JPH02184435A - Manufacture of long composite molded object - Google Patents

Abstract

PURPOSE:To prevent the deformation due to thermal expansion and contraction and to improve rigidity and impact resistance by dispersing a number of hollow particles in the synthetic resin of a core layer or in the synthetic resin on both surfaces of the core layer. CONSTITUTION:A long composite formed object A is composed of a core layer 10 and a skin layer 20. The core layer 10 is composed of a reinforcing layer 11, synthetic resin 12 and a number of hollow particles 13. A number of hollow particles 13 are dispersed in the synthetic resin on both surfaces of the core layer 10. As the synthetic resin 12, the thermosetting resin such as unsaturated polyester resin and diallylphthalate resin are used. The reinforcing fiber is mixed in the range of at most 60vol% with the synthetic resin 12. As the hollow particle 13, the organic hollow particle such as acryl resin ballon, styrene resin ballon or the inorganic hollow particle such as glass ballon and shirasu ballon, is used. The particles has the average diameter of 30-200mum and is contained in the resin in the range of 5-50vol% to the surface of the core layer 10.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a long composite molded article with improved heat expansion/contraction, rigidity, and impact resistance and excellent durability, and a method for producing the same.

(Prior Art) Building materials such as rain gutters are molded into long lengths from thermoplastic resin such as vinyl chloride resin and are widely used.

However, such thermoplastic resin molded articles have the disadvantage that they are susceptible to thermal expansion and contraction (low rigidity), so they deform due to seasonal changes and temperature changes between day and night, and are prone to cracking.

As a molded product that has improved these drawbacks, we have developed a molded product in which a core material layer in which reinforcing fibers are fixed with a synthetic resin such as an unsaturated polyester resin is covered with an outer skin layer of a thermoplastic resin such as vinyl chloride resin. Long composite molded bodies such as gutters have been proposed (Japanese Unexamined Patent Application Publication No. 58-209560, Utility Model Application No. 59-1999)
(See Publication No. 147823).

(Problems to be Solved by the Invention) However, although such long composite molded articles are well improved in thermal expansion and contraction, the improvement in impact resistance is insufficient, and they cannot be used for long periods of time. If so, there is a problem that the core material layer may crack or delaminate due to impact.

The present invention is intended to solve the above-mentioned problems, and its purpose is to provide a long composite molded article with improved deformation due to thermal expansion and contraction, rigidity, and impact resistance, and excellent durability, and a method for manufacturing the same. It is about providing.

(Means for Solving the Problems) A long composite molded article of the present invention is a long composite molded article in which a core layer in which reinforcing fibers are fixed with a synthetic resin is covered with an outer skin layer of a thermoplastic resin. It is characterized in that a large number of hollow particles are dispersed in the synthetic resin of the core material layer or in the synthetic resin of both surfaces of the core material layer.

In addition, the method for producing a long composite molded article of the present invention involves passing reinforcing fibers through a synthetic resin liquid in which a large number of hollow particles are suspended, and producing two sheets of synthetic resin-impregnated fibers in which a large number of hollow particles are dispersed on one side. The other sides of this synthetic resin-impregnated fiber material are bonded together to form a core material layer in which a large number of hollow particles are dispersed in the synthetic resin on both sides, and the core material layer is coated with a thermoplastic resin. It is characterized by forming an outer skin layer.

The above configuration achieves the above object.

The present invention will be described below with reference to the drawings.

FIG. 1 is a partially cutaway perspective view showing an example of the elongated composite molded article of the present invention, and FIG. 2 is an enlarged view of the part (A) in FIG. 1.

In FIGS. 1 and 2, A is a long composite molded body of an eaves gutter, and is composed of a core layer 10 and an outer skin layer 20. The long composite molded body A may be made into a desired shape such as a corrugated plate, a decking material, etc. in addition to eaves gutters.

As shown in FIG. 2, the core material layer 10 is composed of reinforcing fibers 11, synthetic resin 12, and a large number of hollow particles 13. A large number of hollow particles 13 are dispersed in the synthetic resin 12 on both sides of the core layer 10. Many hollow particles 1
3 is a synthetic resin 12 on both sides of the core layer 10 as shown in the figure.
Although it is preferable that the synthetic resin 12 of the core material layer 10 be dispersed therein, it may be dispersed over the entire surface of the synthetic resin 12 of the core material layer 10.

