning device 90 such as a caterpillar tensioning machine.

In this way, a fiber-reinforced synthetic resin molded body 20 as shown in FIG. 2 is manufactured.

In addition, in FIG. 4, after being heated and softened and shaped into a desired shape by a heating forming device 50,
It is introduced into the crosshead mold 70 of the extruder. However, without using the heating forming device 50, the core material IO may be heated and softened and immediately introduced into the crosshead mold 70 of the extruder.

(Function) In the present invention, a fiber-reinforced synthetic resin molded article obtained by impregnating reinforcing fibers with a mixed resin liquid of a thermosetting resin and a thermoplastic resin and molding the same is a fiber-reinforced synthetic resin molded article in which only a thermosetting resin liquid is added to the reinforcing fibers. The thermoplastic resin softens better when heated and softened than those impregnated and molded, so it is easier to bend into the desired shape and has excellent formability. , it also has excellent fusion properties with this thermoplastic resin.

In addition, a fiber-reinforced synthetic resin molded product made by using the above-mentioned fiber-reinforced synthetic resin molded product as a core material and integrally covering this core material with a thermoplastic resin has improved deformation due to thermal expansion and contraction due to the reinforcing fibers, and the mixed resin The impact resistance is improved by the ductility effect of the thermoplastic resin inside and by uniformly dispersing the thermosetting resin and the thermoplastic resin to form a microscopic seabird structure.

Furthermore, the reinforcing fibers are impregnated with a mixed resin liquid of thermosetting resin and thermoplastic resin to form a core material, and when this core material is introduced into the crosshead mold of the extruder, the thermoplastic resin in the core material is well melted by the heat of both the crosshead mold and the heat of the thermoplastic resin melt-extruded from this mold, and adheres well to the reinforcing fibers. Moreover, the thermoplastic resin extruded from the crosshead mold is strongly pressed against the thermoplastic resin in the core material by extrusion pressure, and is completely fused and integrated.

(Example) Examples and comparative examples of the present invention are shown below.

First, glass roving (14400: manufactured by Nittobo)
The O was defibrated and introduced into the impregnation tank 30 in a large number of strips arranged in the longitudinal direction, where unsaturated polyester resin ($75
10: 80% by weight of 12 (manufactured by Nippon Upica) and 1 of vinyl chloride-vinyl acetate-maleic acid copolymer resin (manufactured by Tokuyama Sekisui)
A mixed resin liquid 14 containing 20% by weight of 3 is impregnated with a solution in which benzoyl peroxide is added, and after passing through a pair of pinch rolls 31, this is heated to 120°C in a heating drying oven 40 to be cured. A fiber-reinforced synthetic resin molded article 10 was manufactured.

The obtained fiber-reinforced synthetic resin molded body 1o has a thickness of 0.5
m, width 300 InI11, glass roving content 6° volume %.

Next, the above fiber-reinforced synthetic resin molded body 1o is formed into a core material 10.
This core material 1o is formed into a rectangular eave gutter shape at 80 to 100°C using a heating forming device 50, passed through a curing furnace 60, and then passed through a crosshead mold 7 of an extruder 71.
A vinyl chloride resin containing a stabilizer and the like was melt-extruded on the surface at 170''C to a thickness of 0.5IllII+ to form an integral coating.

Thereafter, the surface was finished using a sizing device 8o, and the product was cooled and taken out using a tensioning machine 9o to produce a fiber-reinforced synthetic resin molded article 20 in the shape of a long eave gutter having a thickness of 1.51 cm.

The line speed at this time was 3a+/min. Further, the above-mentioned crosshead mold 70 used had a land length of 2° Oa+ and a rectangular gutter-like gap.

Thermal stretchability, impact resistance, and durability of this fiber-reinforced synthetic resin molded body 2o were evaluated by the following methods. The results are shown in Table 1.

(1) A heat-stretchable fiber-reinforced synthetic resin molded body is cut into a length of 4111 to obtain a test piece, placed in a constant temperature constant temperature room, and the length tzo at 20"C is measured, and then at 60"C. Raise the temperature to 60
The length L6° at °C was measured, and the linear expansion coefficient α was calculated using the following formula. α・(L6゜-L2゜)/(40'CXLzo
)・(2) A test piece was created by cutting the impact-resistant fiber-reinforced synthetic resin molding into 20w x 20aw*, and a 1.5 kg weight was dropped onto this test piece using a DuPont impact tester, and the test piece was tested. The impact strength was measured from the falling distance at which the product broke.

(3) Durability The fiber-reinforced synthetic resin molded body was cut into 1 m length to make a test piece, and after conducting 1000 cycles of heating and cooling tests at -10 to 70°C in a thermostatic room, the test piece was was cut, and its cross-sectional state was observed using an electron microscope.

