JP3109197B2 - Automobile part molded product by laminate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article of an automobile part such as a bumper backup beam, a door beam, a seat shell, a bumper, etc., which is lightweight and has excellent mechanical strength.

[0002]

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

However, this stampable sheet has a large dispersion in strength depending on the location of the structure due to poor fiber dispersibility, and has a low strength as a structure due to a low fiber content, and is required for the structure. The properties are not fully satisfied.

As another example, there is a molded product obtained by kneading a thermoplastic resin and a reinforcing fiber and injection molding.

[0005] However, the molded article obtained by the injection molding has a low fiber length and thus has a low strength, and does not sufficiently satisfy the characteristics required for the structure.

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

[0007]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, completed the present invention.

[0008] That is, the present invention provides a method for forming a thermal prepreg on an arbitrary layer of a sheet-like prepreg laminate containing 40 to 85% by weight of a reinforcing fiber arranged in one direction with a thermoplastic resin, or on the front and back surfaces of the prepreg laminate. In a molded product of a laminate obtained by pressing a molding material in which a plastic resin sheet is arranged and heating it to a semi-molten state, the molded product is an automobile part molded product, and a reinforcing member arranged in one direction An object of the present invention is to provide a molded article of an automobile part by a laminate, wherein the longitudinal direction of the fiber is arranged most in the direction requiring the most strength.

[0009]

[0010]

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

The thermoplastic resin constituting the molding material composed of a thermoplastic resin and a reinforcing woven fabric or a reinforcing fiber arranged in one direction includes, for example, polystyrene, polypropylene, polyethylene, AS resin, ABS resin, ASA
Resin (polyacrylonitrile / polystyrene / polyacrylate), polymethyl methacrylate, nylon, polyacetal, polycarbonate, polyethylene terephthalate, polyphenylene oxide, fluororesin, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether There are ketone, polyimide, polyarylate and the like.

[0012] As a reinforcing body constituting a prepreg comprising a thermoplastic resin and a reinforcing body woven fabric or a reinforcing fiber arranged in one direction, for example, glass fiber, carbon fiber,
Aramid fibers, silicon carbide fibers and the like are typical. A prepreg obtained by impregnating fibers arranged in one direction with a thermoplastic resin is usually a yarn in which 200 to 12,000 monofilaments having a thickness of 3 to 25 μm are bundled or
A roving is used in which a predetermined number of rovings are arranged in one direction and impregnated with a thermoplastic resin.

A prepreg formed by impregnating a woven fabric fiber with a thermoplastic resin is prepared by bundling 200 to 12,000 monofilaments having a thickness of 3 to 15 μm into a woven fabric yarn, and driving 5 to 80 yarns per 25 mm of the woven fabric width. A woven fiber woven with a thermoplastic resin impregnated is used. The weaving method of the woven fabric fibers includes plain weave, satin weave, bias weave and twill weave, and any of them can be used.

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

In the case of glass fibers, it is necessary to select an optimum coupling agent according to the resin to be combined, and specific examples thereof 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 a polycarbonate resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane and the like are used.

In the case of polyethylene terephthalate or polybutylene terephthalate, 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, vinyl trimethoxysilane, vinyl-tris- (2-methoxyethoxy) silane, γ-methacryloxy-propyltrimethoxysilane and the like are used.

As long as polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyarylate, or fluororesin, the above-described coupling agents can be used, but other N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-aminophenyltriethoxysilane, and the like can be used.

In cases other than glass fibers, an amine-curable epoxy resin is often treated as a coupling agent, and specific examples thereof include bisphenol-A-epichlorohydrin resin, epoxy novolak resin, alicyclic epoxy resin, and fatty acid. Group epoxy resin and glycidyl ester type resin can be used.

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

That is, a solution prepared by dissolving a coupling agent in an amount of 0.1 to 3% by weight in the fiber from which the sizing agent has been removed is dipped, sprayed,
Complete impregnation by means such as coating. The fiber containing the coupling agent solution is dried at 60 to 120 ° C., and the coupling agent reacts on the fiber surface. The drying time is sufficient to evaporate the solvent, and is about 15 to 20 minutes.

As a solvent for dissolving the coupling agent, water whose pH is adjusted to about 2.0 to 12.0 depending on the surface treating agent to be used is used, and an organic solvent such as ethanol, toluene, acetone and xylene is used. They may be used alone or in combination.

There are various methods for impregnating a reinforcing material with a thermoplastic resin to form a prepreg, and the most common methods include the following two methods.

One is a method in which, if the resin is soluble in a solvent, the resin is converted into a solution, impregnated into a reinforcing member, and then the solvent is removed while defoaming to form a thin plate. One more thing,
This is a method in which 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 body (fiber) contained in the prepreg is from 40 to 85% by weight, and if it is less than 40% by weight, there is an inconvenience that the resin content is large and the strength becomes low. If the content exceeds% by weight, the content of the reinforcing body (fiber) is large, so that the degree of impregnation of the resin becomes poor, the content of bubbles in the prepreg increases, the strength decreases, and the properties required for the structure cannot be satisfied.

