JPH11199755A - Molding material composition, its production, and process for molding it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding material composition which needs no thermocompression apparatus, is easily handleable and a moldable and curale in situ, a process for producing it, and process for molding it. SOLUTION: There is provided a molding material composition comprising (A) a normally liquid epoxy resin, (B) an epoxy curing agent, (C) a thickener having an effective component being a thermoplastic resin powder containing at least one type of repeating units of a monomer selected among acrylic esters, methacrylic esters, dienes, and monomers copolymerizable therewith and having a core/shell structure, (D) an inorganic filler, and (E) a material having the property of self-generating heat by a physical means and has the property of being thickened and cured upon being heated by a physical means.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy-based molding material which is easy to handle and can be molded on site, and which can be cured by heating by physical means such as electromagnetic induction, electric current and ultrasonic waves, and a method for producing and molding the same. It is.

[0002]

2. Description of the Related Art A so-called FRP in which a thermosetting resin is reinforced with a fiber reinforcing material is used in various fields such as fishing boats, boats, tanks, pipes, industrial members, and housing members. In addition, sheet molding compounds (hereinafter abbreviated as SMC) and bulk molding compounds (hereinafter abbreviated as BMC) are widely used as molding methods from the viewpoints of work efficiency and work environment.

[0003] SMC was put into practical use in the early 1970's, and its demand is expanding in various fields such as industrial parts, parts for automatic companies, bathtubs and the like. The SMC is composed of reinforced short fibers and a matrix resin, and is produced by impregnating the reinforced short fibers with a molding material composition and forming a sheet into a B-stage. In the case of BMC, it is manufactured as a B stage in a bulk state instead of a sheet state. The matrix resin used for SMC and BMC includes unsaturated polyester, vinyl ester resin, epoxy resin, phenol resin and the like.

On the other hand, epoxy resins having excellent characteristics of fatigue resistance and heat resistance are being studied for use as SMC and BMC in a wide range of fields because of their characteristics. However, such an epoxy resin is cured in a molding die by a heat compression molding apparatus at 150 ° C. or higher in order to exhibit high strength and high hardness.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molding material which is easy to handle without using a heat compression molding apparatus, can be molded and cured on site without heating, and a method for producing and molding the same. is there.

[0006]

Means for Solving the Problems The present inventors have made intensive studies on these problems, and as a result, completed the present invention.

That is, the present invention provides (A) an epoxy resin which is liquid at room temperature, (B) an epoxy curing agent, (C) a thickener containing a thermoplastic resin powder as an active ingredient, (D) an inorganic filler, A) a molding material composition comprising a material having self-heating properties by physical means, having a property of thickening by the heat generated by the physical means and being curable, preferably a physical means,
Electromagnetic induction, ultrasonic waves, and electric current, preferably the material having self-heating property (E) is one or more selected from metal powder, metal foil, wire mesh, carbon fiber, and carbon sheet. That preferably the epoxy resin
(A) 5 to 150 parts by weight of a thickener (C) containing a thermoplastic resin powder as an active ingredient, and 1 inorganic filler (D) per 100 parts by weight.
The thickener (C) is preferably a thermoplastic resin powder composed of a core / shell type copolymer composed of a core layer and a shell layer, more preferably a thickener (C). The viscous agent (C) is a thermoplastic resin powder containing at least one monomer unit selected from acrylates, methacrylates, dienes and monomers copolymerizable therewith. , Preferably a thickener (C)
The shell layer of the thermoplastic resin powder is composed of an acrylate or methacrylate methacrylate polymer that expresses solubility by heating the epoxy resin, preferably a thickener (C) The shell layer of the thermoplastic resin powder of the acrylate or methacrylate copolymer containing N-substituted acrylamide, preferably the shell layer of the thermoplastic resin powder of the thickener (C), To a copolymer having a free carboxyl group, a metal cation is added and the copolymer is cross-linked by ionic or coordination bonds, preferably, further containing a fiber reinforcing material (E), (A) Epoxy resin liquid at room temperature, (B) epoxy curing agent, (C) thickener containing thermoplastic resin powder as active ingredient, (D) inorganic filler, powdered self-heating material (E) After kneading, to increase the viscosity by heating, further (A) epoxy resin liquid at room temperature, (B) epoxy curing agent, (C) a thickener containing thermoplastic resin powder as an active ingredient, (D) inorganic filler Is applied on a film after kneading, and a material (E) having self-heating property is impregnated thereon by a fibrous physical means and impregnated, and a method for producing a molding material characterized by thickening by heating, (A) epoxy resin liquid at room temperature, (B) epoxy curing agent, (C) thickener containing thermoplastic resin powder as an active ingredient, (D) inorganic filler, (E)
After kneading by physical means, applied on the film, sandwiched by a sheet-like physical means material having self-heating properties, the method of manufacturing a molding material characterized by thickening by heating, by the above manufacturing method The present invention relates to a molding method, a molding material composition, a production method, and a molding method, wherein the obtained molding material is shaped and then cured by any one of electromagnetic induction, ultrasonic waves, and electric current.

