JPS6056116B2 - Reinforcement material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a reinforcing material that contributes to weight reduction as reinforcement for plate materials.

Conventionally, various reinforcing measures have been applied to car body steel plates in automobiles and the like.

For example, for outer panels that have a relatively wide and flat shape but are thin, such as loops, fenders, hoods, trunks, outer panels, and doors, the structure must have appropriate rigidity against external forces. Due to necessity, a method is used in which an inner plate made of a metal reinforcing member is attached by spot welding or adhesive. However, with this method, the weight of the metal reinforcing members is heavy, and this goes against the trend of thinning the outer skin, which was designed to reduce the weight of car bodies.This method increases weight and cost, and also complicates the installation process. It had drawbacks. In addition, as shown in Utility Model Publication No. 55-10165, for example, for the purpose of vibration isolation and reinforcement of the outer panel of the vehicle body,
A method is also known in which a polymeric material such as asphalt rubber, epoxy resin, acrylic resin, phenol resin, or unsaturated polyester resin is coated or pasted on the back side of the outer panel to a considerable thickness and over a considerable area. In this method, the rigidity is said to be proportional to the cube of the thickness, so by increasing the thickness, it is possible to increase the rigidity, but due to the increase in the amount of resin, the weight increases and the cost increases. It has the same drawbacks as the metal reinforcing member, such as the fact that the metal reinforcing member is
This invention was made in view of the above-mentioned conventional circumstances, and aims to provide a reinforcing material that is lightweight, inexpensive, and significantly improves the rigidity of the object to which it is attached. Consists of a first thermosetting resin composition layer blended with a resin so as to have a high transition temperature, and a second thermosetting resin composition layer containing a resin blended so as to have a low glass transition temperature similar to the above. The second thermosetting resin composition layer of an uncured or semi-cured thermosetting reinforcing resin sheet (hereinafter simply referred to as reinforcing resin sheet) in which at least one layer of the laminated sheet contains a fiber base material. A bead-forming material that is formed to have a narrower width than the sheet and that forms a bead-shaped bulge on the sheet before the sheet is cured is attached to the side, and the portion of the sheet that protrudes wider than the width of the bead-forming material is attached to the side of the sheet. The reinforcing material has a structure in which the hem portion on the thermosetting resin composition layer side of No. 2 is attached to an object to be attached.

The present invention will be explained below based on the drawings.

FIGS. 1 and 2 show an embodiment of the reinforcing material according to the present invention. The reinforcing material 1 is made of a first resin compounded with a resin so that the glass transition temperature when heated and cured is high. Thermosetting resin composition layer E and upper. An uncured or semi-cured sheet having a fiber base material 2 in at least one layer of a laminated sheet consisting of a second thermosetting resin composition layer F which is blended with a resin so as to have a low glass transition temperature as described above. A reinforced resin sheet 3 prepared in a flexible prepreg state, and a bead forming material 4 made of a foamed resin sheet attached to the side surface of the second thermosetting resin composition layer F of the reinforced resin sheet 3. The bead forming material 4 is formed to be narrower than the reinforcing resin sheet 3. The hem portions 3a, 3a on the second thermosetting resin composition layer F side of the reinforcing/reinforcing resin sheet protruding from the width of the bead forming material 4 may be attached to an object to be attached, for example, the back surface 5a of an automobile door outer panel 5. It forms the mounting surface.
As shown in FIG. 2, the reinforcing material 1 is attached to the back surface 5a of the door outer panel 5 with its attached surfaces 3a, 3a, and by heating after attachment, the viscosity of the reinforcing resin sheet 3 is temporarily reduced. As a result, the mounting surfaces 3a, 3a come into closer contact with the door outer panel 5, while the bead forming material 4 foams and its cross section becomes larger, and the reinforcing resin sheet 3 is pushed up from the bases 3c, 3c of the mounting surface 3a, before hardening. A bead-like swollen portion 3b is formed, and as the heating progresses over time, the reinforcing resin sheet 3 hardens.
The state shown in FIG. 3 is reached. ) Next, the above-mentioned fiber base material 2, reinforcing resin sheet 3, and bead forming material 4 will be explained in detail.

