JPH11263865A - Expandable reinforcement composition and reinforcement of car body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel expandable reinforcement composition and a reinforcement method of car bodies using the expandable reinforcement composition. SOLUTION: An expandable reinforcement composition comprises (A) 100 pts.wt. epoxy resin which comprises a mixture of a bisphenol A epoxy resin and a dimer acid-modified product of a bisphenol A epoxy resin, (B) 10 to 50 pts.wt. methacrylate polymer in the form of a powder, (C) 3 to 30 pts.wt. heat-activated curing agent for epoxy resins, (D) 0.5 to 15 pts.wt. heat-activated curing catalyst for epoxy resins, (E) from 0.5 to 15 pts.wt. thermally decomposing organic blowing agent, (F) 50 to 200 pts.wt. inorganic filler, (G) 2 to 15 pts.wt. bubble inhibitor and (H) 2 to 15 pts.wt. carbon black. Furthermore, a reinforcement method of car bodies which are equipped with box members comprising steel plates comprises steps wherein the above-mentioned expandable reinforcement composition is disposed on the steel plate part corresponding to the interior of the box member, subsequently, the steel plate is attached and the box members are assembled, then, the assembled box members are exposed to electrocoating treatment and the expandable reinforcement is expanded in the baking process of this treatment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel foamable reinforcing material composition and a method for reinforcing a vehicle body using the foamable reinforcing material composition. More specifically, the foamable reinforcing material composition of the present invention comprises (A) a bisphenol A type epoxy resin represented by the following general formula [I], and a bisphenol A type dimer acid represented by the following general formula [II] (B) 10 to 50 parts by weight of a powdery methacrylate-based polymer, (C) 3 to 30 parts by weight of a heat-active curing agent for an epoxy resin, and (D) based on 100 parts by weight of an epoxy resin comprising a mixture with a modified product. ) Thermally active curing catalyst for epoxy resin 0.5 to 15 parts by weight, (E) thermally decomposable organic foaming agent 0.5 to 15 parts by weight, (F) inorganic filler 50 to 200 parts by weight, (G) bubble prevention agent 2 15 parts by weight and (H) 2 to 15 parts by weight of carbon black. Furthermore, the method of reinforcing a vehicle body of the present invention includes the step of mounting the foam reinforcing material composition on a steel sheet formed in advance, assembling a box-shaped member using the steel sheet, in a baking step at the time of electrodeposition coating of the vehicle body, For example, 10-3 at 140-230 ° C
By heating for 0 minutes, the rigidity of the vehicle body can be improved by foaming and filling.

[0002]

2. Description of the Related Art In general, in a vehicle body structure of an automobile, a skeleton of each part of the vehicle body is firmly formed in consideration of running stability, riding comfort, noise and vibration performance. The conventional body skeleton has a box-shaped closed cross-section structure and is manufactured in various cross-sectional shapes.However, in order to reduce the weight of the vehicle body due to social demands for fuel efficiency improvement from the viewpoint of depletion of fossil fuel and atmospheric environment, Each of them has a thin plate structure, and it is common to use a metal reinforcing material to compensate for the decrease in rigidity. Also,
On the other hand, Japanese Patent Laid-Open Publication No. 48-2631 proposes a vehicle body structure in which a rigid urethane foam is filled in the closed section to reinforce the vehicle body skeleton. The filling of the foam has a high effect of suppressing wall buckling and significantly improves the rigidity of the box-shaped member, so that the weight of the vehicle body is not significantly increased as compared with the method of reinforcing the vehicle body with a metal reinforcing material. The rigidity can be improved.

[0003] As a resin foam type filler,
In addition to urethanes, there are olefin resin foam fillers (Seakalastomer 240, manufactured by Nippon Sika Co., Ltd.) and epoxy resin foam fillers (OROTEX815, manufactured by Iida Sangyo Co., Ltd.). / Filling type.