Next, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The molding material of the present invention refers to a property of increasing viscosity by heat generated by physical means such as electric current, electromagnetic induction, and ultrasonic waves without impairing the characteristics of the epoxy resin and without using a heating device. SMC or BMC molding materials which are hardenable and curable, preferably as molding materials.

The epoxy resin (A) of the present invention which is liquid at normal temperature
May be any liquid resin having one or more epoxy groups in one molecule, and a solid epoxy resin can be used by dissolving in a liquid epoxy resin. Examples thereof include condensates of ordinary bisphenol A and epichlorohydrin, glycidyl ethers such as condensates of bisphenol F and epichlorohydrin, aliphatic glycidyl ethers, alicyclic epoxides, and condensates of phthalic acid derivatives and epichlorohydrin. Diglycidyl ester, hydantoin type epoxy resin, novolak type epoxy resin, glycidylamine type epoxy resin, dimer acid modified epoxy resin, NBR modified epoxy resin, urethane modified epoxy resin, etc., used alone or as a mixture of two or more can do.

As the epoxy curing agent (B), a heat-activated curing agent is preferably used, and any curing agent which exerts a curing action by heating may be used. For example, dicyandiamide, 4,4'-diaminodiphenyl Sulfone,
Imidazole derivatives such as 2-n-pentadecylimidazole, isophthalic acid dihydrazide, N, N'-dialkyl urea derivatives, N, N'-dialkyl thiourea derivatives, melamine, guanamine and the like. The amount used is determined according to the epoxy equivalent of the epoxy resin (A) used and the curing conditions, but preferably the epoxy resin (A)
It is 1 to 15 parts by weight for 100 parts by weight.

The above-mentioned imidazole derivatives, N, N'-dialkylurea derivatives, alkylaminophenol derivatives and the like can also be used as accelerators. The necessary and sufficient compounding amount for curing the curing agent and the accelerator can be easily determined by a preliminary test.

The thickener (C) is a resin powder containing at least one monomer unit selected from acrylates, methacrylates, dienes and monomers copolymerizable therewith. And a thermoplastic resin powder composed of a core layer and a shell layer as an active ingredient.

The thickener (C) is preferably a resin powder containing at least one monomer unit selected from acrylates, methacrylates, dienes and aromatic vinyl compounds. A thermoplastic resin powder composed of a shell and a shell layer is used as an active ingredient. Examples of the acrylate and methacrylate used for the component of the thickener (C) include, for example, ethyl (meth) acrylate, n-
Butyl (meth) acrylate, methyl methacrylate,
Butyl (meth) acrylate, n-propyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl methacrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (Meth) acrylate, n-octyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like.

The diene monomers include conjugated diene compounds such as butadiene, isoprene, 1,3-pentadiene, cyclopentadiene and dicyclopentadiene, and non-conjugated diene compounds such as 1,4-hexadiene and ethylidene norbornene. And the like.

The monomers copolymerizable therewith include styrene, α-methylstyrene, vinyltoluene, pt
Aromatic vinyl compounds such as -butylstyrene and chlorostyrene; acrylamide compounds such as acrylamide, N-methylolacrylamide and N-butoxymethylacrylamide; methacryl such as methacrylamide, N-methylolmethacrylamide and N-butoxymethylmethacrylamide. Examples include amide compounds, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl acrylate, and the like. Preferred are the above-mentioned aromatic vinyl compounds.

One or more monomers selected from the above monomer components are used as the core layer, and two or more monomers are used for the shell layer. In addition, the shell layer has a structure in which solubility with respect to the epoxy resin is exhibited by heating, so that a double bond capable of undergoing radical polymerization with an N-substituted acrylamide, acrylate or methacrylate monomer is formed. A crosslinking monomer having at least two or more monomers and a monomer having a free carboxyl group are copolymerized.