First, the reinforced resin sheet 3 includes a first thermosetting resin/composition layer E, which is blended with a resin so that the glass transition temperature when heated and cured is usually 70° C. or higher; Usually 6
The fiber base material 2 is fused and integrated with at least one layer of a laminated sheet consisting of a second thermosetting resin composition layer F in which the resin is blended so that the temperature is 0° C. or lower (generally 0° C. or higher). It can be made by The above-mentioned first and second thermosetting resin composition layers are each made by blending a thermosetting resin such as an epoxy resin with a heat-activated curing agent, and adding various additives as necessary. It can be formed by sheet molding in an uncured or semi-cured state according to a conventional method.

When forming this sheet, by appropriately setting the type of thermosetting resin, the type of curing agent, and other additives, or by setting the blending amount of each component, the first and second heat The glass transition temperature of the curable resin layer after heating and curing is adjusted as described above. Epoxy resins, which are typical thermosetting resins used to form each composition layer, include ordinary glycidyl ether type, glycidyl ester type, glycidyl amine type, linear aliphatic epoxide type, and alicyclic epoxide type. There are various types of epoxy resins such as molds, and one type can be used alone or two or more types can be used in combination depending on the physical properties of each composition layer.

In addition, the heat-activated curing agent for epoxy resins may be any ordinary curing agent that exhibits a curing effect when heated, and generally 8
It is sufficient that it is active in the temperature range of 0 to 200°C, for example, dicyandiamide, 4,4″-diaminodiphenylsulfone, imidazole derivatives such as 2-n-heptadecyl imidazole, isophthalic acid dihydrazide, N-
N-dialkyl urea derivatives, N-N-dialkylthiourea derivatives, etc. are used.

The amount used is usually 1 to 1 part per 10 parts of epoxy resin.
The proportion may be 5 parts by weight. In addition to the thermosetting resin and curing agent such as the epoxy resin mentioned above, the composition has a cohesive force to the extent that it can be formed into a sheet, and also to prevent sagging or to lower the melt viscosity and improve wettability. Various additives are used as necessary for these purposes.

For example, for the purpose of improving sheet forming ability, polyvinyl butyral, polyamide, polyamide derivatives, polyester, polysulfone, polyketone, bisphenol A
Thermoplastic resins such as high molecular weight epoxy resins derived from and epichlorohydrin, or rubber components such as butadiene-acrylonitrile copolymers or derivatives thereof can be blended.

The amount used is preferably about 5 to 10 parts by weight per 100 parts by weight of the thermosetting resin. Furthermore, for the purpose of lowering the melt viscosity and improving wettability, reactive diluents such as butyl glycidyl ether and monoglycidyl ether of long-chain alcohols, phthalic acid plasticizers such as dioctyl phthalate, and phosphorus such as triclean diphosphate are added. Acid plasticizers etc. can be added.

The amount of these components is preferably about 5 to 30 parts by weight per 100 parts by weight of the thermosetting resin. In addition, fillers such as calcium carbonate, talc, asbestos powder, silicic acids, carbon black, and colloidal silica can be used to prevent the composition from sagging.

At this time, when the reinforcing material of the present invention is made using a thermosetting resin composition containing the filler and is used for reinforcing a door outer panel, etc., the amount of the filler added is determined by Care should be taken to use it to the extent that it does not impair the adhesive strength with other materials. Among the above-mentioned fillers, asbestos powder is preferably used, and the amount used is preferably determined by the amount of the polymer component in the composition (i.e., thermosetting resin and optionally used thermoplastic resin, rubber). Total amount of ingredients) 2 to 2 per 10 parts
It is considered to be the salivary part. Among the first and second thermosetting resin composition layers formed in this way, it is particularly desirable that the second thermosetting resin composition layer has tackiness in its normal state.

This is because temporary adhesion before heat curing becomes easier when applied to a door outer panel or the like. Of course, the first thermosetting resin composition layer may also have adhesive properties. The fiber base material 2 is embedded in one or both of the first and second thermosetting resin composition layers. Examples of such fiber base materials include inorganic fiber cloths such as glass fibers and asbestos fibers, organic fiber cloths such as hemp, cotton, nylon, polyester, and polypropylene, and sheet-like fiber base materials such as nonwoven fabrics made of polyester fibers and polypropylene fibers. Suitably used. Particularly preferred are inorganic fiber cloths, a typical example of which is glass fiber cloth. The thickness of the reinforced resin sheet 3 of the present invention varies depending on the type of metal plate and the degree of reinforcement, but generally the thickness of the first thermosetting resin composition layer is 0.01 to 1077!77! degree, preferably 0.1 to 5w1n1 in the second thermosetting resin composition layer.
About 1 to 30 wrIn, preferably 0.3 to 15 wrIn, and the overall thickness is usually about 0.1 to 407rn, preferably 0.3
~20 Ugly. Next, the foamable resin sheet as the bead forming material 4 has the property of foaming when heated above the decomposition temperature of the foaming agent contained therein,
The above-mentioned reinforcing resin sheet 3 provided on this sheet is formed to be narrower than the above-mentioned "sheet 3" so that it can come into close contact with the door outer plate surface on at least both sides in the width direction of the bead forming material 4.