The reinforcing fibers 11 include rovings such as glass fibers, carbon fibers, alumina fibers, and aramid fibers, nonwoven fabrics,
Mats, woven fabrics, nets, etc. are used.

Thermal expansion and contraction in the longitudinal direction is a major problem in elongated bodies, and in particular, when roving is used as the reinforcing fiber 11 and a large number of rovings are arranged in the longitudinal direction as shown in the figure, the resulting elongated composite molded body A In the present invention, it is preferable to arrange the rovings in the longitudinal direction since the coefficient of linear expansion closely matches the theoretical value.

The reinforcing fibers 11 are fixed with a synthetic resin 12, and as the synthetic resin 12, a thermosetting resin such as an unsaturated polyester resin, diallyl phthalate resin, epoxy resin, urethane resin, or phenol resin is used. A thermosetting agent, a photocuring agent, and other accelerators are usually added to this thermosetting resin.

Moreover, as the synthetic resin 12 for fixing the reinforcing fibers 11,
Vinyl chloride resin, vinylidene chloride resin, acrylic resin,
Thermoplastic resins such as vinyl acetate resin, ethylene-vinyl acetate copolymer resin, and olefin resin are also used.

It is generally preferable to use the reinforcing fiber 11 in an amount of 60% by volume or less based on the synthetic resin 12. When reinforcing fiber is used at 60% or more by volume of synthetic resin,
Cracks and delamination of the core material layer are likely to occur due to impact.

The hollow particles 13 dispersed in the synthetic resin 12 of the core material layer 10 are organic hollow particles such as acrylic resin balloons, styrene resin balloons, and phenolic resin balloons, or inorganic hollow particles such as glass balloons, shirasu balloons, and ceramic balloons. Hollow particles are used.

The above hollow particles 13 generally have an average particle size of 30 to 200.
Generally, 5 μm is used for the core material layer 10.
It is preferably contained in a range of 50% by volume. If it is less than 5% by weight, the effect of improving impact resistance is small, while if it is more than 50% by volume, adhesion of the hollow particles becomes poor and desired physical properties cannot be obtained.

The core material layer 10 is coated with an outer skin layer 20 of thermoplastic resin. As the thermoplastic resin for the outer skin layer 20, vinyl chloride resin, vinylidene chloride resin, acrylic resin, olefin resin such as polyethylene or polypropylene, polyamide resin, engineering resin such as polyphenylene sulfide or polyether sulfone, etc. are used.

Note that the outer skin layer 20 contains an inorganic salt such as calcium carbonate,
It is preferable to include metal powder such as aluminum, short glass fiber, or wood powder as a filler having a small linear expansion coefficient.

Although the core material layer 10 and the outer skin layer 20 may be directly bonded, it is preferable that they be bonded via a synthetic resin adhesive 30 as shown in the figure. As the synthetic resin adhesive 30, curable adhesives such as epoxy, urethane, and acrylic adhesives, hot melt adhesives such as ethylene-vinyl acetate, polyester, and polyamide are used.

Note that it is preferable that such an adhesive 30 contains a filler similar to that described above. (Thus, the elongated composite molded article A of the present invention is constructed.

FIGS. 3 and 4 are explanatory diagrams showing an example of the method for manufacturing the elongated composite molded body A of the present invention.

In FIG. 3, first, a liquid synthetic resin 12 is put into an impregnating tank 40, and a large number of hollow particles 13 are suspended in the liquid synthetic resin 12 in a portion of the impregnating tank 40 partitioned by guide rolls 41 and 42. .

Next, a large number of rovings 11 are fed out from the left and right bobbins, arranged in a large number of rows in the longitudinal direction, immersed in a resin liquid, passed under a pair of guide rolls 41 and 42, and pulled up. Two sheets of synthetic resin-impregnated fiber material 14 in which particles 13 are dispersed are obtained. These two sheets of synthetic resin 12 and miscellaneous materials 14 are bonded together using a pair of pinch rolls 50 and dried in a drying oven 60 to form a sheet 1-shaped prepreg 10.
Get ゛.

In Fig. 4, the above sheet-like prepreg 10゛ is
First, the roll forming device 60
The core material layer 1 is heated and softened in C, shaped into a square eaves gutter shape, and then hardened, and then completely hardened in a thermosetting zone 61 to form a core material layer 1 in which a large number of hollow particles 13 are dispersed in the synthetic resin 12 on both sides.
form 0.