[0004]

However, in the reinforcing method using a urethane resin, the urethane undiluted solution is injected into the box-shaped closed-section member and foamed from the joint between the small hole of the box-shaped member and the closed-section box-shaped member at the time of injection and foaming. Since a considerable amount of material leakage occurs, measures must be taken to prevent this, and it is considered difficult to apply the method to production lines of automobiles. In recent years, from the viewpoint of improving the working environment, the foaming method using CFCs has been replaced by a foaming method using water in recent years. There is a problem that it is difficult to achieve. Further, in the case of the olefin-based resin foam material, a low molecular weight polyethylene wax or the like is used as the base olefin resin, so that the mechanical performance of the material is not sufficient, and even when the material is filled in the box-shaped member, the rigidity of the box-shaped member is reduced. The improvement effect is not enough yet.

On the other hand, in the case of epoxy resin foam,
The disadvantage of the poor impact resistance of epoxy resins must be compensated for. The load input to the vehicle body is not always static, and impact load may be applied to the vehicle body due to uneven road surface during running. Requirement of toughness and toughness.
The method of improving the impact resistance is roughly classified into a method of improving the chemical structure itself of the epoxy resin and a method of adding a separately prepared impact modifier to the epoxy resin. An epoxy resin that can sufficiently satisfy impact properties cannot be obtained. On the other hand, in the latter method, (1) a method of adding a soluble elastomer monomer to an uncured epoxy resin and simultaneously polymerizing the two, (2) a method of adding a compatible elastomer polymer, and (3) a method of adding fine particles A method for dispersing a polymer for improving impact resistance is known.
For (1), an interpenetrating network structure: IPN (Inter-Pen
However, this method generally has disadvantages such as a decrease in the softening point of the product and a variation in mechanical properties. Regarding the method (2), various examples in which an elastomer component such as a butadiene-acrylonitrile copolymer rubber (CTBN or ATBN) having a carboxyl group or an amino group at the terminal is added to modify the rubber are proposed, and some of them are proposed. Has been put to practical use. However, those obtained by this method cannot be said to be sufficiently satisfactory in terms of impact resistance and toughness for use in reinforcing the rigidity of the vehicle body. Further, in the method (3), many impact modifiers such as polyamide resins have been proposed, but all of them are mechanically kneaded, so that a considerable amount of non-uniformity remains in the dispersion of particles. However, there is a disadvantage that mechanical performance is difficult to stabilize.

If the viscosity of the resin sharply decreases in the foaming temperature range, it is difficult to retain the gas generated from the foaming agent in the resin, and it is difficult to foam to form a foam. In order for foam cells to be stably present in the foam,
Temperature dependence of the resin viscosity in the foaming temperature range must be controlled. For this purpose, it is necessary to add an elastomer or the like having high compatibility with the epoxy resin to control the temperature dependence of the viscosity, or to control the temperature dependence of the viscosity by physical crosslinking. However, the method of controlling the viscosity by adding the elastomer has a disadvantage that the rigidity inherent in the epoxy composition is reduced, and when the viscosity is controlled by the crosslinking involving a chemical reaction, the crosslinking density is influenced by the reaction conditions. In addition, since it cannot be strictly controlled, the viscosity is too high and the foaming becomes insufficient, so that there is a possibility that the box-shaped member of an automobile is not sufficiently filled. In addition, when the gas generated from the foaming agent is retained in the resin, if the size of the bubble cells is not uniform, stress concentration tends to occur, so that there is a problem that the shear adhesive strength is reduced.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, (A) general formula [I]:

Embedded image (Where n is a number less than 1 on average) and a bisphenol A type epoxy resin represented by the general formula [I
I]:

Embedded image (B) a powdered methacrylate-based polymer with respect to 100 parts by weight of an epoxy resin comprising a mixture with a bisphenol A-type dimer acid-modified product represented by the formula (wherein R is an alkylene having 1 to 50 carbon atoms): 10 to 50 parts by weight, (C)
3 to 30 parts by weight of heat-active curing agent for epoxy resin, (D)
Heat-activated curing catalyst for epoxy resin 0.5 to 15 parts by weight,
(E) Pyrolytic organic foaming agent 0.5 to 15 parts by weight, (F)
50 to 200 parts by weight of inorganic filler, (G) anti-foaming agent 2
By blending 15 parts by weight and (H) 2 to 15 parts by weight of carbon black, foam cells are uniformly dispersed at the time of foaming, and a foamable reinforcing material composition capable of exhibiting sufficient adhesive force by being in close contact with a steel sheet. And completed the present invention.