Such foamable resin sheets are made by combining various thermosetting or thermoplastic polymers with a blowing agent and, if necessary, a foaming aid, a curing agent, a curing accelerator, a crosslinking agent, a crosslinking aid, a filler, and a coloring agent. , stabilizers, etc., and knead this mixture using a mixing roll, etc., and then form a sheet according to a conventional method under temperature conditions where the blowing agent does not decompose (slight decomposition is fine). It can be made by

) Thermosetting or thermoplastic polymers used above include thermosetting resins such as epoxy resins, phenolic resins, and polyester resins, polyethylene, ethylene-vinyl acetate copolymers, adhesive polyolefins, etc. The foaming agent may be any foaming agent that foams when the reinforced resin sheet is heated and cured and does not foam during sheet molding, such as azo compounds, nitroso compounds, hydrazide compounds, and the like.

The thickness of this foamable resin sheet is usually about 0.2 to 5TnIn, preferably about 0.5 to 2TnIn, and the foaming ratio during heating is practically desirably 2 to 3@.

Next, to explain in more detail the process of curing the reinforcing material 1, the reinforcing material 1 is brought into close contact with the door outer panel 5 as shown in FIG. The elastic resin sheet is foamed, and the curing of the sheet 3 is completed each time the foaming is completed.

As a result, as shown in FIG. 3, a fiber-reinforced resin layer having bead-shaped bulges 3b is formed by the expansion force caused by foaming. As the heating means, a conventional heating method such as a hot air circulation heating furnace, an infrared heating furnace, a high frequency induction heating furnace, etc. can be adopted. Further, it is also possible to simultaneously heat the car body during the car body painting process in the car manufacturing line. In such heating, the reinforcing resin sheet 3 is combined with a first thermosetting resin composition layer having a high glass transition temperature upon heating and curing, and a second thermosetting resin composition layer having a similar low glass transition temperature. Since the resin composition layer is composed of a resin composition layer and a bead forming material is attached to the second layer side so that this side faces the object to be attached, the layer having a high glass transition temperature located on the outside is Depending on the first layer, the glass of the first layer can be heated not only at room temperature but also at high temperatures of 40'C or higher, for example from 40'C. The strength of the fiber-reinforced resin layer in an environment up to the transition temperature is increased, and very good results are brought about in the rigidity of the door outer panel 5.

On the other hand, a second glass with a low glass transition temperature is placed opposite to the object to be attached.
This hardening layer suppresses the occurrence of distortion in the door outer panel 5 due to this shrinkage. I can do that. The reinforcing material of the present invention is not limited to car bodies such as the outer panels of automobile doors mentioned above, but can be widely applied to other generally thin metal plates such as various vehicles, washing machines, home appliances such as televisions, etc.・I can do it.

As described in detail above, according to the present invention, when constructing a reinforcing material using a reinforcing resin sheet and a bead forming material, the reinforcing resin sheet has a temperature similar to that of the first layer having a high glass transition temperature. Since the bead forming material is attached to the side of the second layer, the side to which it is attached is brought into close contact with the object to be attached and heated and cured, so that it can be cured at room temperature. Not only can a large reinforcing effect be obtained under high temperatures, but the door outer panel will not be distorted during the above operation, and the construction will be simple.

Next, examples of this invention will be described.

