JPS5929156A - Reinforced thermoplastic resin laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

The present invention also relates to a reinforced thermoplastic resin laminate having a strength equal to or less than 1 by laminating a fiber-reinforced thermosetting resin layer on a thermoplastic resin molded body. Reinforced thermoplastic resin molded articles have excellent physical properties that thermoplastic resins have, such as corrosion resistance and anti-wear properties; It has the advantages of having weather resistance and creep resistance, as well as being lightweight and economical.Therefore, it is widely used in chemical industry materials, water piping materials, reactors, etc. Although the mechanical strength of the laminate can be expected to be the sum of the respective mechanical strengths of the thermoplastic resin molded body and the fiber-reinforced thermosetting resin layer,
In reality, the mechanical strength is not even close to that of a thermoplastic resin molded body alone.3 In order to improve the mechanical strength, = j$ r
A single layer of polyuretano-based F limer provided between the iJ plastic resin molding and the fiber-reinforced thermosetting resin layer has also been used, but even if it can achieve a certain degree of improvement, it is not necessarily 1 minute. stomach. An object of the present invention is to solve the problems of the prior art described in - and to provide a reinforced thermoplastic resin laminate having excellent mechanical strength. To summarize the present invention, the reinforced thermoplastic resin laminate of the present invention is a reinforced thermoplastic resin laminate in which a thermoplastic resin molded body is reinforced with a fiber-reinforced thermosetting resin layer. It is characterized in that a rubber elastic layer containing a thickness maintaining material is provided between the thermosetting resin layer and the thermosetting resin layer, which has adhesive properties on both sides. The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, have discovered the following facts and arrived at the present invention. In other words, the mechanical strength of the reinforced thermoplastic resin laminate is not the sum of the mechanical strengths of the thermoplastic resin molded body and the fiber-reinforced thermosetting resin layer, but rather the thermoplastic resin molded body alone. The reason why the mechanical strength of υ is also significantly inferior is that
For directly forming and laminating a semi-hardening resin layer on a thermoplastic resin molded body; for example, unsaturated polyester resin is applied thinly to one side of a polyvinyl chloride resin test piece, then cured and laminated. The bending strength, Fi, and impact strength of the polyvinyl chloride resin test piece were significantly lower than those of the polyvinyl chloride resin test piece alone. In this case, the elongation on the side where the unsaturated polyester resin is laminated is t? t. If the test piece is suddenly bent with this side facing outward, the unsaturated polyester resin layer will be cut and the entire test piece will break. In other words, instantaneous notch effect occurs in the polyvinyl chloride resin layer by cutting the rigid unsaturated polyester resin layer (a phenomenon in which the strength decreases due to the concentration effect when stress is applied due to the presence of notches). This causes the entire test piece to break, and even in the case where the fiber-reinforced unsaturated polyester resin J- is directly laminated onto the polyvinyl chloride resin molded body, the mechanical strength of the reinforced thermoplastic resin laminate is This phenomenon also occurs when an F* layer of unsaturated polyester resin or other thermosetting resin is applied to a thermoplastic resin molded product other than a polyvinyl chloride resin molded product. Based on one or more of the above facts, the present inventors also tried providing a single layer of primer such as polyurethane as an intermediate layer as described above, but satisfactory mechanical strength could not be obtained (comparative example described below). Therefore, the present inventors conducted further studies and focused on using a specific material for the intermediate layer (1. First, a thermal T3J plastic resin molded product, a thickness-maintaining molded rubber elastic material as a specific monthly charge). By gluing the body layer and then coating and laminating only a thermosetting resin on it, the bending strength and impact strength of the reinforced thermoplastic resin laminate are higher than that of the thermoplastic 4☆1 resin test piece. In other words, when the thermosetting resin layer was bent outward by 17 degrees (1+11), a cut surface appeared on a part of the thermosetting resin layer. However, the cut did not propagate at all to the rubber elastic layer containing the thickness retaining material, and the entire laminate corresponded to one bend, and no folding occurred. etc. have developed the present invention into a complete history,
l, l Komono,) 11 is held; (entering gono,
Place an elastic body at the interface, (piece + 1111 iC heat jj J
When the fiber-reinforced thermosetting resin was bonded to another IHL, the mechanical strength of the resulting reinforced thermoplastic resin laminate was determined by