Examples of the N-substituted acrylamide include N-acryloylpyrrolidine, N, N-dimethylacrylamide, N-isopropylacrylamide, N-isopropylacrylamide,
Hexylacrylamide, N-octylacrylamide, N-dodecylacrylamide, and the like can be used.

Specific examples of the crosslinkable monomer having at least two double bonds capable of radical polymerization with an acrylate or methacrylate monomer include:
Ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate hexanediol diacrylate, oligoethylene diacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane Examples thereof include aromatic divinyl monomers such as trimethacrylate, hexanediol dimethacrylate, oligoethylene dimethacrylate, and divinylbenzene, triallyl trimellitate, triallyl isocyanurate, and the like. The amount of the crosslinkable monomer should not exceed 0.5% in the core / shell copolymer. This is because the degree of crosslinking is too high and does not swell in the epoxy resin as the matrix.

Specific examples of the monomer having a free carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and cinnamic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid and chloromaleic acid. Dicarboxylic acids such as acids, monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate,
Monoesters of unsaturated dicarboxylic acids such as monomethyl itaconate, monoethyl itaconate and monobutyl itaconate are exemplified.

The method for producing the particulate copolymer having the core layer / shell layer is not particularly limited, but is preferably produced by a continuous multi-stage seed emulsion polymerization of at least two stages. That is, the first-stage monomer is subjected to emulsion polymerization using a radical polymerization initiator such as a peroxide initiator or a redox initiator as a polymerization initiator in the presence of an emulsifier to contain a core component. To obtain a seed latex. Next, as a second stage, a monomer of the shell component is added to the seed latex containing the core component obtained in the first stage, and in the presence of an emulsifier, a peroxide initiator as a polymerization initiator, redox Emulsion polymerization is performed using a radical polymerization initiator such as an initiator to form a shell component. With such a multi-stage seed emulsion polymerization, the particle size is 300 to 50.
A particulate copolymer or latex having a core / shell layer of 00 Å can be produced.

In this case, the polymerization of the shell layer component may be performed subsequent to the polymerization of the core layer component, or may be performed after the seed latex of the core layer component produced in the first step is partially aggregated. When a monomer having a free carboxyl group is used as one of the components of the shell layer, after the second polymerization, a metal cation is added to form an ion or coordinate bond between the carboxyl groups of the shell layer. As the metal cation, for example, monovalent metal ions such as potassium, sodium, lithium, and cesium, and divalent metal ions such as calcium, zinc, tin, chromium, and lead can be used. Monovalent or divalent ions of metals belonging to the genus I to II are preferred. Examples of the cation supplier include inorganic acids such as oxides, hydroxides, phosphates, carbonates, nitrates, sulfates, chlorides, nitrites and sulfites of the above-mentioned metals. Formic, acetic, propionic, butyric, octylic, capric, palmitic,
Stearic acid, oleic acid, erucic acid, linolenic acid,
Salts of organic acids such as succinic acid, adipic acid, naphthenic acid and thiocarboxylic acid, acetylacetone salts, alcoholates such as ethoxide and methoxide and the like can be mentioned. Among these metal cations, hydroxides and carboxylate salts of monovalent metals are particularly effective in terms of reaction efficiency and mechanical strength of molded articles. The monovalent and divalent cation donors are characterized in that in a solution, an ionic crosslinking reaction is possible within a few minutes at room temperature.

In the case of a latex containing a core layer / shell layer type copolymer obtained by the above-mentioned multi-stage polymerization, the drying method is spraying by a multi-blade type rotary disk type, a disk type rotary disk type, a nozzle type or the like. By drying, a powdery core / shell copolymer is obtained. For this drying,
Generally, the core / shell-type copolymer aggregates in units of spray droplets to form aggregated particles of about 20 to 100 μm. The degree of agglomeration depends on the drying conditions, and a step of pulverizing and loosening after drying may be provided. In addition, after the emulsion polymerization, latex particles are coagulated and separated by a salting out method or a freezing method, and a wet cake prepared by dehydration is dried with a fluidized bed or the like to obtain aggregated particles.