In addition, the test piece before and after the above test was 20 mm wide,
It was cut into a length of 200M, and the end of the coating layer on one side was peeled off to measure the T-peel strength, and the strength after the test was expressed as the adhesion retention rate relative to the strength before the test.

In Example 1, 20% by weight of vinyl chloride-vinyl acetate maleic acid copolymer resin was added to polyvinyl chloride resin (TS-
1000R (manufactured by Tokuyama Sekisui Co., Ltd.) was changed to 20% by weight, but in the same manner as in Example 1, a fiber-reinforced synthetic resin molded body 20 having a thickness of 1.5 mm and a long eave gutter shape was manufactured.

This fiber-reinforced synthetic resin molded body 20 has thermal elasticity,
Impact resistance and durability were evaluated. The results are shown in Table 1.

1 cliff penetration 1 Example 1 except that the core material 11 obtained by heating to 80°C and semi-curing was used instead of heating to 120°C in the heating drying oven 40 in Example 1. Go in the same way as
A fiber-reinforced synthetic resin molded body 20 in the shape of a long eave gutter having a thickness of 1.5 m+w was manufactured.

This fiber-reinforced synthetic resin molded body 20 has thermal elasticity,
Impact resistance and durability were evaluated. The results are shown in Table 1.

In Example 1, the vinyl chloride-vinyl acetate maleic acid copolymer resin 13 was not mixed at all, and only the unsaturated polyester resin 12 was used, and the thickness of the core material 10 was 0.9.
The same procedure as in Example 1 was carried out except that the diameter was set to mm.

The obtained elongated eaves gutter-shaped fiber-reinforced synthetic resin molded article was evaluated for thermal elasticity, impact resistance, and durability. The results are shown in Table 1.

Table 1 In addition, in the T-peel strength measurement of the test pieces before and after the cold test, it was impossible to peel off any of the test pieces of Examples 1 to 3. Further, the test piece of Comparative Example 1 had a T-peel strength of 2 kg/cm before the cold/hot test.

(Effects of the Invention) As described above, the fiber-reinforced synthetic resin molded article of the present invention, which is obtained by impregnating reinforcing fibers with a mixed resin liquid of a thermosetting resin and a thermoplastic resin and molding the same, can be formed into a desired shape precisely. It is easy to bend, has excellent shapeability, and also has excellent fusion properties with thermoplastic resins.

In addition, the fiber-reinforced synthetic resin molded product of the present invention, which is formed by using the above-mentioned fiber-reinforced synthetic resin molded product as a core material and integrally covering this core material with a thermoplastic resin, has improved deformation and impact resistance due to thermal expansion and contraction. Ru.

Further, in the fiber-reinforced synthetic resin molded article obtained by the method of the present invention, the core material and the thermoplastic resin coated thereon are strongly fused, and delamination is improved. Therefore, even if it is used for a long time in an environment with severe temperature changes, it will not deform, crack, or peel between layers, and has excellent durability.

[Brief explanation of the drawing]

FIG. 1 is a partially cutaway sectional view showing an example of the fiber-reinforced synthetic resin molded article of the present invention, and FIG. 2 is a partially cutaway sectional view showing another example of the fiber-reinforced synthetic resin molded article of the present invention. FIG. 3 is a schematic diagram showing an example of a method for manufacturing the fiber-reinforced synthetic resin molded product shown in FIG. 1, and FIG. 4 is a schematic diagram showing an example of the manufacturing method for the fiber-reinforced synthetic resin molded product shown in FIG. be. 10...Fiber-reinforced synthetic resin molded body (core material), 11...
- Reinforcing fiber, 14... Mixed resin of impregnated thermosetting resin and thermoplastic resin, 20... Fiber-reinforced synthetic resin molded body, 21... Covered thermoplastic resin, 30...
Impregnation tank, 40... Heating drying oven, 50... Forming device, 60... Curing oven, 70... Crosshead mold of extruder, 80... Sizing device, 90... Tensioning device .

Claims (1)

[Claims] 1. A fiber-reinforced synthetic resin molded article obtained by impregnating reinforcing fibers with a mixed resin liquid of a thermosetting resin and a thermoplastic resin and molding the same. 2. A fiber-reinforced synthetic resin molded article made by integrally covering a core material with a thermoplastic resin by impregnating reinforcing fibers with a mixed resin liquid of a thermosetting resin and a thermoplastic resin and molding the same. 3. Impregnate the reinforcing fibers with a mixed resin liquid of thermosetting resin and thermoplastic resin, mold this to form a core material, introduce this core material into the crosshead mold of the extruder, and mold the above thermoplastic resin. A method for producing a fiber-reinforced synthetic resin molded article, which comprises melting a resin and melting and extruding a thermoplastic resin to coat and integrate the resin.