The prepreg thus obtained is laminated in an arbitrary number so as to exhibit the highest strength according to the intended use of the structure. For example, in the case of a long beam-shaped structure, the layers whose mechanical strength is the most dominant are positioned and laminated so that the fiber length is the longest in the longitudinal direction.

As the thermoplastic resin sheet, for example, polystyrene, polypropylene, polyethylene, AS resin, A
BS resin, ASA resin (acrylonitrile / styrene /
(Acrylate resin), polymethyl methacrylate nylon, polyacetal, polycarbonate, polyethylene terephthalate, polyphenylene oxide, fluororesin, polyphenylene sulfide, polysulfone,
Examples include polyethersulfone, polyetherketone, polyetheretherketone, polyimide, and polyarylate.

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

When importance is placed on the strength, the thermoplastic resin sheet is disposed 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 is melted, and then integrated under pressure or vacuum to obtain a molding material.

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

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

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

Here, the dimensions of the prepreg to be charged are such that the prepreg is sufficiently distributed to a place where strength is required as a finished laminate.

The mold surface temperature of the matched die is selected to be equal to or lower than the resin melting temperature. For example, when using polypropylene,
The mold surface temperature is set to 60 to 100 ° C. and a temperature at which the finished laminate has a good surface appearance is selected.

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

As another molding method, while heating the laminate to a temperature higher than the melting temperature in a mold mounted on a press,
At a pressure of 1 to 300 kg per 1 cm ^{2 of} molded product surface area, 1
After pressurizing for 0 second to 60 minutes, cooling to a temperature below the glass transition temperature of the resin, and removing the mold, a so-called press molding method, or heating to a temperature above the melting point of the resin under vacuum,
After shaping and defoaming at a pressure of 0 kg / cm ² or less, a so-called autoclave molding method in which the material is cooled to a glass transition temperature or less and then demolded can be used.

The melting temperature of the resin is, for example, polystyrene, polypropylene, polyethylene, AS resin,
210 ° C. for ABS resin, ASA resin (acrylonitrile / styrene / acrylate resin), polymethyl methacrylate, nylon, polyacetal, 230 for polyethylene terephthalate and fluorine resin
° C, 250 ° C for polyphenylene oxide, 270 ° C for polycarbonate, 320 ° C for polyphenylene sulfide and polysulfone, 360 ° C for polyethersulfone, 370 ° C for polyetheretherketone, polyether 39 for ketone
0 ° C. and 390 ° C. for polyimide and polyarylate.

The laminate of the present invention eliminates variations in strength depending on the location of the structure and has excellent mechanical strength, and is used as a molded article of automobile parts such as a bumper backup beam, a door beam, and a seat shell. .

[0042]

The present invention will be described below in more detail with reference to examples and comparative examples.

A sheet-like prepreg using fibers arranged in one direction, which is used in the embodiment of the present invention, is disclosed in JP-A-61-22.
No. 9535, surface-treated with γ-methacryloxy-propyltrimethoxysilane
The yarn in which 1600 monofilaments were bundled was drawn with uniform tension to a width of 200 mm while being pulled, brought into contact with a thermoplastic resin melted while being pulled, and impregnated with a hot roll to impregnate the resin. In addition, a sheet-shaped prepreg using a woven fabric is prepared by forming the woven fabric into a roll shape having a width of 200 mm.
As described in No. 535, the resin was produced by contacting with a hot-melted thermoplastic resin while applying tension and pulling, and impregnating the resin with a hot roll while squeezing the resin.

A matrix resin used for the prepreg,
Table 1 shows the reinforcing fiber and the reinforcing body (fiber) content. Here, the following treatment was performed on the glass woven fabric before impregnation with the resin. (Formation of Glass Woven Fabric) Glass Woven Fabric (Unitika H201
FT) was heat-cleaned at 400 ° C. for 10 hours, and then dried at a temperature of 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. Was.

FIG. 1 shows the shapes of molded products obtained from the molds used in the examples and comparative examples.

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

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

Example 1 Twelve prepregs A were cut into a length of 1300 mm 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 a 1300 mm long, 205 mm wide engraving mold heated to a temperature of 210 ° C., clamped, pressurized at a pressure of 40 tons for 10 minutes, and then heated to 80 ° C.
After cooling to a mold, 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 overlapped on the dent portion of the mold, that is, the rib portion of the laminate, on this molding material, and used as a material for stamping molding.

The 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 in a preheating device maintained at 60 ° C. for 3 minutes, taken out, and placed in a mold capable of forming a bumper backup beam having the shape shown in FIG. Inject, close the mold within 10 seconds, bumper backup beam surface 1 for 60 seconds
The mold was released after pressing at 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 observation results of the breaking load and the filling state of the ribs.