The molding material composition of the present invention is preferably prepared by adding a thermoplastic resin powder, preferably comprising a core layer / shell layer type particulate copolymer, to 100 parts by weight of an epoxy resin by using a thickener (C).
5 to 150 parts by weight, more preferably 20 to 50 parts by weight. If the amount is less than 5 parts by weight, even if the viscosity is increased by heating, the viscosity is only slightly increased, and the solid state is not obtained. On the other hand, if it exceeds 150 parts by weight, it cannot be mixed without being sufficiently dispersed in the epoxy resin.
The epoxy resin of the present invention may optionally contain additives such as a curing accelerator, a reactive diluent, a non-reactive diluent, a pigment and an internal release agent.

The inorganic filler (D) of the present invention includes, for example, calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barite, baryta, silica, silica sand, dolomite limestone, gypsum , Aluminum fine powder, hollow balloon, alumina, glass powder, aluminum hydroxide, fluorite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide and the like. These inorganic fillers are selected in consideration of workability, strength, appearance, economy, and the like of the obtained molded product, but calcium carbonate, aluminum hydroxide, silica, and the like are preferably used.
The addition amount is preferably 100 to 500 parts by weight, more preferably 150 to 300 parts by weight, based on 100 parts by weight of the epoxy resin (A).

Material having self-heating property by physical means (E)
Is preferably a material having self-heating property by any means such as electromagnetic induction, ultrasonic wave, electric current, etc.
Metal powders such as iron powder and copper powder, metal foils such as iron foil, copper foil and gold foil, metal fiber materials such as iron and copper (knitted, woven, mesh), carbon fibers (sheet, mat, knitted, woven, (Net-like). In the case of metal powder, electromagnetic induction is more difficult as the particle size is smaller. Therefore, a powder having a particle size of 100 μm or more is usually used. In the case of a metal foil, the thickness is not particularly limited, but is preferably 100 μm or less from the viewpoint of workability and physical properties. Further, in the case of a metal net, if the net is too large, curing unevenness is caused at the time of molding. Therefore, the net must usually be a maximum of 1 cm. Further, it is desirable that the carbon fiber and the carbon sheet have a volume specific resistance of 5 to 1000 Ω · cm necessary for generating heat by energization.
Further, a mixture of carbon fibers and other fibers, or a felt paper obtained by laminating them may be used.

The present invention provides various additives conventionally used in unsaturated polyester molding material compositions for SMC, such as a fiber reinforcing material, a low-shrinking agent, and a mold release so long as the object of the present invention is not impaired. Agents and the like can also be added as desired.

As the fiber reinforcing material, those usually used as a reinforcing material may be used, for example, glass fiber, polyester fiber, phenol fiber, polyvinyl alcohol fiber,
There are aromatic polyamide fibers, nylon fibers and carbon fibers. Examples of these forms include chopped strands, chopped strand mats, rovings, and woven fabrics. These fiber reinforcing materials are selected in consideration of the viscosity of the composition, the strength of the obtained molded article, and the like. Chopped strand length is usually 5-60 for SMC
mm and 2-8 mm for BMC.

Examples of the low shrinkage agent include thermoplastic resins such as polystyrene, polyethylene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polycaprolactam, saturated polyester, styrene-acrylonitrile copolymer, polybutadiene, and polybutadiene. Rubber-like polymers such as isoprene, styrene-butadiene copolymer and acrylonitrile-butadiene copolymer are exemplified.
The purpose is normally achieved when the amount of these additives is 4 to 10 parts by weight.

Examples of the release agent include higher fatty acids such as stearic acid, higher fatty acid salts such as zinc stearate, and alkyl phosphates. The release agent is preferably used in a proportion of 0.5 to 5 parts by weight based on 100 parts by weight of the epoxy resin (A).

In addition to these components, a coloring agent, an antifoaming agent, a viscosity reducing agent and the like can be used as required.

The molding material of the present invention comprises, as a thickener (C), a thermoplastic resin powder, preferably an acrylate, a methacrylate or a diene, instead of an alkaline earth metal oxide or hydroxide. A resin powder containing at least one monomer unit selected from copolymerizable monomers, preferably a thickener comprising a thermoplastic resin powder composed of a core layer and a shell layer as an active ingredient The difference is that the agent (C) is used and that no external heating device is used in the thickening process accompanying its use. That is, it is characterized in that a material having a self-heating property is added or impregnated into a molding material composition by a physical means such as electromagnetic induction, ultrasonic wave and electric current without heating.