In the following), parts mean parts by weight. Example 1 Epicoat #828 (bisphenol A type liquid epoxy resin manufactured by Yuka Shell Co., Ltd.), Epicoat #100
2 (bisphenol A type solid epoxy resin manufactured by Yuka Shell Co., Ltd.) 4 (2), Platamide HlO3P (copolymerized nylon resin manufactured by Nihon Rilsan Co., Ltd.) (A) Part D. An epoxy resin composition consisting of 5 parts of P hardener (hardening agent made by Maruwa Biochemical Co., Ltd.), 5 parts of dicyandiamide (1) epoxy resin latent hardening agent made by Hon Carbide Co., Ltd., 5 parts of talc (2), and 2 parts of asbestos powder. The resulting resin mass is kneaded using a normal mixing wheel and then mixed using a direct pressure press to a thickness of 0.
A 4Tf$i sheet was formed, and a glass fiber cloth (WK3O3OA manufactured by Nitto Bosei Co., Ltd.) was further millanated to form a first epoxy resin composition layer.

Next, 65 parts of Epicoat #1004 (bisphenol A type solid epoxy resin manufactured by Yuka Shell Co., Ltd.), 35 parts of flexible epoxy resin (tripropylene glycol diglycidyl ether manufactured by Sakamoto Pharmaceutical Co., Ltd.), and dicyandiamide (
5 parts of epoxy resin latent curing agent manufactured by Nippon Carbide Co., Ltd.
An epoxy resin composition consisting of talc 5 (2) and 2 parts of asbestos powder was kneaded using a mixing roll in the same manner as described above, and formed into a sheet using a direct pressure press to form a sheet with a thickness of 0.
．． 8Tm! An uncured second epoxy resin composition layer consisting of n.

This second epoxy resin composition layer was bonded to the first epoxy resin composition layer to obtain a reinforced epoxy resin sheet.

The glass transition temperature of the first and second epoxy resin composition layers of this sheet after heating and curing was 110°C for the first layer;
The temperature was 50°C in the second layer. However, the heat curing conditions were 150° C. for 60 minutes. Separately, ethylene-vinyl acetate copolymer (Evaflex P manufactured by Mitsui Polychemical Co., Ltd.)
-2807) 100 parts, foaming agent (FE- manufactured by Eiwa Kasei Co., Ltd.)
9) 6 parts were uniformly kneaded with a mixing roll, pelletized with a pelletizer, and then formed into a sheet with a press molding machine at an extrusion temperature of 120°C to a thickness of 1 Tfn.
A foamable resin sheet (bead forming material) was obtained.

Next, the reinforced epoxy resin sheet was cut into a 5 d width, and 1
Now, glue the above foamed resin sheet cut into cm width.
This was used as the reinforcing material of this invention. This reinforcing material was attached to a 0.7wt thick steel plate so that the second epoxy resin composition side, that is, the side to which the foamable resin sheet was attached, was on the inside, and then heated in an atmosphere of 150°C. It was heated during the heat. As a result, a reinforcing layer consisting of a foamed layer strongly fixed to the copper plate and a fiber-reinforced resin layer in which bead-shaped bulges were formed by the foamed layer was obtained. When the following strength test was conducted using the steel plate reinforced in this way as a test piece, the maximum bending stress was 55k9/50 at 20°C.
TnIft width, and the maximum bending stress of the steel plate alone without any reinforcement measures was 8k9/50m width, but it was found that an extremely excellent reinforcing effect was obtained.

Furthermore, when a similar strength test was conducted at 50℃, 40
The width was k9/50m, and the high temperature properties were also good. Further, no whisker phenomenon was observed visually in the steel plate after heat hardening. <Strength test> Two vertical flat plates, each of which has an inverted U-shaped cross section with a radius of curvature of 5 mm, are placed in parallel with a distance of 100T0n between the tips.
A test piece with a width of 5" is horizontally supported on a support stand having a width of 507T0n), and a radius of curvature of 1" is set in the center from the top.
0Tr0n (1) Vertical flat plate exhibiting a U-shaped cross section (width 50
Maximum bending stress (K9/5) when a load is applied (w0n)
- Width) was measured.

Example 2 60 parts of Epicote #828 (mentioned above), Epicote #10
02 (mentioned above) 35 parts, phenoxy resin (manufactured by Union Carbide) 5 parts, Kyuazol 2MZ Ichiyaku 1NE (epoxy resin latent curing agent made by Shikoku Kasei Co., Ltd.) 5 parts, dicyandiamide (mentioned above) 5 parts, talc chief and asbestos powder 2
An epoxy resin composition consisting of 0.5 Wr! The sheet was formed into a sheet having a thickness of n, and a glass fiber cloth (1) WE26-104 manufactured by Tobo Co., Ltd.) was further laminated thereon to form a first epoxy resin composition layer.