Next, the real melt adhesive 30 is applied to the outer surface of this gutter-shaped core material layer 10 using a hot melt coating device 70 equipped with a coating mold, and then introduced into a crosshead mold 71 of an extruder. Coated by melt extrusion of thermoplastic resin,
An outer skin layer 20 is formed.

After that, surface finishing is performed using the sizing device 80.
It is cooled and taken over by a ratchet tensioner 90 to produce a long eave gutter composite molded body A. In this way, the elongated composite molded article A of the present invention is obtained.

In the above method, the synthetic resin 12 on both sides of the core layer 10
A large number of hollow particles 13 are dispersed therein to obtain a long composite molded body A. However, without suspending a large number of hollow particles 13 in the liquid material of the synthetic resin 12 in the impregnation tank 40, the liquid material is stirred and a large number of hollow particles 13 are dispersed. By uniformly mixing and dispersing the hollow particles 13 in the liquid material of the synthetic resin 12, a long composite molded body in which a large number of hollow particles 13 are dispersed throughout the synthetic resin 12 of the core layer IO can be obtained. .

(Function) In the elongated composite molded article of the present invention, the core layer is reinforced with reinforcing fibers, and the overall rigidity is high and the coefficient of linear expansion is low. However, a large number of hollow particles in the resin of the core material layer are dispersed between the reinforcing fibers, and the impact is absorbed by these hollow particles. In particular, the effect becomes greater when a large number of hollow particles are dispersed in the resin on both sides of the core layer. Furthermore, the presence of a large number of hollow particles reduces thermal conductivity, which reduces temperature changes and reduces repeated stress.

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

In this example, a long composite molded body not shown in FIGS. 1 and 2 was manufactured by the method shown in FIGS. 3 and 4.

First, benzoyl peroxide (
A resin liquid for impregnation was prepared by mixing 2 parts by weight of Percure 0 (manufactured by Nippon Oil & Fats).

Pour this resin liquid into an impregnating tank, and place a Shirasu balloon (Zanquilite Y02) in the part of the impregnating tank partitioned by guide rolls.
Glass rovings (#4400, manufactured by Nittobo Co., Ltd.) arranged in large numbers in the longitudinal direction are immersed in this resin liquid, passed under guide rolls, and pulled up and dried.
Thickness 1.1mm, width 300mm, glass roving content 27.3% by volume, glass balloon content 27.3
A sheet-like prepreg with a volume of % was obtained.

The central 0.5 mm of this sheet-like prepreg is composed of resin and glass roving, and the 0.3 m both sides of the central part are made of resin and glass roving.
m was composed of resin, glass roving, and shirasu balloon.

The above sheet-like prepreg was softened by heating at 60 to 80°C using a roll forming device, shaped into a square eaves gutter shape, and then cured, and then completely cured in a thermosetting zone to form a core material layer. .

Next, an ethylene-vinyl acetate-based hotmel I-type adhesive (Takemelt XM223
: manufactured by Takeda Pharmaceutical Co., Ltd.) was applied to a thickness of 50 μm at 170°C.

After that, the resin was introduced into the crosshead mold of the extruder, and the vinyl chloride resin mixed with stabilizers was heated at 180°C.
The coating was melt-extruded and coated to a thickness of 0.15 mm to form an outer skin layer.

Thereafter, the surface was finished using a sizing device, cooled, and pulled out using a tensioning machine to produce a long eaves/gutter composite molded product with a thickness of approximately 1.4 mm. The line speed at this time was 3 m/min.

Thermal stretchability and impact resistance of this eave gutter composite molded article were evaluated using the following methods. The results are shown in Table 1.

(1) A heat-stretchable eaves gutter molded body was cut into a length of 4 m to make a test piece, and this was placed in a constant temperature constant temperature room and the length L2° was measured at 20°C.
Next, increase the temperature to 60°C and length L6 at 60°C.
0 was measured, and the linear expansion coefficient α was calculated using the following formula. α-(L
+, o Lzo)/(40°CXLzo).

(2) Cut the impact-resistant eaves gutter molding into 20 mm x 20 mm to create a test piece, and test this test piece with a DuPont impact tester at 1°5.
A weight of 1 kg was dropped, and the impact strength was measured from the falling distance at which the test piece was damaged.

