JP2009061701A - Method for manufacturing pultruded article and shaped article produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in not only quick hardening property but also in the adhesiveness of a matrix with a fiber reinfocing material and which can be suitably used in pultrusion. <P>SOLUTION: The manufacturing method for pultruded articles is characterized by that the pultrusion is carried out using the resin composition containing (A) an epoxy resin, (B) a hardener for the epoxy resin, (C) a (metha)acrylate, (D) a hardener for the (metha)acrylate, and (E) a layered silicate having organophilicity and a fibrous reinforcing material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method of manufacturing a pultruded product and a molded product obtained by the manufacturing method.

  The fiber reinforced resin composition comprising a matrix containing a thermosetting resin and a fiber reinforcing material can be molded by hand lay-up molding, spray-up molding, resin injection molding, sheet molding compound (SMC) molding. Method, bulk molding compound (BMC) molding method, filament winding molding method, pultrusion molding method and the like.

  Among these, the pultrusion molding method has an advantage that continuous molding can be performed and a long molded product having high strength (particularly strength in the length direction) can be obtained. The outline of the pultrusion method is as follows. That is, after arranging the long fiber reinforcing material, the step of impregnating the fiber reinforcing material with the thermosetting resin through the resin tank in which the thermosetting resin is stored (impregnation step), and after the impregnation step The process of forming the fiber reinforcement into a predetermined molded product shape (molding process) while removing excess thermosetting resin from the fiber reinforcement, and heating the fiber reinforcement after the shaping process And a step (curing step) for curing through the step, and a step (traction step) for continuously extracting the cured product (or semi-cured product) after the curing step.

  Here, in order to industrially perform the pultrusion method with high productivity, it is necessary to increase the drawing speed of the cured product. On the other hand, if the traction step is performed while the curing of the thermosetting resin is insufficient in the curing step, a part of the gelled resin remains in the heating mold, making it difficult to perform routine work. It becomes. In addition, the resin breaks during the pulling process, and a problem that a defect occurs in the obtained molded product is likely to occur. For this reason, there is a demand for a thermosetting resin having a fast curing property that can be sufficiently cured in the heating mold or immediately after leaving the heating mold even if the drawing speed is increased.

  As thermosetting resins having such fast curing properties, radical polymerization type thermosetting resins such as unsaturated polyester resins and vinyl ester resins have been widely used, and thermosetting resins that can be used in pultrusion methods have been widely used. Some are disclosed (for example, refer to Patent Documents 1 and 2). Patent Document 1 contains an epoxy group obtained by reacting an ethylenically unsaturated carboxylic acid in an amount of 0.2 to 0.7 equivalent to 1 equivalent of an epoxy group of an epoxy resin having two or more epoxy groups. A vinyl ester resin (A), a radical polymerizable monomer and / or an epoxy diluent (B), an organic peroxide (C), an epoxy resin curing agent (D) based on an acid anhydride, and a latent The resin composition for pultrusion molding characterized by containing a heat-resistant epoxy resin hardening accelerator (E) is described. Patent Document 2 discloses a reinforced resin composed of carbon fiber and a resin, the carbon fiber is surface-treated with a sizing agent, and the resin is composed of an unsaturated matrix resin component and an epoxy resin component. Is a carbon fiber reinforced resin characterized by being 10:90 to 90:10.

However, in the conventional pultrusion resin composition, the adhesion between the matrix and the fiber reinforcing material may be insufficient. On the other hand, in recent years, there is a demand for a molded product having excellent mechanical strength as the molded product becomes larger. For this reason, there is a need for a pultrusion resin composition capable of bonding the matrix and the fiber reinforcement more strongly than the conventional pultrusion resin composition.
JP 2005-226014 A JP 2006-249395 A

  The present invention has been made in view of the above problems, and an object of the present invention is a resin composition that is excellent in not only fast curability but also adhesiveness between a matrix and a fiber reinforcing material and can be suitably used for pultrusion molding. Is to provide.

  The present inventors have previously disclosed an epoxy resin composition having a predetermined configuration (Japanese Patent Application Laid-Open No. 2004-99786), and as a result of intensive studies, based on such an epoxy resin composition, fast curing is disclosed. The present inventors have found that a resin composition suitable for pultrusion molding that is excellent in properties and excellent in adhesion between the matrix and the fiber reinforcing material can be obtained.

  That is, the method for producing the pultruded product of the present invention includes epoxy resin (A), epoxy resin curing agent (B), (meth) acrylate (C), (meth) acrylate curing agent (D), and organic affinity. It is characterized by performing pultrusion using a resin composition containing a layered silicate (E) having a property and a fiber reinforcing material.