Further, the present invention relates to a method for reinforcing a vehicle body. In reinforcing a vehicle body provided with a box-shaped member made of a steel plate, a portion of the steel plate corresponding to the inside of the box-shaped member is provided with the foamable reinforcing member. Material composition, then assemble the steel plate, assemble the box-shaped member, and then subject the assembled box-shaped member to an electrodeposition coating process, and in the baking step of this process, the foamable reinforcing material composition It is characterized by foaming an object.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. Examples of the epoxy resin derived from bisphenol A used as the component (A) in the composition of the present invention include those represented by the general formulas [I] and [II]. In the general formula [I], n is a number of 0 or more, and those having an average value of less than 1 are preferable because they are liquid at ordinary temperature. The general formula [II]
Is a dimer acid modified product of bisphenol A type epoxy resin. In Formula 2, R is preferably an alkylene having 1 to 50 carbon atoms. The resins of the above general formulas [I] and [II] are mixed and used, and the mixing ratio thereof is not particularly limited, but the bisphenol A type epoxy resin is modified with the bisphenol A type epoxy resin dimer acid. Thing is 0.5
It is preferably in the range of 50 to 50% by weight. This amount
If the amount is less than 0.5% by weight, the impact resistance is reduced. If the amount is more than 50 parts by weight, the viscosity cannot be controlled, the foam cells become non-uniform, and stable mechanical performance cannot be obtained.

The powdery methacrylate polymer used as the component (B) in the composition of the present invention is produced by an emulsion polymerization method, and its basic particle size is in the range of 0.1 to 3 μm. Examples of the methacrylate-based monomer in the raw material portion used in this case include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and stearyl methacrylate; alkyl glycol (meth) acrylate such as butoxyethyl methacrylate; and alkylene glycol mono (meth) acrylate. Is mentioned. These may be used alone or in combination of two or more, and among them, methyl methacrylate is particularly optimal.

The Tg of the methacrylate polymer must be 70 ° C. or higher. If the temperature is lower than 70 ° C., the storage stability becomes insufficient when mixed with an epoxy resin. Also, there must be no partial crosslinking. The presence of the crosslinked structure increases the viscosity at the time of heating, making it impossible to foam sufficiently. The amount of the heat-active curing agent (B) is not particularly limited, but is usually 10 to 50 parts by weight based on 100 parts by weight of the epoxy resin (A). When the amount is less than 10 parts by weight, the impact resistance is reduced. When the amount is more than 50 parts by weight, the viscosity is remarkably increased, the composition becomes brittle, and the mechanical performance is significantly impaired.

The heat-active curing agent for the epoxy resin used as the component (C) in the composition of the present invention includes, for example, imidazole such as dicyandiamide, 4,4'-diaminodiphenylsulfone and 2-n-heptadecylimidazole. Derivatives, isophthalic dihydrazide, N,
N-dialkyl urea derivatives, N, N-dialkyl thiourea derivatives, acid anhydrides such as tetrahydrophthalic anhydride, isophorone diamine, m-phenylenediamine,
-Aminoethylpiperazine, melamine, guanamine, boron trifluoride complex compound, trisdimethylaminomethylphenol and the like. These may be used alone or in combination of two or more. Among them, dicyandiamide is particularly preferred. in this case,
To achieve sufficient foaming, the baking temperature of
The baking time is preferably in the range of 0 to 210 ° C, and the baking time is in the range of 10 to 30 minutes.

The amount of the component (C) is not particularly limited, but is usually 3 to 30 parts by weight per 100 parts by weight of the epoxy resin (A). If the amount is less than 3 parts by weight, the composition is not sufficiently cured and the rigidity is remarkably reduced. If the amount exceeds 30 parts by weight, an excessive exothermic reaction occurs during curing, causing partial decomposition and thermal deterioration, It causes a significant impairment of the mechanical performance of the composition. The curing agent has a reaction temperature of 140 to 230.
It is preferably used for epoxy resins in the range of ° C.

The heat-active curing catalyst for epoxy resin used as component (D) in the composition of the present invention includes:
For example, modified polyamines such as an amine adduct which is an epoxy compound-added polyamine, a Michael-added polyamine, a Mannich-added polyamine, a thiourea-added polyamine, and a ketone-blocked polyamine, may be used alone or in combination of two or more. Among them, an amine adduct, which is an epoxy compound-added polyamine, is particularly preferable.