When the present invention is an SMC, its production method is such that a predetermined ratio of an epoxy curing agent is added to a liquid epoxy resin (A) at room temperature using a known mixer such as a planetary mixer or a kneader. (B), a thickener (C) containing a thermoplastic resin powder as an active ingredient, an inorganic filler (D), and a material (E) having self-heating properties, such as a metal powder, are sufficiently stirred and mixed. When metal powder is used, it is necessary to add a fiber reinforcement. The position where the fiber reinforcing material is added when producing SMC is usually before the mixture rolling step in the SMC production equipment. Mixture (A) prepared by mixing machine
(B) (C) (D) (E) is applied to one or both of the two release films by a coating device such as a flow coater or a doctor knife to a constant thickness of preferably 0.3 to 10 mm, The fiber reinforced material is cut with a chopper and sprayed thereon, then bonded together with the coated surface inside, and rolled by a rolling machine to obtain a sheet preferably having a thickness of 0.5 to 20 mm. It is wound with a roller in the state of being covered.

When a continuous long material such as a metal foil, a wire mesh, a carbon sheet, or the like is used as the self-heating material (E), for example, the epoxy resin (A) which is liquid at normal temperature may be, for example,
Using a known mixer such as a planetary mixer or a kneader, a predetermined ratio of an epoxy curing agent (B), a thickener (C) containing a thermoplastic resin powder as an active ingredient, and an inorganic filler (D) are sufficiently mixed. Stir and mix. The mixture (A) (B) (C) (D) prepared by the mixer is applied to one or both of the two release films by a coating device such as a flow coater or a doctor knife, preferably in a thickness of 0.3 to 10 mm. , A metal foil, a wire mesh, a continuous long object such as a carbon sheet is sandwiched in the center, and the coated surface is inwardly bonded and rolled by a rolling machine, preferably in a thickness of 0.5 to 20.
mm sheet is wound with a roller with both sides covered with a release film.

When carbon fiber is used as the self-heating material (E), the epoxy resin (A) which is liquid at normal temperature
For example, using a known mixer such as a planetary mixer or a kneader, a predetermined ratio of an epoxy curing agent (B), a thickener (C) containing a thermoplastic resin powder as an active ingredient, and an inorganic filler (D) ) And mix well. Mixtures (A), (B), (C), and (D) prepared by the mixer are:
One or both of the two release films are applied by a coating device such as a flow coater or a doctor knife to a constant thickness of preferably 0.3 to 10 mm, and carbon fibers are cut thereon by a chopper and dispersed. Then, the sheet is rolled by a rolling mill to obtain a sheet preferably having a thickness of 0.5 to 20 mm, and wound on a roller with both sides covered with a release film.

In the thickening step, the temperature varies depending on the type and amount of the thickener (C). Preferably, the thickening can be completed at a specific temperature of 35 ° C. to 160 ° C. in a short time. Select the agent. Preferred thickening times are possible from 15 minutes to 2 hours. The releasability of the obtained SMC release film is extremely good.

In the case where the present invention is a BMC, its manufacturing method is not limited to the case of using a continuous long material such as a metal foil, a wire mesh, a carbon sheet or the like as a material having self-heating properties, that is, a case of using a metal powder, a carbon fiber or the like. Using a known mixer such as a planetary mixer or a kneader, a predetermined ratio of an epoxy curing agent (B) and a thermoplastic resin powder are added to the epoxy resin (A) which is liquid at room temperature as an active ingredient. The viscous agent (C), the inorganic filler (D), and the metal powder or carbon fiber are sufficiently stirred and mixed. When metal powder is used, it is preferable that the fiber reinforcing material is also stirred and mixed at the same time.

In this BMC thickening step, the mixed composition is taken out into a bag made of polyethylene or the like, sealed, and preferably thickened at a specific temperature between 35 ° C. and 160 ° C. Since the shape is bulk, it is preferable that 30 minutes to 3 hours are required until the thickening is completed. The shape of BMC is pellet,
Although various shapes and sizes such as a pebble shape and a brick shape are possible, the diameter or one side is preferably a size of 0.7 cm to 1 m. The viscosity of the composition after thickening is 20,000 poise or more at 25 ° C., and preferably 50,000 to 100,000 poise.

When a metal foil, a wire netting, or a carbon sheet is used as a material having self-heating when the present invention is a BMC, the epoxy resin (A) which is liquid at ordinary temperature is used as in the case of the metal powder described above. For example, a planetary mixer,
Using a known mixer such as a kneader, a predetermined ratio of an epoxy curing agent (B), a thickener (C) containing a thermoplastic resin powder as an active ingredient, and an inorganic filler (D) are sufficiently stirred and mixed.