[
- It turns out that it is the sum of the mechanical strength of both [Also. In the thermal i3J plastic resin and 1.7 according to the present invention, poly f
n-pyrene, high, medium or low density 1 button polyethylene. Super polymer M: polyolefin such as polyethylene and polype/thene, nylon 6, nylon 11, nylon 12,
Homo- or polyamides such as nylon 6,6 and nylon 6.10, saturated polyesters such as polyethylene terephthalate and polyethylene terephthalate, J3 base resins such as polyvinyl chloride and chlorinated polyvinyl chloride, polycarbonate, polymethyl methacrylate and polyphenylene Oxylides and the like can be mentioned. Further, examples of molded bodies of these resins include sheets, containers, pipes, joints, and flanges, but the shape is not limited to Ih as long as it meets the purpose of the present invention. Thickness maintaining materials in the present invention include, for example, glass, carbon, polyacrylonitrile, -r setter I phosphoric acid, nylon, polyester fibers, linen, cotton, etc. , woven fabrics or non-woven fabrics such as silk and cellulose, and porous bodies such as ti:L;fl+paper, which constitute the rubber elastic layer in the present invention. The structure is formed by penetrating it with a type of adhesive. In addition, as the rubber adhesive for the elastic layer in the present invention, Nitrile Rubo!・Adhesive, Borik "] Rosoleno rubber adhesive, Butyl rubber adhesive Urethane rubber adhesives, natural comb adhesives, rubber thread acrylic acid, high grade esters, etc. can be mentioned, and when used, they can further improve the heat resistance and strength retention of the reinforced ifi II T plastic resin laminate of the present invention. It is desirable for the thermosetting resin layer to adhere to both the thermoplastic resin molded body and the fiber-reinforced thermosetting resin layer, and to prevent curing. As a thermosetting resin for the resin layer forming material, t''21, for example, t1
! Examples include Japanese polyester resin, phenol resin, Evokin resin, urea resin, melamine (☆1 resin, diallyl phthalate resin, alkyd resin, silicone resin, and polyimide resin), and by reinforcing these with various fibers in a conventional manner. It can be applied as a fiber-reinforced thermosetting resin.The rubber elastic body containing a thickness retaining material (hereinafter referred to as a gono-based adhesive), which plays an effective role in the present invention, has the following effects. (1) As mentioned above, by using this as an intermediate layer, it is possible to prevent the fiber-reinforced thermosetting resin layer from directly adhering to the surface of the thermal nJ plastic resin molding.1-1 Heat i
It is possible to prevent a decrease in the mechanical strength of the jT plastic resin molded body. (2) The effect of (1) can be achieved by using a rubber adhesive to bond the thermoplastic resin molded base and the fiber-reinforced thermosetting resin layer with sufficient strength. (3) Heat n]' When applying a thermosetting adhesive to the surface of the plastic resin molding and then bonding the fiber-reinforced thermosetting resin layer while the adhesive is still unsolidified, pressurize the adhesive. Therefore, sufficient adhesion force cannot be obtained unless the layer is given 41%. A strange phenomenon occurs. However, since the thickness maintaining material in the present invention is sufficiently impregnated with a viscous rubber adhesive, the interfacial tension of the material prevents the fiber-reinforced thermosetting resin layer (ji' RP l@) from being strongly applied. It can withstand pressure, and the thickness of the adhesive layer can be controlled to a desired constant thickness. (4) By using a material with a high Young's modulus and strength as the thickness maintaining material, it can serve to improve the mechanical strength of the rubber elastic layer. Reinforced thermoplastic resin laminate of the present invention t'2, front t'46
F... As a result, the total mechanical strength of the thermoplastic resin molded body and the fiber-reinforced thermosetting resin layer (-1) has been significantly improved, and the strain stress at the joint due to large expansion and contraction of the thermoplastic resin molded body has been significantly improved. In the following, the present invention and its effects will be specifically explained with reference to Examples and Comparative Examples, but the present invention is not limited to these in any way. Hydraulic fracture strength gradient 2 was measured by the following test method: (1) Civil Ruby Impact Test Method
A rectangular parallelepiped-shaped specimen with a width of 10 and a thickness of 10 gates) was prepared, and this was prepared according to the Japanese Industrial Standards (, 1, [SK 711
1) Using a VC standard σ Redan Jarby impact tester,
Mounted horizontally on a supporting base with a distance between fulcrums of 60 bolts and fixed 1
- The heat of the test piece is applied by hammer VC at the center between