Example 2 The longitudinal direction of the molding material was 0 °, and the longitudinal direction of the reinforcing body of prepreg A was 90 °, 0 °, 0 °, 0 ° from the surface.
0 °, 90 °, 90 °, 0 °, 0 °, 0 °, 0 °, 90
1300mm length, 300m width
m, and a bumper backup beam was obtained by stamping molding in the same manner as in Example 1 except that the molding material was put into a mold and used as a molding material. A bending test was carried out in the same manner as in Example 1.
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 the results of observation of the breaking load and the state of filling the ribs are shown in Table 4.

Example 4 A bumper backup beam was obtained in the same manner as in Example 1 except that prepreg C was used instead of prepreg A, and resin sheet 2 having a thickness of 1 mm was used instead of resin sheet 1. A bending test was performed 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 5 A bumper backup beam was obtained in the same manner as in Example 1 except that prepreg D was used instead of prepreg A, and resin sheet 3 having a thickness of 1 mm was used instead of resin sheet 1. A bending test was performed 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 6 A bumper backup beam was obtained in the same manner as in Example 1 except that prepreg E was used instead of prepreg A, and resin sheet 4 having a thickness of 1 mm was used instead of resin sheet 1. A bending test was performed 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 7 Prepreg A was formed into a laminate in the same manner as in Example 1, and was preheated for 3 minutes in a preheating apparatus maintained at a temperature of 200 ° C. 100 mm thick 2 with resin sheet 5 attached to the end of the extruder
It was extruded through a 0 mm sheet forming die and supplied at a thickness of 1 mm onto a bumper backup beam mold heated to 60 ° C. Immediately, the preheated prepreg was transferred onto the resin sheet 5 and stamped 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 the results of observation of the breaking load and the state of filling the ribs are shown in Table 4.

Example 8 A prepreg A was prepared to have a size of 1
Two layers were stacked, and the resin sheet 1 was further stacked on the dent portion of the mold, that is, the rib portion of the laminate, and autoclave molding was performed.

The temperature is raised to 200 ° C. at a temperature rising rate of 10 ° C./min, maintained at a molding pressure of 20 kg / cm ² for 10 minutes, then cooled to 60 ° C. at a temperature decreasing rate of 10 ° C./min, demolded, and backed up by a bumper. Got the beam.

A bending test was performed 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 When the fiber direction of the prepreg was 0 °, 0
°, 90 °, 0 °, 90 °, 0 °, laminated in the 90 ° direction, 0 ° direction length 1300mm, 90 ° direction length 200
mm, and put in a 1300 mm long, 205 mm wide engraving mold heated to a temperature of 210 ° C., clamped, and pressurized at a pressure of 40 tons for 10 minutes in the same manner as in Example 1. Then, after cooling to 80 ° C., a molding material having a thickness of 1.1 mm was obtained.

The above-mentioned molding material having a thickness of 1.1 mm is placed on and under the sheet 1 having a thickness of 1 mm such that the fiber direction of the outermost layer is 0 °, and the resin layer is laminated. The molding material was used as the center layer. The molding material was taken out after heating for 3 minutes in a preheating device kept at a temperature of 300 ° C., and kept at 60 ° C. It was put into a mold capable of forming a bumper backup beam having the shape shown in FIG. 1, the mold was closed within 10 seconds, and the mold was depressurized after applying pressure at 200 tons for 60 seconds. This bumper backup beam was subjected to a three-point bending test in the same manner as in Example 1. Table 4 shows the observation results of the breaking load and the filling state of the ribs.

COMPARATIVE EXAMPLE 1 Two pieces of the molding material 6 were cut into a length of 1300 mm and a width of 150 mm, superposed and heated in a preheating device 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 depressurized after applying a pressure of 400 tons for 60 seconds. A bending test was performed 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.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

As described above, according to the present invention, a high-strength FRTP can be formed into a structural material.

[Brief description of the drawings]

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

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Molding material 2 Thermoplastic resin 3 Reinforcement rib 4 Fixed part

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Satoshi Kishi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Hideo Sakai 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical (56) References JP-A-1-141103 (JP, A) JP-A-2-89626 (JP, A) JP-A-59-89148 (JP, A) JP-A-2-220842 (JP, A) A) Japanese Utility Model Hei 2-106439 (JP, U) (58) Field surveyed (Int. Cl. ⁷ , DB name) B60R 19/02-19/50 B32B 1/00-35/00 B29C 43/00- 43/58 B29B 11/16 B29B 15/08-15/14 C08J 5/04-5/10 C08J 5/24

Claims (1)

(57) [Claims] 1. A thermoplastic resin sheet on an arbitrary layer of a sheet-like prepreg laminate containing 40 to 85% by weight of a reinforcing resin fiber arranged in one direction with a thermoplastic resin, or on the front and back surfaces of the prepreg laminate. In a molded body of a laminate obtained by heating and pressing the molding material in a semi-molten state in which the molded body is disposed, the molded body is an automobile part molded body, and the longitudinal direction of the reinforcing body fibers arranged in one direction. An automobile part molded article made of a laminate, wherein the direction is most arranged in the direction requiring the most strength.