The mixed BMC is subjected to the same thickening step as in the case of the metal powder described above.

The BMC after thickening is once taken out, cut out in a block shape, and a long object such as a metal foil, a wire net, a carbon sheet or the like having self-heating properties is sandwiched between two blocks, and then a generally used compressor is used. Is used to form a block having a thickness of 1 cm to 10 cm to obtain a desired BM.
C is produced.

The method for molding the SMC or BMC containing the produced metal powder, metal foil, wire mesh, etc. does not need to be particularly heated, but is preferably performed using a resin mold or a mold heated to 30 ° C. to 50 ° C. Then, it is shaped into a desired shape. Next, an electromagnetic wave (preferably 0.5 Hz to 28
(GHz) by contact irradiation to the molded article to induce electromagnetic induction, or by contacting ultrasonic waves by an ultrasonic generator to irradiate the molded article to oscillate, preferably cured molding in about 30 seconds to 10 minutes. it can.

In the method of forming SMC or BMC containing carbon fibers and carbon sheets, it is not necessary to heat electrodes by bringing electrodes into contact with both ends of the SMC or BMC.
Compressed with a resin mold and a mold heated to 30 ° C to 50 ° C,
Form into the desired shape. Next, 10-30 W
/ Mm ² is usually supplied with a current of 100 V so as to generate heat.
Preferably, the molding is performed by energizing for 5 to 30 minutes.

[0044]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, “parts” in the text indicates parts by weight.

(Reference Example) Production of thickener (core / shell copolymer) 40 parts by weight of n-butyl acrylate were charged into a reactor equipped with a stirrer, and methyl methacrylate / methacrylic acid copolymer was used as an emulsifier. 1 part by weight of a high molecular emulsifier and 0.1 part by weight of potassium persulfate as a catalyst
After stirring in a 0 part by weight at a polymerization temperature of 80 ° C. for 180 minutes, polymerization was carried out until the polymerization conversion reached 98%. Then, using the obtained latex as a seed, 58 parts by weight of methyl methacrylate and 2 parts by weight of methacrylic acid were added,
Polymerization was performed continuously to obtain a polymer latex. After cooling to room temperature, 100 parts by weight of a 1% by weight aqueous solution of potassium hydroxide was added at room temperature and stirred for 30 minutes. The average particle diameter of the obtained core / shell type latex is 0.2 to 0.1.
It was in the range of 5 μm. The obtained latex was spray-dried at 150 ° C. by spray drying to obtain a core / shell copolymer powder.

Example 1 Composition of Epoxy SMC and Method for Producing and Forming the Same 1 100 parts of Epicron 850 (diphenol epoxide resin: Dainippon Ink and Chemicals, Inc.), 8 parts of dicyandiamide,
20 parts of thickener prepared in Reference Example, 30 calcium carbonate
Parts and 5 parts of iron powder having an average particle diameter of 150 μm were mixed by stirring with a planetary mixer for 30 minutes. The composition was heated to 40 ° C. and supplied to an SMC manufacturing machine, and 0.5 mm of a glass fiber applied to both release films with a doctor knife and cut with a glass cutter was placed thereon. After impregnation with a roller, it is wound on a roll. Roll 9
Store at 0 ° C for 1 hour to thicken. The film removability of the SMC is good. 850 g of manufactured SMC at 40 ° C.
Into a plate of 30 × 30 cm with a heated mold. The shaped article was taken out and cured at room temperature with an ultrasonic irradiation device. Curing time was 30 minutes. The general physical properties of the obtained molded product were measured according to JIS-K-6911, and as a result, the flexural strength was 26 kg / mm ² and the flexural modulus was 1250 k.
g / mm ² .

(Example 2) Epoxy SMC and its manufacturing method and molding method 2 Epicron 850 (Dainippon Ink and Chemicals) 100
8 parts of dicyandiamide in part, thickener 2 prepared in Reference Example
0 parts and 30 parts of calcium carbonate were stirred and mixed with a planetary mixer for 30 minutes. The composition was heated to 40 ° C.
It was supplied to a C production machine, and was applied to both release films with a doctor knife to 0.5 mm. A copper mesh having a mesh interval of 1 mm is sandwiched between both release films, and then impregnated with a roller. The sheet is wound on a roller. The roll is stored at 100 ° C. for 30 minutes to thicken. As in Example 1, the peelability of the film was good. Manufactured SM
C850 g was shaped into a 30 × 30 cm plate using a mold heated to 40 ° C. The shaped article was taken out and cured at room temperature on an electromagnetic induction device for 5 minutes. The general physical properties of the obtained molded product were measured according to JIS-K-6911, and as a result,
Flexural strength 29 kg / mm ² , flexural modulus 1450 kg /
mm ² .