Implementation Inhibition Lambda A long eave gutter with a thickness of about 1.4 mm was prepared in the same manner as in Example 1, except that a styrene resin balloon (manufactured by Block Plastics Co., Ltd.) was used in place of the shirasu balloon. A composite molded body was produced.

In this case, the thickness of the core material layer is 1.1mm, the glass low pink content is 27.3% by volume, the white balloon content is 27.3% by volume, and the center 0.5mm is composed of resin and glass roving. The length of 0.3 mm on both sides was adjusted to consist of resin, glass roving, and glass balloon.

Table 1 shows the evaluation results of heat stretchability and impact resistance of this eave gutter composite molded product.

In Example 1, except that the shirasu balloons were not suspended in the unsaturated polyester resin, a resin liquid was used in which the shirasu balloons were mixed and stirred into the unsaturated polyester resin, defoamed, and uniformly dispersed. In the same manner as in Example 1, shirasu balloons were dispersed throughout the resin of the core material layer to produce a long eaves/gutter composite molded body with a thickness of about 1.4 mm.

In this case, the thickness of the core material layer was adjusted to 1.1 mm, the glass low pink containing N content was adjusted to 27.3% by volume, and the content of the shirasu balloon was adjusted to 27.3% by volume.

Table 1 shows the evaluation results of heat stretchability and impact resistance of this eave gutter composite molded product.

In Example 3, the procedure was carried out in the same manner as in Example 3, except that styrene resin balloons were used instead of shirasu balloons, and the styrene resin balloons were dispersed throughout the resin of the core material layer, and the thickness was A long eave gutter composite molded body of approximately 1.4 mm was manufactured.

In this case, the thickness of the core layer was adjusted to 1.1 mm, the glass roving content was adjusted to 27.3% by volume, and the glass balloon content was adjusted to 27.3% by volume.

Table 1 shows the evaluation results of heat stretchability and impact resistance of this eave gutter composite molded product.

Example 1 In Example 1, the procedure was carried out in the same manner as in Example 1 except that no shirasu balloons were used in the unsaturated polyester resin. 1.4. A eave gutter composite molded body having a length of mmO was manufactured.

In this case, the thickness of the core material layer was adjusted to 1.1 mm, and the glass roving content was adjusted to 27.3% by volume.

Table 1 shows the evaluation results of heat stretchability and impact resistance of this eave gutter composite molded product.

Table 1 (Effects of the Invention) As mentioned above, in the long composite molded article of the present invention, since the core material layer is reinforced with reinforcing fibers, thermal expansion and contraction as a whole is small, and deformation and rigidity due to temperature changes are improved. . In addition, a large number of hollow particles are dispersed in the resin of the core material layer, especially in the resin on both sides of the core material layer, so the effect of these hollow particles improves impact resistance, and also in environments with severe temperature changes. Even when used over a long period of time, the repeated stress generated is small, so deformation, cracking, and delamination do not occur, and the durability is good.

Further, according to the method of the present invention, it is possible to easily produce a long composite molded article in which a large number of hollow particles are dispersed in the resin on both sides of the core layer.

[Brief explanation of the drawing]

FIG. 1 is a partially cutaway perspective view showing an example of the elongated composite molded article of the present invention, and FIG. 2 is a partially cutaway perspective view showing part (A) of FIG. 1, 60...Roll forming device, 61...Thermosetting Zone, 70・
...Hot melt coating device, 71...Crosshead mold, 80...Sizing device, 90...Catapillar tensioning machine.

Claims (1)

[Scope of Claims] 1. In a long composite molded article in which a core material layer in which reinforcing fibers are fixed with a synthetic resin is covered with an outer skin layer of a thermoplastic resin, a large number of fibers are contained in the synthetic resin of the core material layer. A long composite molded article characterized by dispersing hollow particles. 2. In a long composite molded article in which a core material layer in which reinforcing fibers are fixed with a synthetic resin is covered with an outer skin layer of a thermoplastic resin, a large number of hollow particles are contained in the synthetic resin on both sides of the core material layer. A long composite molded body characterized by being dispersed. 3. Pass the reinforcing fibers through a synthetic resin liquid in which many hollow particles are suspended to make two sheets of synthetic resin-impregnated fiber material with many hollow particles dispersed on one side. The other surfaces are bonded together to form a core material layer in which a large number of hollow particles are dispersed in a synthetic resin on both sides, and the core material layer is coated with a thermoplastic resin to form an outer skin layer. A method for producing a long composite molded body.