JPH05147169A - Laminate and manufacture thereof - Google Patents

Abstract

PURPOSE:To eliminate strength dispersion depending on places in a structural body and thus obtain a laminate with an excellent mechanical strength by firmly connecting the interlayers between sheetlike prepregs containing a specific quantity of the reinforcing body and forming materials comprising a thermoplastic resin sheet. CONSTITUTION:The laminate is characterized such that it comprises thermoplastic resin and woven cloth, or reinforcing body fiber arranged in one direction, and also comprises a sheetlike prepreg containing 40-85wt.% reinforcing body fiber and a thermoplastic resin sheet, wherein the interlayers between the forming materials are connected firmly together. The prepreg may be of the type wherein cloth-like fiber woven by putting 5-80 pieces of monofilament- bundled weaving yarn per weaving width of 25mm is impregnated with thermoplastic resin. Defoaming of the forming materials, firm connection of the interlayers and cool-hardening of the materials are conducted in the course of pressurization in the mold, and thereafter demolding is carried out thereby to obtain a laminate. Namely, a laminate is obtained by a forming method of stamping.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention can be used in various fields such as automobile parts and structures such as bumper backup beams, door beams, seat shells, building materials, aircraft structural members, bumpers, etc. which are lightweight and have excellent mechanical strength. And a manufacturing method thereof.

[0002]

2. Description of the Related Art A conventionally known structure comprising a reinforcing fiber and a thermoplastic resin is a stampable sheet used for stamping molding by impregnating a glass fiber swirl mat with polypropylene, for example.

However, this stampable sheet is poor in the dispersibility of the fibers, so that the strength varies widely depending on the location of the structure, and since the content of the fiber is low, the strength of the structure is low and the structure is required. The characteristics are not sufficiently satisfied.

Another example is a molded product obtained by kneading a thermoplastic resin and reinforcing fiber and injection molding.

However, since the molded product obtained by this injection molding has a short fiber length, the molded product has low strength and does not sufficiently satisfy the properties required for the structure.

The present invention comprises a thermoplastic resin and a reinforcing fiber, eliminates the variation in strength depending on the location of the structure,
Moreover, it is an object of the present invention to provide a laminate having excellent mechanical strength and a molding method thereof.

[0007]

[Means for Solving the Problems] The present inventors have completed the present invention as a result of extensive studies to achieve the above object.

That is, the present invention comprises a thermoplastic resin and a woven fabric or reinforcing fibers arranged in one direction, and a sheet prepreg containing 40 to 85% by weight of the reinforcing fibers and a thermoplastic resin sheet. It is intended to provide a laminate characterized in that the layers of the material are strongly bonded.

Further, 40 to 85% by weight of the thermoplastic resin and the reinforcing body woven fabric or the reinforcing body fibers arranged in one direction.
Provided is a method for producing a laminate, which comprises heating a molding material in which a thermoplastic resin sheet is positioned between arbitrary layers of a sheet-like prepreg laminate containing the material and pressing the molding material in a semi-molten state. ..

[0010]

DETAILED DESCRIPTION OF THE INVENTION The laminate of the present invention is obtained by the following materials and molding methods.

Examples of the thermoplastic resin which constitutes the molding material composed of the thermoplastic resin and the reinforced woven fabric or the reinforced fibers arranged in one direction include polystyrene, polypropylene, polyethylene, AS resin, ABS resin and ASA.
Resin (polyacrylonitrile / polystyrene / polyacrylate), polymethylmethacrylate, nylon, polyacetal, polycarbonate, polyethylene terephthalate, polyphenylene oxide, fluororesin, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether Examples include ketones, polyimides, polyarylates and the like.

Examples of the reinforcing body which constitutes the prepreg composed of the thermoplastic resin and the reinforcing body woven fabric or the reinforcing body fibers arranged in one direction include glass fiber, carbon fiber,
Aramid fiber, silicon carbide fiber, etc. are typical. The prepreg obtained by impregnating fibers arranged in one direction with a thermoplastic resin is usually a yarn obtained by bundling 200 to 12000 monofilaments having a thickness of 3 to 25 μm, or
A predetermined number of rovings arranged in one direction and impregnated with a thermoplastic resin is used.