  With this configuration, the resin composition used in the present invention includes (meth) acrylate having excellent fast curability and an epoxy resin having a small volume shrinkage during heat curing. Will also be included. Further, since each of the epoxy resin and (meth) acrylate is separately contained, each resin component is polymerized at the time of curing to form an interpenetrating polymer network (hereinafter sometimes simply referred to as “IPN”) structure. Will be. At that time, the resin composition intercalates between the layers of the layered silicate, or the layer structure of the layered silicate is peeled off to disperse the silicate in the cured product (molded product) (nanocomposite). ).

  Moreover, in 100 mass% of total amounts of the said epoxy resin (A) and the said (meth) acrylate (C), it is preferable that the content rate of the said (meth) acrylate (C) is 5 to 40 mass%. Is a preferred embodiment.

  With this configuration, the resin composition used in the present invention has an excellent balance between rapid curability during curing and volume shrinkage during curing.

  The addition amount of the layered silicate (E) having organic affinity is 0.1 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin (A) and the (meth) acrylate (C). It is a preferred embodiment that the amount is not more than part by mass.

  With this configuration, when the resin composition used in the present invention is cured (molded), the cured product (molded product) contains sufficient silicate.

  Moreover, in the manufacturing method of the pultruded article of this invention, the said resin composition and the said fiber reinforcement material are 10 cm / min or more and 30 cm / min or less to the heating metal mold | die which has the temperature of 50 to 200 degreeC. It is a preferred embodiment to pultrude through.

  The present invention includes a molded product obtained by the above-described production method.

  Since the resin composition used in the present invention is excellent in rapid curability, it is suitable as a matrix for pultrusion molding. For this reason, the manufacturing method of the pultruded product of this invention has manufactured the molded product industrially with sufficient productivity.

  Moreover, the molded product which was excellent in mechanical strength was able to be obtained with the manufacturing method of this invention.

  The method for producing a pultruded product of the present invention includes epoxy resin (A), epoxy resin curing agent (B), (meth) acrylate (C), (meth) acrylate curing agent (D), and organic affinity. It is characterized by performing pultrusion using a resin composition containing a layered silicate (E) and a fiber reinforcing material. Hereinafter, the manufacturing method of the pultruded product of this invention is demonstrated.

(Epoxy resin (A))
The epoxy resin (A) used in the present invention has two or more epoxy groups, and is polymerized separately from the (meth) acrylate (C) when a resin composition including the epoxy group is cured. By doing so, it is preferable that the IPN structure is formed and toughness can be imparted to the obtained molded product. For example, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin and the like can be mentioned. Moreover, the epoxy resin modified | denatured in the other aspect may be sufficient.

  Examples of the glycidyl ether type epoxy resin include those obtained by condensation of epichlorohydrin with polyhydric phenols such as bisphenols and polyhydric alcohols, and specifically include bisphenol A type, brominated bisphenol A type, hydrogenated type. Bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, fluorene type, phenol novolac type, orthocresol novolak type, tris (hydroxyphenyl) methane type, tetraphenylolethane type, etc. It is done.

  Examples of the glycidyl ester type epoxy resin include those obtained by condensation of epichlorohydrin with carboxylic acids such as phthalic acid derivatives and fatty acids.

  Examples of the glycidylamine type epoxy resin include those obtained by reaction of epichlorohydrin with amines, cyanuric acids, and hydantoins.

  The said epoxy resin may be used independently or may be used in combination of 2 or more type.

  The epoxy resin (A) used in the present invention is in a liquid state so that the fiber reinforcing material can be impregnated (attached) to the fiber reinforcing material by immersing the fiber reinforcing material in the resin composition including the epoxy resin (A). Or it is preferable that it is a solid whose melting temperature is 100 degrees C or less.

  When the resin composition used in the present invention contains an epoxy resin, characteristics derived from the epoxy resin can be imparted to the resin composition (or molded product). For example, the volume shrinkage at the time of hardening of the resin composition used by this invention can be restrained low. Moreover, the adhesiveness of a resin composition (matrix) and a fiber reinforcement can be improved. Furthermore, the mechanical properties, heat resistance and chemical resistance of the molded product can be improved.

(Curing agent for epoxy resin (B))
Examples of the curing agent (B) for epoxy resin used in the present invention include those widely used for curing epoxy resins, such as 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2 -Imidazole-based curing agents such as phenylimidazole; Acid anhydride-based curing agents such as hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic acid anhydride; Polyphenol-based curing agents such as novolac-type phenolic resin, Tertiary amine curing agents such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N′-dimethylpiperazine, diazabicycloundecene: dicyandiamide and the like. Moreover, the said hardening | curing agent for epoxy resins may be used independently, or may be used in combination.