The amount of the component (D) of the heat-active curing catalyst for epoxy resin is not particularly limited.
Normally, 0.5 parts per 100 hours of epoxy resin of component (A)
A range of の 15 parts by weight is preferred. If the amount is less than 0.5 part by weight, there is a problem in handling such as a decrease in viscosity and irritation to skin and mucous membranes. If the amount exceeds 15 parts by weight, the compatibility with the epoxy resin becomes poor.

The thermally decomposable organic blowing agent used as the component (E) in the composition of the present invention includes, for example, azo compounds such as azodicarbonamide and azobisisobutyronitrile, and dinitrosopentamethylenetetramine. And a sulfohydrazide compound such as p-toluenesulfonylhydrazide, 4,4'-oxybenzenesulfonylhydrazide, which may be used alone or in combination of two or more. Good, but among these, azodicarbonamide is particularly preferred. The thermal decomposition type organic foaming agent of the component (E) preferably has a thermal decomposition temperature in the range of 100 to 230 ° C.

In the case of using a thermal decomposition type organic foaming agent, zinc white, zinc nitrate, lead phthalate, tribasic lead phosphate, and the like are usually used as foaming aids for controlling an appropriate foaming temperature. Inorganic salts such as tribasic lead sulfate, zinc fatty acid soap, lead fatty acid soap, metallic soap such as cadmium fatty acid soap, boric acid, oxalic acid, succinic acid, acids such as adipic acid, urea, biurea, ethanolamine, glycol,
One or more of glycerin and the like can be mixed and used. In this case, in order to perform sufficient foaming in the automobile coating process, the thermal decomposition start temperature (gas generation start temperature)
Is desirably 100 ° C. or higher.

The amount of the organic foaming agent (E) is not particularly limited, but is usually in the range of 0.5 to 15 parts by weight per 100 parts by weight of the epoxy resin (A). It is. If the amount is less than 0.5 parts by weight, the foaming becomes insufficient, and if it exceeds 15 parts by weight, the control of the foaming is not effective, and stable mechanical performance cannot be obtained.

Examples of the inorganic filler used as the component (F) in the composition of the present invention include calcium silicate, calcium carbonate, talc, clay, mica, aluminum hydroxide, glass beads, and shirasu balloon. These may be used alone or in combination of two or more. Of these, calcium silicate is particularly preferred. The reinforcing effect can be increased by adding a glass chop having a fiber length of about 1 to 6 mm. The filler as the component (F) preferably has an aspect ratio, for example, an aspect ratio of 2: 1 or more. This is because the size of the cell of the foaming agent becomes uniform, and sufficient strength is obtained.

The amount of the inorganic filler used as the component (F) is not particularly limited, but is usually 50 to 100 parts by weight of the epoxy resin (A).
200 parts by weight. If the amount is less than 50 parts by weight, a sufficient reinforcing effect cannot be obtained, and if it exceeds 200 parts by weight, the viscosity is remarkably increased, and the composition becomes brittle, resulting in significantly impairing the mechanical performance. Also, the shape of the inorganic filler is
Any of a needle shape, a column shape, and a plate shape may be used.

Examples of the antifoaming agent used as the component (G) of the present invention include calcium oxide. The amount of the foam inhibitor used as the component (G) is not particularly limited, but is usually 2 to 1 based on 100 parts by weight of the epoxy resin of the component (A).
5 parts by weight. If the amount is less than 2 parts by weight, the size of the cell becomes uneven and the effect of reinforcing the adhesive cannot be sufficiently obtained.
H is remarkably increased, which causes a decrease in coating quality.

The amount of the carbon black used as the component (H) in the composition of the present invention is not particularly limited.
It is 2 to 15 parts by weight with respect to 0 parts by weight. If the amount is less than 2 parts by weight, a sufficient reinforcing effect cannot be obtained, and if it exceeds 15 parts by weight, the viscosity is remarkably increased, and the composition becomes brittle, resulting in significantly impairing the mechanical performance.

The foamable reinforcing material composition of the present invention comprises the epoxy resin (A), the methacrylate resin powder particles (B), the heat-active curing agent (C), and the thermal activity (D). A curing catalyst, an organic foaming agent of component (E), an inorganic filler of component (F), an air bubble inhibitor of component (G), carbon black of component (H), and optional components used as desired. Can be prepared. Examples of the additive component blended in the composition include a plasticizer, a diluent, a stabilizer, a reinforcing agent, a coloring agent, an antioxidant, an ultraviolet absorber, a lubricant, and a thixotropic agent.