A prepreg obtained by impregnating a woven fabric-like fiber with a thermoplastic resin, woven yarn for bundling 200 to 12000 monofilaments having a thickness of 3 to 15 μm is struck in 5 to 80 per 25 mm width of the woven fabric. Woven cloth-like fibers woven with are impregnated with a thermoplastic resin. The weaving method of the woven fabric fibers includes plain weave, satin weave, bias weave, and twill weave, and any of these can be used.

When the reinforcing fiber thus obtained is a glass fiber, the sizing agent is removed by heat cleaning and then treated with a silane-based, titanate-based or zirconium-based coupling agent to adhere to the resin. Use a product with improved properties.

In the case of glass fiber, it is necessary to select the most suitable coupling agent according to the resin to be combined, and specific examples will be given below.

In the case of nylon resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl)-
γ-aminopropyl-trimethoxysilane or the like is used.

As the polycarbonate resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane and the like are used.

If polyethylene terephthalate or polybutylene terephthalate is used, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane,
γ-glycidoxy-propyltrimethoxysilane, γ-
Aminopropyl-trimethoxysilane or the like is used.

In the case of polyethylene, polypropylene, polystyrene, AS resin or ABS resin, vinyltrimethoxysilane, vinyl-tris- (2-methoxyethoxy) silane, γ-methacryloxy-propyltrimethoxysilane and the like are used.

If polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyarylate, or fluororesin is used, the above-mentioned coupling agent can be used, but other than that, In addition, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-aminophenyltriethoxysilane and the like can be used.

In the case of other than glass fiber, amine curing type epoxy resin is often treated as a coupling agent, and specific examples thereof include bisphenol-A-epichlorohydrin resin, epoxy novolac resin, alicyclic epoxy resin, and fat. Group epoxy resins and glycidyl ester type resins can be used.

The method of applying the coupling agent to the fiber surface is as follows.

That is, a liquid obtained by dissolving 0.1 to 3% by weight of the coupling agent in the fibers from which the sizing agent has been removed is dipped, sprayed,
Completely impregnate by means such as coating. The fiber containing the coupling agent solution is dried at 60 to 120 ° C. to react the coupling agent with the fiber surface. The drying time is sufficient to evaporate the solvent, which is about 15 to 20 minutes.

The solvent for dissolving the coupling agent may be water adjusted to a pH of 2.0 to 12.0 or an organic solvent such as ethanol, toluene, acetone or xylene depending on the surface treatment agent used. It may be used alone or as a mixture.

There are various means for impregnating a reinforcing body with a thermoplastic resin to form a prepreg, but the following two are the most general methods.

One is a method in which a resin soluble in a solvent is made into a solution to impregnate the reinforcing body, and then the solvent is removed while defoaming to form a thin plate. One more
In this method, a resin is heated and melted to impregnate a reinforcing body, defoamed, and cooled to form a thin plate.

The range of the content of the reinforcing material (fiber) contained in the prepreg is 40 to 85% by weight. Below 40% by weight, there is a disadvantage that the strength becomes low because the content of the resin is large. If the content exceeds 10% by weight, the content of the reinforcing material (fiber) is large, the impregnation condition of the resin is deteriorated, the content of bubbles in the prepreg is increased, the strength is lowered, and the properties required for the structure cannot be satisfied.

The prepregs thus obtained are laminated in an arbitrary number so as to exhibit the highest strength in accordance with the intended use of the structure. For example, in the case of a long beam-like structure, the layer in which the mechanical strength is most dominant is positioned and laminated so that the fiber length becomes the longest in the longitudinal direction.

Examples of the thermoplastic resin sheet include polystyrene, polypropylene, polyethylene, AS resin, A
BS resin, ASA resin (acrylonitrile / styrene /
Acrylic ester resin), polymethylmethacrylate nylon, polyacetal, polycarbonate, polyethylene terephthalate, polyphenylene oxide, fluororesin, polyphenylene sulfide, polysulfone,
There are polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyarylate and the like.

The thermoplastic resin sheet is placed at an arbitrary position according to the shape of the molded product and the required performance. For example, when importance is attached to the smoothness of the surface of the molded product, it is coordinated on the front and back surfaces of the prepreg laminate.