  The amount of the epoxy resin curing agent (B) used depends on the type of the epoxy resin curing agent, but is preferably 1 part by mass or more with respect to 100 parts by mass of the epoxy resin (A), and 100 parts by mass. The following is preferable.

((Meth) acrylate (C))
The (meth) acrylate (C) used in the present invention has two or more radically polymerizable double bonds, and when the resin composition comprising this is cured, the epoxy resin (A) and Is preferably polymerized separately to form an IPN structure and to impart toughness to the resulting molded article. Specific examples include acrylates or methacrylates. In addition, as long as the (meth) acrylate having two or more radical polymerizable double bonds is included, the (meth) acrylate having one radical polymerizable double bond may be included.

  Specific examples of acrylates include polyethylene glycol diacrylate, polypropylene glycol diacrylate, and trimethylolpropane triacrylate. Specific examples of the methacrylates include polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, and trimethylolpropane trimethacrylate. Said (meth) acrylate may be used independently or may be used in combination of 2 or more type.

  For example, when polyethylene glycol diacrylate or polyethylene glycol dimethacrylate is used as (meth) acrylate (C), the number of ethylene glycol units is preferably 2 or more, more preferably 4 or more, and 8 Or less, more preferably 6 or less. When the number of ethylene glycol units is less than 2, the IPN structure may not be sufficiently developed when the resin composition used in the present invention is polymerized. When the number of ethylene glycol units exceeds 8, the mechanical properties of a cured product (molded product) obtained by curing the resin composition may be deteriorated.

  The content of the (meth) acrylate (C) is preferably 5% by mass or more, more preferably 10% by mass or more, in a total amount of 100% by mass of the epoxy resin (A) and the (meth) acrylate (C). Preferably, 15% by mass or more is more preferable, 40% by mass or less is preferable, 35% by mass or less is more preferable, 30% by mass or less is further preferable, and 25% by mass or less is particularly preferable. When the content of (meth) acrylate (C) is less than 5% by mass, the curing rate of the resin composition is not sufficiently increased, and it may be difficult to sufficiently increase the drawing rate at the time of pultrusion molding. . Moreover, since the content rate of an epoxy resin (A) will inevitably fall when the content rate of (meth) acrylate (C) exceeds 40 mass%, the characteristic resulting from an epoxy resin (A) May not be sufficiently imparted to the resin composition used in the present invention or the molded product of the present invention obtained using such a resin composition.

((Meth) acrylate curing agent (D))
As the curing agent (D) for (meth) acrylate used in the present invention, those used for curing (meth) acrylate such as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1 Organic peroxides such as butylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxybenzoate, and 2,2 Examples include azo radical polymerization initiators such as' -azobisisobutyronitrile, 4,4'-azobis (4-cyanopentanoic acid), and 2,2'-azobis (2,4-dimethylvaleronitrile). . Moreover, said (meth) acrylate hardening | curing agent may be used independently, or may be used in combination of 2 or more type.

  The amount of the (meth) acrylate curing agent (D) used depends on the type of the (meth) acrylate curing agent, but is usually 0.1 parts by mass with respect to 100 parts by mass of the (meth) acrylate (C). Preferably, it is preferably 1 part by mass or more, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less. When the amount of the (meth) acrylate curing agent (D) used is less than 0.1 parts by mass, the (meth) acrylate may not be sufficiently cured. Further, when the amount of the (meth) acrylate curing agent (D) used exceeds 4 parts by mass, the curing of the (meth) acrylate is accelerated, so that the curing of the resin composition proceeds too much in the heating mold. It may take a lot of labor to pull out the cured product from the inside. In addition, the cured product may break in the mold in order to forcibly pull out the cured product.

  The (meth) acrylate curing agent (D) used in the present invention may be solid or liquid, but when the amount of use increases, it dissolves in the resin composition. It is preferable that it is liquid so that it may be obtained.

(Layered silicate with organic affinity (E))
As the layered silicate (E) having an organic affinity used in the present invention, the layered silicate has been subjected to organophilic treatment, and even if it is commercially available, the layered silicate is separately subjected to organophilic treatment. May be obtained. As commercially available products, organophilic bentonite (trade name; organophilic Kunipia, manufactured by Kunimine Industry Co., Ltd., trade name: Sven NO12S, trade name: Sven N400, both manufactured by Hojun Co., Ltd.), organophilic montmorillonite (commodity) Name: Nanocor I.30E, trade name: PGW, both manufactured by Nanocor, trade name: Closeite 10A, manufactured by Southern Clay Products Inc.) and the like. Hereinafter, a method for preparing a layered silicate (E) having an organic affinity by subjecting the layered silicate to an organophilic treatment will be described.