(Example 3) Epoxy SMC and its production method and molding method 3 An SMC was produced in the same manner as in Example 2 except that the copper net was changed to Donacarbo S-221 (a product of Donac Inc.). The film removability of the SMC was good. 850 g of the manufactured SMC was heated to 40 ° C. in a mold for 30 minutes.
It was shaped into a × 30 cm plate. The shaped article was taken out, electrodes were brought into contact with both ends, energized, and cured for 10 minutes. General properties of the obtained molded article 1 was measured in accordance with JIS-K-6911, bending strength 20 kg / mm ^2, was flexural modulus 1250 kg / mm ^2.

(Example 4) Epoxy SMC and its production method and molding method 4 Epicron 850 (Dainippon Ink and Chemicals) 100
8 parts of dicyandiamide in part, thickener 2 prepared in Reference Example
0 parts and 30 parts of calcium carbonate were stirred and mixed with a planetary mixer for 30 minutes. The composition was heated to 40 ° C.
It is supplied to a C production machine, applied with 0.5 mm on both release films with a doctor knife, loaded with 1 inch carbon fiber, impregnated with a roller, and wound on a roll. The roll is stored at 90 ° C. for 1 hour to thicken. The film removability of the SMC is good. Manufactured SM
C850 g was shaped into a 30 × 30 cm plate using a mold heated to 40 ° C. The shaped article was taken out, electrodes were brought into contact with both ends, energized, and cured for 10 minutes. The physical properties of the obtained molded product were measured according to JIS-K-6911, and as a result, the flexural strength was 35 kg / mm ² , and the flexural modulus was 1560.
kg / mm ² .

Example 5 Composition of Epoxy BMC and Method for Producing and Forming the Same 1 Epicron 850 (product of Dainippon Ink and Chemicals) 100
8 parts of dicyandiamide in part, thickener 2 prepared in Reference Example
0 parts, 200 parts of aluminum hydroxide, 5 parts of iron powder having an average particle diameter of 150 μm, and 7 parts of 0.5 inch glass fiber were stirred and mixed with a planetary mixer for 30 minutes. The mixed composition is removed into a polyethylene bag and sealed. The composition is 10
Thicken at 0 ° C / 30 minutes. 810 g of the prepared BMC was shaped into a 30 × 30 cm plate using a mold heated to 40 ° C. The molding method was the same as in Example 1. General properties of the obtained molded article 1 was measured in accordance with JIS-K-6911, bending strength 10 kg / mm ^2, was flexural modulus 1050 kg / mm ^2. Was.

Example 6 Composition of Epoxy BMC, Method for Producing and Molding Method 2 Epicron 850 (Dainippon Ink and Chemicals) 100
8 parts of dicyandiamide in part, thickener 2 prepared in Reference Example
0 parts and 200 parts of aluminum hydroxide were stirred and mixed by a planetary mixer for 30 minutes. The mixed composition is removed into a polyethylene bag and sealed. The composition thickens at 100 ° C./30 minutes. 10 cm × 10 BMC intermediate after thickening
Cut into blocks of 10 cm × 10 cm, sandwiched between the two blocks a 30 cm × 30 cm copper mesh with a 1 mm net spacing, and pressed at 40 ° C. with a hand press on a flat plate to obtain 2 m
m-shaped plate. The molding method was the same as in Example 2. Bending strength of the molded product is 9.8 kg / mm ^2, a flexural modulus of 975 kg / mm ^2.

(Example 7) Composition of epoxy BMC, method for producing and molding method 3 BMC was prepared in the same manner as in Example 6 except that the copper mesh was changed to Donacarbo S-221 (a product of Donac Co., Ltd.). Produced. The molding method was the same as in Example 3. The bending strength of the molded product is 7.5 kg / mm ² and the bending elastic modulus is 830 k.
g / mm ² .