When the strength is emphasized, the thermoplastic resin sheet is arranged near the center layer of the prepreg laminate.

A laminated material composed of a plurality of laminated prepregs and a thermoplastic resin sheet provided with a predetermined amount is heated at a temperature at which the thermoplastic resin melts, and then integrated with pressure or vacuum to obtain a molding material.

At this time, the molding material does not necessarily have to be flat, and may be preformed into a shape close to the intended laminate.

As a method of processing this molding material to obtain a laminate, for example, when glass fibers are used, there are the following methods.

A molding material composed of a plurality of laminated prepregs and a thermoplastic resin sheet provided with a predetermined amount is heated in an oven at a temperature at which the thermoplastic resin melts, and then placed on a mold and the mold is closed.

The dimension of the prepreg to be charged here is such that the prepreg is sufficiently distributed to the place where strength is required in the finished laminate.

The mold surface temperature of the matched die is selected to be not higher than the resin melting temperature. For example, when polypropylene is used,
The mold surface temperature is set to 60 to 100 ° C. and the temperature at which the surface appearance of the finished laminate is good is selected.

The molding pressure is 1 cm ² of the surface area of the laminate.
The pressure is set to 1 to 300 kg and the pressing time is set to 10 seconds to 60 minutes. In the process of pressing in the mold, defoaming of the molding material, firm adhesion between layers and cooling and hardening of the material are performed, and then demolding to obtain a laminate. A laminate can be obtained by a so-called stamping molding method.

As another molding method, while heating the laminated body in a mold attached to a press at a temperature higher than the melting temperature,
1 to 300 kg of pressure per 1 cm ² of surface area of molded product
Press for 0 seconds to 60 minutes, cool to below the glass transition temperature of the resin and then demold, a so-called press molding method, or after heating above the melting temperature of the resin under vacuum,
It is possible to use a so-called autoclave molding method in which after shaping and defoaming at a pressure of 0 kg / cm ² or less, cooling to below the glass transition temperature and then demolding are performed.

The melting temperature of the resin is, for example, polystyrene, polypropylene, polyethylene, AS resin,
ABS resin, ASA resin (acrylonitrile / styrene / acrylic ester resin), polymethylmethacrylate, nylon, polyacetal 210 ° C, polyethylene terephthalate, fluororesin 230
C., 250 ° C. for polyphenylene oxide, 270 ° C. for polycarbonate, 320 ° C. for polyphenylene sulfide or polysulfone, 360 ° C. for polyether sulfone, 370 ° C. for polyether ether ketone, polyether 39 for ketones
The temperature is 0 ° C., and the temperature is 390 ° C. for polyimide and polyarylate.

The laminated body of the present invention is a laminated body which eliminates variations in strength depending on the location of the structure and has excellent mechanical strength, and is used for automobile parts such as bumper backup beams, door beams, seat shells and structures, and construction. Used as various products such as materials and aircraft structural members.

[0042]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

A sheet-like prepreg using unidirectionally arranged fibers used in the examples of the present invention is disclosed in JP-A-61-22.
13 μm surface-treated with γ-methacryloxy-propyltrimethoxysilane as described in US Pat.
100 yarns of 1,600 monofilaments of (1) were bundled with a uniform tension to a width of 200 mm while being pulled, brought into contact with a hot-melted thermoplastic resin while being pulled, and impregnated with a hot roll to impregnate the resin. Further, a sheet-like prepreg using a woven cloth is prepared by rolling the woven cloth into a roll having a width of 200 mm, which is disclosed in JP-A-61-229.
No. 535, it was produced by impregnating the resin with a hot roll while squeezing the resin while bringing it into contact with a hot-melted thermoplastic resin while applying tension and pulling.

Matrix resin used for prepreg,
Table 1 shows the content of the reinforcing fiber and the reinforcing material (fiber). Here, the glass woven fabric was subjected to the following treatment before being impregnated with the resin. (Formation of glass woven fabric) Glass woven fabric (Unitika H201
(FT) is heat-cleaned at 400 ° C. for 10 hours and then dried at 100 to 110 ° C. for 10 minutes while passing through water containing 0.3% by weight of γ-aminopropyltrimethoxysilane, to obtain a glass woven fabric. It was

The shapes of molded articles obtained from the molds used in Examples and Comparative Examples are shown in FIG.