  Examples of the layered silicate used to prepare the layered silicate (E) having organic affinity include those containing, for example, magnesium silicate, aluminum silicate and the like as main components. More specifically, smectite clay minerals such as montmorillonite, magnesia montmorillonite, tetsu montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian nontronite, saponite, hectorite, soconite, and stevensite, vermiculite, There are halosite, mica, swellable fluorine mica, etc., which may be natural or synthesized. These layered silicates may be used alone or in combination of two or more. Preferably, a hydroxyl group is introduced. In particular, smectite layered silicate is preferable.

  The layered silicate (E) having an organic affinity used in the present invention is prepared by subjecting the layered silicate to an organophilic treatment. Examples of the treatment agent used for the organophilic treatment of the layered silicate include a cationic surfactant, and preferably the general formula (1)

[Wherein R ¹ is an alkyl group which may be substituted with a carboxyl group, R ² , R ³ and R ⁴ are the same or different and each comprises a hydrogen atom; a carboxyl group, a carboxylate group, and an amino group. An alkyl group which may be substituted with a group selected from the group; or an aralkyl group, and X represents a halogen atom]
The ammonium salt represented by these is mentioned.

When R ^{1 to} R ⁴ are alkyl groups, examples of the alkyl group include linear or branched alkyl groups having 1 to 20 carbon atoms.

Examples of the carboxylic acid ester which is a substituent on the alkyl group of R ^{2 to} R ⁴ include compounds in which the group bonded to the oxygen atom of the carboxylic acid ester is an alkyl group, an aralkyl group, or the like. Examples of the alkyl group include linear or branched alkyl groups having 1 to 20 carbon atoms. Examples of the aralkyl group include a benzyl group and a phenethyl group.

When R ^{2 to} R ⁴ are an aralkyl group, examples of the aralkyl group include a benzyl group and a phenethyl group.

  Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Specific examples of the formula (1) include hexyl ammonium chloride, octyl ammonium chloride, 2-ethylhexyl ammonium chloride, lauryl ammonium chloride, stearyl ammonium chloride, dimethyl dioctyl ammonium chloride, trioctyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl stearyl. Examples thereof include ammonium salts such as ammonium chloride, lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and ammonium laurate chloride. These ammonium salts may be used alone or in combination of two or more. Any of these ammonium salts can be produced by a known method.

  The layered silicate (E) having an organic affinity used in the present invention can be prepared by exchanging exchangeable cations between layers of the layered silicate with the above cationic surfactant.

  What is necessary is just to perform the preparation method (ion exchange reaction) of layered silicate (E) which has organic affinity using a well-known method. For example, after the layered silicate is swollen with a solvent, a cationic surfactant is added and stirred to replace the metal ions between the layers of the layered silicate with the cationic surfactant. Thereafter, the unsubstituted cationic surfactant may be sufficiently washed, filtered and dried to prepare a layered silicate (E) having organic affinity.

  The solvent used in the above preparation method may be any solvent that does not participate in the polymerization. For example, water; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; acetates such as ethyl acetate and butyl acetate; methyl ethyl ketone; Ketones such as methyl isobutyl ketone; aliphatic alcohols such as i-butanol; cyclic ethers such as tetrahydrofuran and dioxane; alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, etc. Is mentioned. These solvents may be used alone or in combination of two or more.

  The above preparation method is illustrated more specifically as follows. That is, about 1% by mass of layered silicate is gradually added and dispersed in the stirred water. If necessary, the dispersion is applied to a homogenizer or an ultrasonic disperser, or left overnight to promote dispersion and cleavage of the layered silicate. A 5% cationic surfactant (dimethyl distearyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, etc.) solution and a layered silicate dispersion are each heated to about 60 ° C. While stirring the heated layered silicate dispersion, a 5% cationic surfactant solution is gradually added and allowed to react. After completion of the addition, the mixture is further stirred at 60 ° C. for about 1 hour. The precipitate is filtered by suction filtration to obtain a dehydrated cake of layered silicate having organic affinity, and the dehydrated cake is washed about 3 times with warm water. The obtained dehydrated cake is dried at 60 ° C. and pulverized to obtain layered silicate (E) powder having organic affinity.

  In this invention, although the usage-amount of the layered silicate (E) which has organic affinity changes with kinds of the hardening | curing agent (D) for (meth) acrylate, an epoxy resin (A) and (meth) acrylate (C). Is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and 10 parts by mass or less. It is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. When the content of the layered silicate (E) having organic affinity is less than 0.1 parts by mass, sufficient flame retardancy may not be imparted to the molded article of the present invention. Moreover, the adhesiveness of a resin composition (matrix) and a fiber reinforcement may not fully be improved. Moreover, when content of layered silicate (E) which has organic affinity exceeds 10 mass parts, a resin composition may thicken and a moldability may fall. Moreover, the dispersion state of the layered silicate (E) in the resin composition may be deteriorated, and the physical properties of the obtained molded product may be lowered.