[0024]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples. The physical properties of the composition were evaluated by the following methods. (1) Foaming Uniformity A foamable reinforcing material composition is filled in a steel sheet panel material having a cross-sectional shape of 60 mm x 50 mm, and baked at 170 ° C for 20 minutes. It was evaluated visually. ○ Uniform × Non-uniform (2) Member rigidity test A box-shaped cross-section member having a cross-sectional shape of 60 mm × 50 mm and a length of 400 was filled with the foamable reinforcing material composition, and was heated at 170 ° C × 20
After baking for minutes, a bending test as shown in FIG. 1 was performed, and the foamable reinforcing material composition was compared with an unfilled box-shaped cross-sectional member, and the rigidity was evaluated according to the following criteria. Support part span 300mm, speed 10mm / min, stroke 4
It was measured to 0 mm. ○ Sufficiently improved rigidity to a satisfactory level △ Stiffness improved but not at a satisfactory level × No improvement in rigidity (3) Shear adhesion test 100 mm × 25 mm × 1.6 mm cold rolled Unbaked steel plate is baked at 170 ° C for 20 minutes, JIS K6
850 was evaluated. ○ The shear adhesive strength has been sufficiently improved to a satisfactory level △ The shear adhesive strength has been improved but not at a satisfactory level × The shear adhesive strength has not been improved (4) Storage Property 40 ° C, 5 After leaving the room indoors at room temperature for 170 days,
After baking for minutes, the rate of change of the expansion ratio was measured. ○ No change × Decrease in expansion ratio

Example 1 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. With respect to 15 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained, the following general formula II
I:

Embedded image (Wherein n is 0.7)
Epoxy resin and the following general formula IV:

Embedded image (Wherein R is an alkylene having 34 carbon atoms) 100 parts by weight of an epoxy resin comprising a mixture with a bisphenol A type epoxy resin modified with a dimer acid, 11 parts by weight of a curing agent dicyandiamide, and a curing catalyst amine adduct ( 6 parts by weight of an epoxy compound-added polyamine), 4,4'-oxybenzenesulfonyl hydrazide 6, an organic blowing agent
Parts by weight, 130 parts by weight of an inorganic filler calcium silicate, 9 parts by weight of a foam inhibitor calcium oxide, and 9 parts by weight of carbon black are mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. did. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 2 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin and the bisphenol A type epoxy resin modified with a dimer acid of Example 1 is used for 45 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) obtained as described above. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Comparative Example 1 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin and the bisphenol A type epoxy resin modified with a dimer acid in Example 1 was added to 5 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide,
6 parts by weight of curing catalyst amine adduct, organic blowing agent 4,
6 parts by weight of 4'-oxybenzenesulfonyl hydrazide,
130 parts by weight of the inorganic filler calcium silicate, 9 parts by weight of the foam inhibitor calcium oxide, and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Comparative Example 2 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin modified with a dimer acid is used for 60 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 3 Methyl methacrylate was emulsion-polymerized and atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of an epoxy resin, 5 parts by weight of a curing agent dicyandiamide,
6 parts by weight of curing catalyst amine adduct, organic blowing agent 4,
6 parts by weight of 4'-oxybenzenesulfonyl hydrazide,
130 parts by weight of the inorganic filler calcium silicate, 9 parts by weight of the foam inhibitor calcium oxide, and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 4 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 20 parts by weight of dicyandiamide curing agent, 6 parts by weight of amine adduct for curing catalyst, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Comparative Example 3 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 1 part by weight of dicyandiamide curing agent,
6 parts by weight of curing catalyst amine adduct, organic blowing agent 4,
6 parts by weight of 4'-oxybenzenesulfonyl hydrazide,
130 parts by weight of the inorganic filler calcium silicate, 9 parts by weight of the foam inhibitor calcium oxide, and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