Table 2 shows the thermoplastic resin sheets used in the following Examples and Comparative Examples.

The molding material 6 used was that sold by Ube Nitto Kasei Co., Ltd. under the trade name "Azudel". The thermoplastic resin used in "Azudel" is polypropylene and the glass fiber content is 40% by weight.

Example 1 Twelve pieces of prepreg A having a length of 1300 mm were cut and stacked to obtain a molding material having a width of 300 mm and a length of 1300 mm. This molding material was put into an engraving mold having a length of 1300 mm and a width of 205 mm heated to a temperature of 210 ° C., the mold was clamped, and a pressure of 40 tons was applied for 10 minutes, and then 80 ° C.
After cooling to 0, the mold was removed to obtain a molding material having a thickness of 2.2 mm.
A resin sheet-1 having a thickness of 1 mm was superposed on the dented portion of the mold, that is, the rib portion of the laminated body, on this molding material to obtain a stamping molding material.

Stamping molding was performed in the following procedure to obtain a bumper backup beam. That is, the temperature 250
The stamping molding material was heated for 3 minutes in a preheater maintained at ℃ and taken out, and the molding material was placed on the rib side in a mold that can mold the bumper backup beam having the shape shown in FIG. Turn on, close the mold within 10 seconds, and for 60 seconds, bumper backup beam surface 1
The mold was demolded after being pressurized with 200 tons corresponding to a molding pressure of 60 kg per cm ² . This bumper backup beam was subjected to a three-point bending test with both ends fixed under the conditions shown in Table 3 to determine the breaking load. Table 4 shows the results of observation of the breaking load and the filling state of the ribs.

Example 2 With the longitudinal direction of the molding material set at 0 °, the longitudinal direction of the reinforcing body of the prepreg A was 90 °, 0 °, 0 °, 0 ° from the surface,
0 °, 90 °, 90 °, 0 °, 0 °, 0 °, 0 °, 90
Twelve sheets installed at an orientation of °, length 1300mm, width 300m
A bumper backup beam was obtained by stamping molding in the same manner as in Example 1 except that the m-thick layered material was used and the molding material was placed in a mold. A bending test was conducted in the same manner as in Example 1, and the results of observation of the breaking load and the state of filling the ribs are shown in Table 4.
It was shown to.

Example 3 A bumper backup beam was obtained in the same manner as in Example 1 except that prepreg B was used instead of prepreg A.
A bending test was performed in the same manner as in Example 1, and Table 4 shows the observation results of the breaking load and the filling state into the ribs.

Example 4 A bumper backup beam was obtained in the same manner as in Example 1 except that the prepreg C was used instead of the prepreg A, and the resin sheet 2 having a thickness of 1 mm was used instead of the resin sheet 1. A bending test was performed in the same manner as in Example 1, and Table 4 shows the observation results of the breaking load and the filling state into the ribs.

Example 5 A bumper backup beam was obtained in the same manner as in Example 1 except that the prepreg D was used in place of the prepreg A, and the resin sheet 3 having a thickness of 1 mm was used in place of the resin sheet 1. A bending test was performed in the same manner as in Example 1, and Table 4 shows the observation results of the breaking load and the filling state into the ribs.

Example 6 A bumper backup beam was obtained in the same manner as in Example 1 except that the prepreg E was used in place of the prepreg A, and the resin sheet 4 having a thickness of 1 mm was used in place of the resin sheet 1. A bending test was performed in the same manner as in Example 1, and Table 4 shows the observation results of the breaking load and the filling state into the ribs.

Example 7 A prepreg A was laminated in the same manner as in Example 1 and preheated for 3 minutes in a preheater maintained at a temperature of 200 ° C. Width 100 mm with resin sheet 5 attached to the end of the extruder Thickness 2
It is extruded through a 0 mm sheet forming die and supplied to a bumper backup beam die heated to 60 ° C. with a thickness of 1 mm, immediately preheated prepreg is moved onto a resin sheet 5, and stamping is performed under the same conditions as in Example 1. Molding was performed to obtain a bumper backup beam. A bending test was performed in the same manner as in Example 1, and Table 4 shows the observation results of the breaking load and the filling state into the ribs.