Hit from the J plastic resin molded body ntu. 'A! The test piece breaks! Add the energy I for -j' to d and divide this by the original cross-sectional area to find the impact value. (2) Hydrostatic rupture test method drawing It is a longitudinal cross-sectional schematic diagram of the water pressure rupture test equipment used in this example, where 1 is a fiber-reinforced thermosetting resin layer, 2 is a rubber elastic body containing a thickness retaining material. layer, 6 is a thermoplastic resin acid body, 4t side 1 is a jig for water pressure fracture testing, 5 is a jig for preventing water leakage, 6 is water, and 7 is water pressure. A jig is attached to the obtained tubular molded product as shown in the drawing, and at this time, water (2[1'C) is placed inside the tubular molded product (i).The test under load is , in the center of the tubular molded product, with a load of Fiso edge if the tubular molded product has a nominal capacity of 50 rrrm, 75 in the case of 75 darkness, and ILJOKg in the case of 9.100 capacity. Increase the water pressure at a speed of 10 kg/6 m2 per minute (H) and measure the water pressure when the pipe breaks. (thickness o, 5 mm), and further, on the outside thereof, four layers (two layers thick) of glass cloth impregnated with an unsaturated polyester resin (Polyani h P-6845N manufactured by Motakata Toyo Kogyo Co., Ltd.) were laminated. This at 20℃
8 hours broadcast 1~. 1-, the unsaturated polyester resin was completely cured σ to obtain the intended reinforced polyvinyl chloride pipe. A↓The results of all measurements of glossy ruby impact strength and hydraulic fracture resistance of smooth reinforced polyvinyl chloride pipes are shown in Table 1 below. Comparative Example 1 A polyurethane resin sealer (manufactured by Hikari Yoki Kogyo Co., Ltd., Bionianoler) was applied to a polyvinyl chloride pipe (manufactured by Asahi Yokuzai Kogyo Co., Ltd.) with a nominal diameter of 50 mm, a wall thickness of 4.5 mm, and a length of 82 N+. , were laminated (thickness: 15 mm) and cured at room temperature for 2 hours.Next, on the outside thereof, 4 layers (thickness: 2 mm) was laminated.
The unsaturated polyester resin was left to stand for 48 hours at 0°C to completely cure the unsaturated polyester resin, thereby obtaining a reinforced polyvinyl fluoride tube 'f;C. Charpy Fii of the obtained reinforced polyvinyl chloride tube
! The results of measuring the strength and water pressure resistance ItC are shown in Table 1 below. Examples 2 to 6 Use (nominal diameter of polyvinyl chloride pipe and product rP4 number of glass cloth impregnated with unsaturated polyester resin)
C The outside of the tonneau was changed as shown in Table 1 below, as shown in Example 1.
Reinforced PVC pipes were obtained in a similar manner. Table 1 below shows the results of Example 1 and the concavity test conducted on the reinforced polyvinyl chloride pipes subjected to TI. Example 7 Acrylic Acid Esde A5 Rubber Adhesive (Konishi Company CV
-550) A reinforced polychlorinated vinyl tube was obtained in the same manner as in Example 1, except that the thickness of the Japanese paper impregnated with 'li7 was 0.2 mm. The obtained reinforced polyvinyl chloride pipe was subjected to the same test as in Example f1 [1], and the results are shown in Table 1 below. Comparative Examples 2-6 Use 1. The leaf diameter of the polyvinyl chloride 1′C and l)゛f
・;・1゜111 polynisdel (1゜1 fat-deficient impregnated six-calask r1 layer number transfer nl',: H'-' - Comparative example 1 except that one change was avoided) In a similar manner, (reinforced polyvinyl pipe) was used.
i, ? Biography Table 1 shows 7jF -j' rs comparative example 7~? What is the Charpy impact strength and water crush resistance JR, IJ strength of China and Germany?
rI11 was determined and the results are shown in Table 1 below. /・' 7/ As is clear from the table, the reinforced polyvinyl chloride pipe of the example according to the present invention is significantly superior to the conventional comparative example in terms of both ruby impact strength and hydraulic burst strength. ing. As described above, according to the present invention, it is possible to solve the drawbacks of the prior art and provide a reinforced thermoplastic resin finger laminate having excellent mechanical strength. Therefore, the reinforced thermoplastic resin laminate of the present invention can be used in a wide range of technical fields such as chemical industry, piping materials for various liquids, and large containers such as reactors.

[Brief explanation of drawings]

The drawing is a schematic vertical cross-sectional view of a jig for a hydraulic fracture test used in an example of the present invention. 1. Fiber-reinforced thermosetting resin layer, 2. Thickness-retaining material-containing rubber elastic layer, 5. Thermoplastic resin molded article, 4. Hydraulic fracture test jig, 5.- Water leakage prevention jig. 6...Water, 7...Water pressure

Claims (1)

[Claims] (Reinforced thermal 0I plastic resin laminate in which a thermoplastic resin molded body is reinforced with a fiber reinforced thermosetting resin layer,
Reinforcement characterized by providing an elastic body layer between the resin molded body and the fiber-reinforced thermosetting resin layer, which has M-contact properties to both. Thermoplastic 4 (
f1 stacked body.