COMPARATIVE EXAMPLE 4 Methyl methacrylate was emulsion-polymerized and atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 40 parts by weight of dicyandiamide curing agent, 6 parts by weight of amine adduct of curing catalyst, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 5 Methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. The powdery methacrylate polymer (Tg:
90 ° C.) 30 parts by weight of epoxy resin 10 comprising a mixture of bisphenol A type epoxy resin of Example 1 and bisphenol A type epoxy resin dimer acid modified product
0 parts by weight, curing agent dicyandiamide 11 parts by weight, curing catalyst amine adduct 1 part by weight, organic blowing agent 4,4'-oxybenzenesulfonylhydrazide 6 parts by weight, inorganic filler calcium silicate 130 parts by weight, anti-foaming agent oxidation 9 parts by weight of calcium and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above (1)-
The evaluation of (6) was performed. Table 1 shows the evaluation results.

Example 6 Methyl methacrylate was subjected to emulsion polymerization, and this was pulverized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 12 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonyl hydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Comparative Example 5 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of dicyandiamide curing agent, 0.1 part by weight of amine adduct of curing catalyst, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Comparative Example 6 Methyl methacrylate was subjected to emulsion polymerization, and this was pulverized by spray drying to obtain a powdery polymer having a particle size of 1 μm. An epoxy resin 100 composed of a mixture of a bisphenol A type epoxy resin and a bisphenol A type epoxy resin modified with a dimer acid is added to 30 parts by weight of the thus obtained powdery methacrylate polymer (Tg: 90 ° C.).
Parts by weight, curing agent dicyandiamide 11 parts by weight, curing catalyst amine adduct 20 parts by weight, organic blowing agent 4,4'-oxybenzenesulfonyl hydrazide 6 parts by weight, inorganic filler calcium silicate 130 parts by weight, air bubble inhibitor calcium oxide 9 parts by weight and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above (1)-
The evaluation of (6) was performed. Table 1 shows the evaluation results.

Example 7 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 1 part by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 8 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 12 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Comparative Example 7 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 0.1 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Comparative Example 8 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 20 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 9 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 60 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and carbon black 9
Parts by weight were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 10 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 180 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

COMPARATIVE EXAMPLE 9 Methyl methacrylate was emulsion-polymerized and atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of dicyandiamide curing agent, 6 parts by weight of amine adduct of curing catalyst, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 30 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and carbon black 9
Parts by weight were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Comparative Example 10 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 250 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 11 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 3 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 12 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 12 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Comparative Example 11 Methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. The powdery methacrylate polymer (Tg:
90 ° C.) 30 parts by weight of epoxy resin 10 comprising a mixture of bisphenol A type epoxy resin of Example 1 and bisphenol A type epoxy resin dimer acid modified product
0 parts by weight, curing agent dicyandiamide 11 parts by weight, curing catalyst amine adduct 6 parts by weight, organic blowing agent 4,4'-oxybenzenesulfonylhydrazide 6 parts by weight, inorganic filler calcium silicate 130 parts by weight, anti-foaming agent oxidation 1 part by weight of calcium and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above (1)-
The evaluation of (6) was performed. Table 2 shows the evaluation results.

Comparative Example 12 Methyl methacrylate was emulsion-polymerized and atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 20 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 13 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 3 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Example 14 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin modified with a dimer acid is used for 30 parts by weight of the thus obtained powdery methacrylate polymer (Tg: 30 ° C.). 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 12 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Comparative Example 13 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 1 part by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Comparative Example 14 Methyl methacrylate was subjected to emulsion polymerization, and this was pulverized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 20 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Example 15 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent 4,4'-oxybenzenesulfonylhydrazide, 130 parts by weight of inorganic filler calcium silicate, bubble prevention 9 parts by weight of calcium oxide and 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Example 16 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product was prepared with respect to 15 parts by weight of the thus obtained powdery methacrylate polymer (Tg: 90 ° C.). 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent azodicarbonamide, 130 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 17 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin and the bisphenol A type epoxy resin modified with a dimer acid of Example 1 is used for 45 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) obtained as described above. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent azodicarbonamide, 130 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 18 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of an epoxy resin, 5 parts by weight of a curing agent dicyandiamide,
A planetary mixer comprising 6 parts by weight of a curing catalyst amine adduct, 6 parts by weight of an organic blowing agent azodicarbonamide, 130 parts by weight of an inorganic filler calcium silicate, 9 parts by weight of a foam inhibitor calcium oxide, and 9 parts by weight of carbon black. And mixed at room temperature to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed.
Table 1 shows the evaluation results.