Example 8 The prepreg A was set to a size suitable for the mold having the shape shown in FIG.
Two layers were stacked, and the resin sheet 1 was further stacked on the recessed portion of the mold, that is, the rib portion of the laminated body, and autoclave molding was performed.

The temperature was raised to 200 ° C. at a rate of 10 ° C./min, the pressure was kept at 20 kg / cm ² for 10 minutes, and then the temperature was lowered to 60 ° C. at a rate of 10 ° C./min. Got the beam.

A bending test was conducted in the same manner as in Example 1, and the results of observation of the breaking load and the state of filling the ribs are shown in Table 4.

Example 9 With the fiber direction of the prepreg set at 0 °, the prepreg was sequentially set to 0 from the surface.
Laminated in 90 °, 90 °, 0 °, 90 °, 0 ° and 90 ° directions, 0 ° direction length 1300 mm, 90 ° direction length 200
As a laminated body of mm, it was put into an engraving die having a length of 1300 mm and a width of 205 mm, which was heated to a temperature of 210 ° C., clamped, and pressed at a pressure of 40 tons for 10 minutes, as in Example 1. Then, after cooling to 80 ° C., a molding material having a thickness of 1.1 mm was obtained.

On the sheet-1 having a thickness of 1 mm, the molding material having a thickness of 1.1 mm described above is arranged so that the fiber direction of the outermost layer is 0 °, and the resin is laminated. The molding material was used as the central layer. This molding material was heated in a preheater maintained at a temperature of 300 ° C. for 3 minutes, taken out, and kept at 60 ° C. The bumper backup beam having the shape shown in FIG. 1 was put into a mold capable of being molded, the mold was closed within 10 seconds, and the mold was depressurized after being pressurized with a pressure of 200 tons for 60 seconds. A three-point bending test was performed on this bumper backup beam in the same manner as in Example 1. Table 4 shows the results of observation of the breaking load and the filling state of the ribs.

Comparative Example 1 Molding material 6 was cut into two pieces each having a length of 1300 mm and a width of 150 mm, which were superposed and heated in a preheater at 200 ° C. for 10 minutes, and then kept at 60 ° C. to form a bumper backup beam. The molding material 6 was put into the mold, the mold was closed within 10 seconds, and the mold was released after being pressurized at a pressure of 400 tons for 60 seconds. A bending test was performed in the same manner as in Example 1, and Table 4 shows the observation results of the breaking load and the filling state into the ribs.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

As described above, according to the present invention, it is possible to mold a high-strength FRTP structural material.

[Brief description of drawings]

FIG. 1 is a combination view of a plan view and a front view of bumper backup beam molded products molded in Examples and Comparative Examples.

FIG. 2 is an enlarged view of an AA cross section of FIG.

[Explanation of symbols]

 1 Molding material 2 Thermoplastic resin 3 Reinforcing rib 4 Fixed part

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Kishi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd. (72) Hideo Sakai 1190 Kasama-cho, Sakae-ku, Yokohama, Kanagawa Mitsui Toatsu Chemical Within the corporation

Claims (6)

[Claims] 1. A sheet-like prepreg comprising a thermoplastic resin and a woven cloth or a reinforcing material arranged in one direction, the reinforcing material being 40 to 85% by weight, and a layer of a molding material made of a thermoplastic resin sheet. A laminated body characterized by being strongly bonded. 2. The laminate according to claim 1, wherein the reinforcing body is made of glass fiber, carbon fiber or synthetic fiber. 3. The laminated body according to claim 1, wherein the reinforcing fibers arranged in one direction are arranged in the longest direction in the direction in which the strength is required most. 4. The layers of the molding material are arranged in an arbitrary orientation in the longitudinal direction of the reinforcing fiber.
The laminate described. 5. A thermoplastic resin sheet is arranged between any layers of a sheet-shaped prepreg laminate containing 40 to 85% by weight of a thermoplastic resin and a woven woven fabric of a reinforced body or reinforced fibers arranged in one direction. A method for producing a laminate, which comprises heating a molding material to a semi-molten state and pressing it. 6. The method for producing a laminate according to claim 5, wherein a molding material composed of a sheet-like prepreg and a thermoplastic resin sheet is heated and pressed at a melting temperature.