Example 8 Epoxy BMC Composition, Production Method and Molding Method 4 Epicron 850 (product of Dainippon Ink and Chemicals, Inc.) 1
To 00 parts, 8 parts of dicyandiamide, 20 parts of the thickener prepared in Reference Example, 200 parts of aluminum hydroxide, and 7 parts of 0.5-inch carbon fiber were stirred and mixed by a planetary mixer for 30 minutes. The mixed composition is removed into a polyethylene bag and sealed. The composition thickens at 100 ° C./30 minutes. 810 g of the prepared BMC was shaped into a 30 × 30 cm plate using a mold heated to 40 ° C. The molding method is Example 7.
Was performed in the same manner as described above. The general physical properties of the obtained molded article are
As a result of measurement according to SK-6911, the flexural strength was 11 kg / mm ² and the flexural modulus was 1150 kg / mm ² .

[0054]

According to the present invention, molding materials such as SMC and BMC which are easy to handle and can be hardened and molded by physical means such as energization, electromagnetic induction, ultrasonic waves, etc. without using a heat and pressure molding apparatus. A composition, a production method thereof, and a molding method can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 7/02 C08K 7/02 7/16 7/16 C08L 51/00 C08L 51/00 51/04 51/04 101/00 101 / 00

Claims (14)

[Claims] 1. An epoxy resin which is liquid at room temperature, (B) an epoxy curing agent, (C) a thickener containing a thermoplastic resin powder as an active ingredient, (D) an inorganic filler, and (E) a physical means. A molding material composition comprising a material having a self-heating property and having a property of increasing viscosity by heat generated by physical means and being curable. 2. The molding material composition according to claim 1, wherein the physical means is one of electromagnetic induction, ultrasonic waves, and electric current. 3. The molding material according to claim 1, wherein the self-heating material (E) is at least one selected from metal powder, metal foil, wire mesh, carbon fiber, and carbon sheet. Composition. 4. A thickener (C) comprising a thermoplastic resin powder as an active ingredient in an amount of 5 to 100 parts by weight of the epoxy resin (A).
The molding material composition according to claim 1, comprising 150 parts by weight and 100 to 500 parts by weight of an inorganic filler (D). 5. The molding material composition according to claim 1, wherein the thickener (C) is a thermoplastic resin powder comprising a core / shell type copolymer composed of a core layer and a shell layer. Stuff. 6. A thermosetting agent comprising a thickener (C) containing at least one monomer unit selected from acrylates, methacrylates, dienes and monomers copolymerizable therewith. The molding material composition according to claim 1, wherein the molding material composition is a plastic resin powder. 7. The shell layer of the thermoplastic resin powder of the thickener (C) is made of an acrylate-based or methacrylate-based methacrylate-based polymer that exhibits solubility in an epoxy resin when heated. The molding material composition according to claim 1, characterized in that: 8. The method according to claim 1, wherein the shell layer of the thermoplastic resin powder of the thickener (C) is made of an acrylate or methacrylate copolymer containing N-substituted acrylamide. Molding material composition. 9. The shell layer of the thermoplastic resin powder of the thickener (C) is a copolymer obtained by adding a metal cation to a copolymer having a free carboxyl group and crosslinking by a ionic or coordination bond. The molding material composition according to claim 1, which is present. 10. The molding material composition according to claim 1, further comprising a fiber reinforcing material (E). 11. An epoxy resin which is liquid at normal temperature, (B) an epoxy curing agent, (C) a thickener containing a thermoplastic resin powder as an active ingredient, (D) an inorganic filler, and a powdery self-heating property. A method for producing a molding material, comprising kneading a material (E) having the following, and then increasing the viscosity by heating. 12. Kneading (A) an epoxy resin which is liquid at room temperature, (B) an epoxy curing agent, (C) a thickener containing a thermoplastic resin powder as an active ingredient, and (D) an inorganic filler, followed by coating on a film. A method for producing a molding material, wherein a material (E) having self-heating properties is placed thereon by a fibrous physical means, impregnated with the material, and the viscosity is increased by heating. 13. An epoxy resin which is liquid at room temperature, (B) an epoxy curing agent, (C) a thickener containing a thermoplastic resin powder as an active ingredient, (D) an inorganic filler, and (E) a physical means. A method for producing a molding material, comprising: applying a material having self-heating properties to a sheet-like material by means of kneading, applying a sheet-like material having self-heating properties, and increasing the viscosity by heating. 14. A molding method characterized by shaping a molding material obtained by any one of the manufacturing methods according to claim 11 and then curing the molding material by any of electromagnetic induction, ultrasonic waves, and electric current.