Example 19 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of an epoxy resin, 20 parts by weight of a curing agent dicyandiamide, 6 parts by weight of a curing catalyst amine adduct, 6 parts by weight of an organic blowing agent azodicarbonamide, 130 parts by weight of an inorganic filler calcium silicate, and 9 parts by weight of a foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 20 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of an epoxy resin, 11 parts by weight of a curing agent dicyandiamide, 1 part by weight of a curing catalyst amine adduct, 6 parts by weight of an organic blowing agent azodicarbonamide, 130 parts by weight of an inorganic filler calcium silicate, 9 parts by weight of a foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 21 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of an epoxy resin, 11 parts by weight of a curing agent dicyandiamide, 12 parts by weight of a curing catalyst amine adduct, 6 parts by weight of an organic blowing agent azodicarbonamide, 130 parts by weight of an inorganic filler calcium silicate, and 9 parts by weight of a foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 22 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. Epoxy resin 100 parts by weight, curing agent dicyandiamide 11 parts by weight, curing catalyst amine adduct 6 parts by weight, organic blowing agent azodicarbonamide 1 part by weight, inorganic filler calcium silicate 130 parts by weight, bubble prevention agent calcium oxide 9 parts by weight And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 1 shows the evaluation results.

Example 23 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 12 parts by weight of organic blowing agent azodicarbonamide, 130 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 24 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent azodicarbonamide, 60 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide ,
And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 25 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent azodicarbonamide, 180 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 26 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of an epoxy resin, 11 parts by weight of a curing agent dicyandiamide, 6 parts by weight of a curing catalyst amine adduct, 6 parts by weight of an organic blowing agent azodicarbonamide, 130 parts by weight of an inorganic filler calcium silicate, and 3 parts by weight of a foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 27 Methyl methacrylate was emulsion-polymerized and atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of an epoxy resin, 11 parts by weight of a curing agent dicyandiamide, 6 parts by weight of a curing catalyst amine adduct, 6 parts by weight of an organic foaming agent azodicarbonamide, 130 parts by weight of an inorganic filler calcium silicate, 12 parts by weight of a foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 2 shows the evaluation results.

Example 28 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent azodicarbonamide, 130 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide , And 3 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Example 29 Methyl methacrylate was subjected to emulsion polymerization, which was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent azodicarbonamide, 130 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide , And 12 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Example 30 Methyl methacrylate was subjected to emulsion polymerization, and this was atomized by spray drying to obtain a powdery polymer having a particle size of 1 μm. A mixture of the bisphenol A type epoxy resin of Example 1 and the bisphenol A type epoxy resin dimer acid modified product is used for 30 parts by weight of the powdery methacrylate polymer (Tg: 90 ° C.) thus obtained. 100 parts by weight of epoxy resin, 11 parts by weight of curing agent dicyandiamide, 6 parts by weight of curing catalyst amine adduct, 6 parts by weight of organic blowing agent azodicarbonamide, 130 parts by weight of inorganic filler calcium silicate, 9 parts by weight of foam inhibitor calcium oxide And 9 parts by weight of carbon black were mixed at room temperature using a planetary mixer to prepare a foamable reinforcing material composition. On the other hand, the above evaluations (1) to (6) were performed. Table 3 shows the evaluation results.

Example 31 As shown in FIG. 2, the foamable reinforcing material composition of the present invention was applied to a steel sheet 2 which was formed in advance so as to constitute a center pillar / waist portion of a vehicle body and a roof rail / center pillar joint portion, as shown in FIG. 1 was pasted. Next, the steel sheet 2 was welded, and after assembling the vehicle body 3, it was washed with a chemical conversion treatment liquid in order to improve the adhesion of the coating film on the vehicle body 3. Further, after the body 3 was immersed in the electrodeposition bath 4 to perform rust prevention treatment, the body 3 was placed in the baking furnace 5 and the electrodeposition coating film was baked at 170 ° C. for 20 minutes. The water-soluble reinforcing material composition 1 was sufficiently foamed and cured to form a uniform foamed material 6. Thus, the foamable reinforcing material composition of the present invention can be favorably used in an actual line, and the rigidity of the box-shaped structural material of the vehicle body can be reliably improved.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