  The shape of the layered silicate (E) having organic affinity used in the present invention is preferably in the form of powder or fine particles in consideration of dispersibility in the resin composition.

(Resin composition)
The resin composition used in the present invention includes the above-mentioned epoxy resin (A), epoxy resin curing agent (B), (meth) acrylate (C), (meth) acrylate curing agent (D), and organic affinity. It is comprised including the layered silicate (E) which has. For this reason, when this resin composition is cured, the epoxy resin (A) and the (meth) acrylate (C) are separately polymerized to form an IPN structure. As a result, a cured product (molded product) having excellent toughness can be obtained.

  In addition, the resin composition intercalates between the layers of the layered silicate (E) or peels off the layer structure of the layered silicate (E) to disperse the silicate in the cured product (molded product). Will be allowed to. As a result, characteristics (for example, flame retardancy) resulting from such (layered) silicate can be imparted to the molded article of the present invention. Moreover, the adhesiveness of a resin composition (matrix) and a fiber reinforcement can be improved further.

(Fiber reinforcement)
The fiber reinforcing material used in the present invention may be a known fiber reinforcing material conventionally used for fiber reinforced resins. Examples of the fiber reinforcement include organic fiber reinforcement such as vinylon fiber, nylon fiber, polyester fiber, and aramid fiber, and inorganic fiber reinforcement such as glass fiber, carbon fiber, ceramic fiber, whisker, and metal fiber. In particular, glass fiber is preferable, and roving is more preferable. In addition, when the molded product of the present invention requires a predetermined strength not only in the length direction but also in a direction perpendicular to the length direction, a conventionally known fiber reinforcement mat is also used as a fiber reinforcement. May be.

  The content of the fiber reinforcement is 100% by volume of the molded product excluding the layered silicate (E) having organic affinity in consideration of the strength and moldability of the molded product when glass fiber is used as the fiber reinforcement. It is preferably 40% by volume or more, more preferably 50% by volume or more, preferably 90% by volume or less, and more preferably 80% by volume or less. When the content of the fiber reinforcement is less than 40% by volume, the resin composition adheres and accumulates in the mold to reduce a predetermined cross-sectional area, resulting in a loss of the shape of the molded product, Continuous molding may be difficult. On the other hand, if it exceeds 90% by volume, the friction in the mold and the load for pulling out the fiber reinforcing material become too large, and continuous molding may be difficult.

(Additive)
The resin composition used in the present invention may contain various additives as long as the object of the present invention is not impaired. Examples of such additives include antioxidants, stabilizers, ultraviolet absorbers, curing accelerators, mold release agents, adhesion imparting agents, flame retardants, flame retardant aids, pigments, inorganic fillers, and the like.

  In particular, the release agent is preferably contained in the resin composition in order to facilitate drawing (peeling) of the cured product (or semi-cured product) from the heating mold. Such release agents include fatty acids such as stearic acid and waxes. The content of the release agent is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 10 parts by mass or less with respect to 100 parts by mass in total of the epoxy resin (A) and (meth) acrylate (C). Is preferable, and 7 mass parts or less are more preferable.

(Pultrusion molding)
The production method of the present invention is characterized in that pultrusion molding is performed together with a fiber reinforcement using the above-described resin composition as a matrix. More specifically, the production method of the present invention includes a step of arranging long fiber reinforcements, a step of passing the fiber reinforcements through a resin tank in which the resin composition is stored, and an extra portion from the fiber reinforcements. While removing the resin composition, the step of shaping into a desired shape, and passing the shaped fiber reinforcement through a heating die while passing through the die at a predetermined speed and temperature (described later) A step of curing, and a step of continuously extracting a cured (or semi-cured) product from the outlet of the heating mold. In this specification, the speed at which the resin composition and the fiber reinforcing material pass through the mold is the speed at which the cured (or semi-cured) product is continuously extracted from the outlet of the heating mold (drawing speed). Treat as synonymous.

  In the above process, as a method for preparing the resin composition, for example, the epoxy resin (A) and the (meth) acrylate (C) are mixed in an arbitrary ratio, and then a layered silicate having an organic affinity (E ) And mixing for about 2 to 20 hours while maintaining the temperature at about 20 to 80 ° C. to sufficiently disperse the layered silicate (E), and then the epoxy resin curing agent (B) and (meta) ) A method of blending and mixing an appropriate amount of the curing agent for acrylate (D).