Next, Epicoat #1004 (mentioned above) Kabe, Epicoat #871 (dimer acid-modified epoxy resin manufactured by Yuka Shell Co., Ltd.) 8(2), D. An epoxy resin composition consisting of 5 parts of P hardener (mentioned above), 5 parts of dicyandiamide, talc (branch) part and 2 parts of asbestos powder was molded into a sheet with a thickness of 0.5 mm in the same manner as in Example 1. An epoxy resin composition was prepared.

This second epoxy resin composition layer was bonded to the first epoxy resin composition layer to obtain a reinforced epoxy resin sheet.

The glass transition temperature of the first and second epoxy resin composition layers of this sheet after heating and curing is 120°C for the first layer;
The temperature was 45°C in the second layer. However, the conditions for heat curing are as follows:
The temperature is 150°C for 60 minutes. Next, apply the above reinforced epoxy resin sheet to 5C7F! The foamed resin sheet obtained in Example 1, which had been cut into a width of 1 cm, was adhered to the second epoxy resin composition layer side of this sheet to obtain a reinforcing material of the present invention.

When a steel plate was reinforced using this reinforcing material in the same manner and under the same conditions as in Example 1, the maximum bending stress was 20°C.
An extremely excellent reinforcing effect of 65k9/50m 1t width was obtained.

Furthermore, when the strength was measured at 50℃, it was found to be 48k9/
The high temperature properties were also good with a width of 50wn. Further, no whisker phenomenon was visually observed during heat curing. Comparative Example 1 The first epoxy resin composition of Example 2 was formed into a sheet with a thickness of 0.6 WL, and a glass fiber cloth (WK3O3OA manufactured by Nittobo Co., Ltd.) was laminated thereon.

This sheet was cut into 5 cm wide pieces, and then the foamed resin sheet obtained in Example 1 cut into 1 cm wide pieces was adhered to obtain a reinforcing material. Using this reinforcing material, a copper plate was reinforced using the same operations and under the same conditions as in Example 1, and the maximum bending stress was 50 kg/507177! When the steel plate was heated and hardened, a whisker phenomenon occurred.

Comparative Example 2 Using the second epoxy resin composition of Example 1,
．． A sheet with a thickness of 27 m was formed, and a glass fiber cloth (WK3O3OA manufactured by Nitto Boseki Co., Ltd.) was laminated thereon.

This sheet was cut into 5 cm wide pieces, and then the foamed resin sheet obtained in Example 1 cut into 1 cm wide pieces was adhered to obtain a reinforcing material. When a steel plate was reinforced using this reinforcing material in the same manner and under the same conditions as in Example 1, no heat-hardened whisker phenomenon occurred.

However, it was found that the maximum bending stress was 48kg/50wt width at 20°C, and 20k9/50m width at 50°C, indicating poor characteristics.

[Brief explanation of the drawing]

FIG. 1 is a perspective view showing one embodiment of the reinforcing material of the present invention, FIG. 2 is a sectional view showing the reinforcing material in a state in which it is installed before heating, and FIG. 3 is a sectional view showing the state after heating. 1...Reinforcement material, 2...Fibre base material, 3.
...Reinforced resin sheet, 3a... Mounting surface,
3b...Bead-shaped bulging portion, 4...Bead forming material, E...First thermosetting resin composition layer, F......No. No. 2 thermosetting resin composition layer.

Claims (1)

[Claims] 1. A first thermosetting resin composition layer in which the resin is blended so that the glass transition temperature when cured by heating is high, and a resin blended in the same manner as above so that the glass transition temperature is low. The second thermosetting resin sheet of an uncured or semi-cured thermosetting reinforcing resin sheet in which at least one layer of a laminated sheet comprising a second thermosetting resin composition layer contains a fiber base material. A bead forming material that is formed to be narrower than the sheet and that forms a bead-like bulge on the sheet before the sheet is cured is attached to the resin composition layer side, and the bead forming material is extended wider than the width of the bead forming material. A reinforcing material characterized in that a hem portion of the sheet on the second thermosetting resin composition layer side forms a mounting surface. 2 Claim 1 in which the fiber base material is glass fiber cloth
Reinforcement material as described in section.