[Table 5]

[0075]

As described above, the present invention provides a bisphenol A type epoxy resin and a bisphenol A in which powdery methacrylate polymer resin particles are dispersed.
A foaming reinforcing material composition obtained by blending a curing agent, a curing catalyst and an air bubble inhibitor with an epoxy resin comprising a mixture with a type epoxy resin dimer acid modified product is mounted on a preformed steel sheet, and the steel sheet is used. After assembling the box-shaped member, when foaming and filling are performed in the baking process during vehicle body adhesion painting, the foamed cells become uniform, thereby improving the shear adhesive strength between the foamable reinforcing material composition and the steel sheet. It has become possible. As a result, it is expected that the body frame will be reinforced lightly, improving the riding comfort of the vehicle, reducing noise and vibration, and filling the box-shaped closed-section member with a high-rigidity foam, resulting in a vehicle collision. Energy absorption hardening at the time can also be expected.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a method for measuring an improvement in rigidity of a box-shaped cross-section member according to the present invention.

FIG. 2 is a process chart showing an example in which the foamable reinforcing material composition of the present invention is applied to a vehicle body reinforcing method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Foamable reinforcing material composition before hardening 2 Steel plate 3 Car body 4 Electrodeposition bath 5 Baking furnace 6 Foaming material

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B62D 29/04 C08K 3/00 C08K 3/00 C08L 63/00 A C08L 63/00 B29C 67/22 (72) Inventor Kazuki Ogoshi Central Tokyo 1-10-1, Kyobashi-ku, Tokyo Asahi Corporation (72) Katsuhiko Suzuki, inventor Katsuhiko Suzuki 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Nissan Motor Co., Ltd. (72) Takayuki Fukui 2 Takaracho, Kanagawa-ku, Yokohama, Kanagawa Address Nissan Motor Co., Ltd.

Claims (9)

[Claims] (A) 100 parts by weight of an epoxy resin comprising a mixture of a bisphenol A type epoxy resin and a bisphenol A type epoxy resin dimer acid modified product; (B) 10 to 50 parts by weight of a powdery methacrylate polymer; (C) 3 to 30 parts by weight of a thermally activated curing agent for an epoxy resin, (D) 0.5 to 15 parts by weight of a thermally activated curing catalyst for an epoxy resin, (E) 0.5 to 15 parts by weight of a thermally decomposable organic foaming agent, A foamable reinforcing material composition comprising: F) 50 to 200 parts by weight of an inorganic filler; (G) 2 to 15 parts by weight of an anti-foaming agent; and (H) 2 to 15 parts by weight of carbon black. 2. The foamable reinforcing material composition according to claim 1, wherein (B) the powdery methacrylate polymer has a particle size of 0.1 to 3 μm and a glass transition temperature of 70 ° C. or more. Stuff. 3. The heat-activated curing agent for epoxy resin (C),
The foamable reinforcing material composition according to claim 1, wherein the composition reacts in a range of 140 to 230 ° C. 4. The method according to claim 1, wherein the heat-activated curing catalyst for the epoxy resin is a modified polyamine.
3. The foamable reinforcing material composition according to item 1. 5. The foamable reinforcing material composition according to claim 1, wherein the thermal decomposition onset temperature of the thermal decomposition type organic foaming agent (E) is in the range of 100 to 230 ° C. 6. The foamable reinforcing material composition according to claim 1, wherein the shape of the (F) inorganic filler is a needle shape, a column shape or a plate shape. 7. The foamable reinforcing composition according to claim 1, wherein the inorganic filler has an aspect ratio of 2: 1 or more. 8. A method for reinforcing a vehicle body provided with a box-shaped member made of a steel plate, wherein a portion of the steel plate corresponding to the inside of the box-shaped member is provided. Place the foamable reinforcing material composition described, then assemble the steel plate, assemble the box-shaped member, and then subject the assembled box-shaped member to an electrodeposition coating process, the baking step of this process The method of reinforcing the vehicle body, wherein the foamable reinforcing material composition is foamed. 9. In the baking step, 140 to 230
The method for reinforcing a vehicle body according to claim 8, wherein heating is performed at 10C for 10 to 30 minutes.