  The temperature applied to the fiber reinforcement after squeezing the excess resin composition (temperature in the heating mold) and the speed of passing through the mold are determined by the epoxy resin (A) in the resin composition. The epoxy resin curing agent (B), the (meth) acrylate (C), and the (meth) acrylate curing agent (D) are appropriately adjusted depending on the type and content.

  For example, bisphenol A type epoxy resin as epoxy resin (A), 2-ethyl-4-methylimidazole as curing agent for epoxy resin (B), polyethylene glycol diacrylate as (meth) acrylate (C), (meta ) When 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate is used as the acrylate curing agent (D), the temperature in the heating mold is 50 ° C. or higher. Is preferably 55 ° C or higher, more preferably 60 ° C or higher, preferably 200 ° C or lower, more preferably 190 ° C or lower, and further preferably 180 ° C or lower. preferable. If the temperature is less than 50 ° C., the resin composition may be pulled out in an uncured state. Further, when the temperature exceeds 200 ° C., the curing reaction occurs abruptly, so that cracks may occur in the obtained molded product. In addition, the resin composition is excessively hardened in the heating mold, and the resistance at the time of pulling out increases, so that stable continuous molding cannot be performed. May cause.

  Moreover, it is preferable that it is 10 cm / min or more, and it is preferable that it is 30 cm / min or less at the speed | rate (drawing speed) which draws a hardening (or semi-hardened) thing from the exit of a heating metal mold | die. When the drawing speed is less than 10 cm / min, curing in the heating mold is completed at an early stage (that is, around the inlet of the heating mold), and the resistance during drawing may increase. is there. Moreover, when the drawing speed exceeds 30 cm / min, the resin composition may be drawn from the mold outlet in an uncured state.

  In the heating mold used in the present invention, it is preferable to separately control the inlet temperature of the mold and the temperature of other portions other than the inlet by a heater or the like. In particular, the mold inlet temperature is higher than the working temperature of the epoxy resin curing agent (B) and (meth) acrylate curing agent (D) used to suppress gelation of the resin composition removed at the inlet. It is preferable to keep it low. On the other hand, the temperature of the part other than the entrance of the mold is equal to or higher than the working temperature of the curing agent for epoxy resin (B) and the curing agent for (meth) acrylate used to cure the resin composition. It is preferable to make it. By dividing the heating zone into two or more stages, the resin composition can be cured by subsequent heating and shaped and molded satisfactorily while suppressing gelation in the vicinity of the inlet.

  More specifically, when a resin composition containing the above-described epoxy resin (A) is molded using a relatively short pultrusion molding apparatus having a heating mold length of 800 to 1000 mm, the heating mold is used. Is divided into three equal parts in the length direction, the heating zone is divided into three stages, the mold inlet area is 50 ° C. to 80 ° C., the central area is 150 ° C. to 180 ° C., and the outlet area is 170 ° C. It is preferable to set so that it will be in the range of ℃ to 190 ℃. In such a temperature setting, the drawing speed may be 15 cm / min to 25 cm / min.

  In addition, in the manufacturing method of this invention, you may perform a preheating process before guide | inducing a resin composition and a fiber reinforcement to a metal mold | die as needed.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these, and can be implemented with appropriate modifications within a range that can meet the gist of the preceding and following descriptions. These are all included in the technical scope of the present invention. In the following Examples and Comparative Examples, “parts” and “%” mean parts by mass or mass%.

(Evaluation methods)
First, the evaluation method of the molded product produced by the Example and the comparative example is demonstrated below.

<Bending stress and flexural modulus>
Based on JIS K6911, the bending stress and the bending elastic modulus of the molded product were determined using an electronic universal testing machine 1186 (manufactured by Instron Corporation).

<Tensile stress and tensile modulus>
Based on JIS K7054, five A-type test pieces are prepared from the molded product, and a tensile test is performed on the test piece at a speed of 1 mm / min using an electronic universal testing machine 1186 (manufactured by Instron Corporation). Tensile stress and tensile modulus of elasticity were determined.

<Thermal stability>
Using a thermogravimetric analyzer TGA / DTA320 (manufactured by Seiko Instruments Inc.), the mass change of the molded product was measured under the conditions of a heating rate of 10 ° C./min and a carrier gas (air) flow rate of 150 ml / min. The thermal stability of the molded product was evaluated by determining the 1% mass loss temperature and the 5% mass loss temperature of the molded product.

<Flame retardance>
In accordance with ISO 5660 part1, a test piece having an area of 0.0016 m ² , a thickness of 3.4 mm, and a mass of 10 g is obtained from the molded product, and a heat generation test apparatus cone calorimeter III C3 type (manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used. Then, the flame retardancy of the molded product was evaluated by heating the test piece with a radiation heat amount of 50 kW / m ² and determining the maximum heat generation rate by the oxygen consumption measurement method.

<Ignition time>
When the test piece was heated for the above-mentioned flame retardancy evaluation, it was obtained by measuring the time from the start of heating to the ignition of the test piece.

Preparation Example 1
(Preparation of resin composition)
As shown in Table 1, as epoxy resin (A), bisphenol A type epoxy resin (product name; Epicoat 828, manufactured by Japan Epoxy Resin Co., Ltd.) 80 parts, (meth) acrylate (C) as polyethylene glycol diacrylate ( Product name: 4EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) 20 parts, organically modified bentonite (product name: Sven NO12S, Hojun Co., Ltd.) 3 parts as an organic affinity layered silicate (E), The mixture was vigorously stirred at 80 ° C. for 4 hours under reduced pressure. After cooling to room temperature, 3.2 parts of 2-ethyl-4-methylimidazole (trade name; Epicure EMI24, manufactured by Japan Epoxy Resin Co., Ltd.) as a curing agent for epoxy resin (B), a curing agent for (meth) acrylate (D ) 0.5 parts of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (trade name; Kayaester TMPO70, manufactured by Kayaku Akzo Co., Ltd.), glycerides and synthetic resins as mold release agents 5 parts of a liquid mixture (trade name; MoldWiz INT-1846N2, manufactured by Axel Plastics Research Laboratories Inc.) was added and stirred sufficiently (over 30 minutes) to prepare a resin composition containing layered silicate (E). .

Example 1
(Production of molded products)
Using a pultrusion molding apparatus (manufactured by Nippon Polyester Co., Ltd., maximum traction force 2.5 ton machine) storing the resin composition obtained in Preparation Example 1 in a resin tank, glass fiber (product name: glass roving RS440RR) -524AE, manufactured by Nittobo Co., Ltd.) was guided through a resin tank through a guide to a die. The resin composition-impregnated fiber reinforcement passed through the die has a three-stage temperature zone (inlet temperature: 60 ° C., intermediate temperature: 160 ° C., outlet temperature: 175 ° C.), height 3.4 mm, width 100 mm, and length The cured product (semi-cured product) was drawn from the die exit at a drawing speed of 18 cm / min, and a molded product of the present invention having a width of 100 mm and a height of 3.4 mm was obtained.

  Based on JIS K 7052, the volume content of the glass fiber in 100% by volume of the molded product excluding the layered silicate (E) having organic affinity was measured and found to be 57% by volume.

  Various characteristics of the obtained molded product were measured. The results are shown in Table 2.

  In Table 2, “longitudinal direction” means the drawing direction of the cured product, and “orthogonal direction” means a direction perpendicular to the drawing direction.

Preparation Examples 2-3
(Preparation of resin composition)
Epoxy resin (A) as shown in Table 1, epoxy resin curing agent (B), (meth) acrylate (C), (meth) acrylate curing agent (D), and layered silicate having organic affinity ( A resin composition of a resin composition and a layered silicate (E) was prepared in the same manner as in Preparation Example 1, except that a predetermined amount of E) was used.

  In Table 1, DICY represents dicyandiamide, TMP3A represents trimethylolpropane triacrylate, BPO represents benzoyl peroxide, and liquoax represents a powder release agent (Montanic acid, manufactured by Clariant Japan Co., Ltd.).

Examples 2-4
(Production of molded products)
The molding of the present invention was carried out in the same manner as in Example 1 except that the resin compositions obtained in Preparation Examples 1 to 3 were used and molded at the fiber reinforcement content, mold temperature, and drawing speed as shown in Table 2. An article was made.

  Various characteristics of the obtained molded product were measured. The results are shown in Table 2.

Reference Preparation Examples 1-4
(Preparation of resin composition)
Epoxy resin (A) as shown in Table 1, epoxy resin curing agent (B), (meth) acrylate (C), (meth) acrylate curing agent (D), and layered silicate having organic affinity ( A resin composition of a resin composition and a layered silicate (E) was prepared in the same manner as in Preparation Example 1, except that a predetermined amount of E) was used.

Reference Comparative Examples 1-4
(Production of molded products)
Using the resin compositions obtained in Reference Preparation Examples 1 to 4, a molded product was obtained in the same manner as in Example 1 except that it was molded at the fiber reinforcement content, mold temperature, and drawing speed as shown in Table 2. Attempts were made to produce any of these, but none of them could be molded.

Comparative Preparation Examples 1 and 2
(Preparation of resin composition)
Comparative Preparation Example 1 is the same as Preparation Example 1 except that the layered silicate (E) is not used in Preparation Example 1, and Comparative Preparation Example 2 is for (meth) acrylate in Preparation Example 1. Resin compositions were prepared in the same manner as in Preparation Example 1 except that the curing agent (D) was not used.

Comparative Example 1
(Production of molded products)
The molding of the present invention was carried out in the same manner as in Example 1 except that the resin composition obtained in Comparative Preparation Example 1 was molded at the fiber reinforcement content, mold temperature, and drawing speed as shown in Table 2. An article was made.

  Various characteristics of the obtained molded product were measured. The results are shown in Table 2.

Comparative Example 2
(Production of molded products)
Using the resin composition obtained in Comparative Adjustment Example 2, a molded product was produced in the same manner as in Example 1 except that the resin composition was molded at the fiber reinforcement content, mold temperature, and drawing speed as shown in Table 2. Was attempted, but could not be molded.

Comparative Preparation Example 3
(Preparation of resin composition)
As shown in Table 1, 100 parts of orthophthalic acid unsaturated polyester (product name; Polyhope G-386, manufactured by Japan Composite Co., Ltd.) as the unsaturated polyester resin, 1,1,3,3-tetramethyl as the curing agent 2.1 parts of butyl peroxy-2-ethylhexanoate (trade name; Kaya Ester TMPO70, manufactured by Kayaku Akzo Co., Ltd.), liquid condensate in which glyceride and organic acid derivative are combined as a release agent (trade name) 2 parts of MoldWiz INT-54, manufactured by Axel Plastics Research Laboratories Inc.) and vigorously stirred under reduced pressure for 30 minutes to prepare a resin composition.

Comparative Example 3
(Production of molded products)
Using the resin composition obtained in Comparative Preparation Example 3, a molded product was prepared in the same manner as in Example 1 except that the resin composition was molded at the fiber reinforcement content, mold temperature, and drawing speed as shown in Table 2. did.

  Various characteristics of the obtained molded product were measured. The results are shown in Table 2.

Comparative Preparation Example 4
(Preparation of resin composition)
For Comparative Preparation Example 4, a resin composition was prepared in the same manner as Comparative Preparation Example 3 except that the layered silicate (E) was further used in Comparative Preparation Example 3.

Comparative Example 4
(Production of molded products)
A molded product was produced in the same manner as in Example 1 except that the resin composition obtained in Comparative Preparation Example 4 was molded at the fiber reinforcement content, mold temperature, and drawing speed as shown in Table 2. did.

  Various characteristics of the obtained molded product were measured. The results are shown in Table 2.

  From the results of Example 2 and Comparative Example 1, the molded article (Example 2) of the present invention molded using the resin composition containing the layered silicate (E) contains the layered silicate (E). It was found to be harder and stronger than the molded product (Comparative Example 1) molded using the resin composition that was not used.

  Moreover, from the result of Example 2 and Comparative Example 1, and Comparative Example 3 and Comparative Example 4, the layered silicate (E) is contained in the mixed resin of the epoxy resin (A) and (meth) acrylate (C). Thus, the obtained molded product shows an improvement effect in both bending stress and flexural modulus (contrast with Example 2 and Comparative Example 1), whereas the unsaturated polyester contains layered silicate (E). Even if it was made, it turned out that the bending stress of the obtained molded article falls on the contrary (comparison with the comparative example 3 and the comparative example 4).

  The resin composition used in the production method of the present invention is excellent in storage stability and fast curability, and therefore can be suitably used as a matrix in a pultrusion method.

  In addition, the molded product of the present invention obtained by pultruding the resin composition and the fiber reinforcing material has a high strength per weight because of excellent adhesion between the resin composition (matrix) and the fiber reinforcing material, Moreover, since it is lightweight and is excellent in toughness, flame retardancy, and corrosion resistance, it can be used as a large-sized molded product, and can be suitably used for, for example, a cover of a large-scale water and sewage treatment tank.

Claims (5)

  Resin composition containing epoxy resin (A), epoxy resin curing agent (B), (meth) acrylate (C), (meth) acrylate curing agent (D), and layered silicate having organic affinity (E) A method for producing a pultruded product, characterized by performing pultrusion using an article and a fiber reinforcing material.   The content of the (meth) acrylate (C) is 5% by mass or more and 40% by mass or less in a total amount of 100% by mass of the epoxy resin (A) and the (meth) acrylate (C). A method for producing the pultruded product as described.   The addition amount of the layered silicate (E) having organic affinity is 0.1 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the total amount of the epoxy resin (A) and the (meth) acrylate (C). The method for producing a pultruded product according to claim 1 or 2, wherein:   4. The pultrusion molding of the resin composition and the fiber reinforcing material through a heating mold having a temperature of 50 ° C. or more and 200 ° C. or less at a speed of 10 cm / min or more and 30 cm / min or less. The method for producing a pultruded product according to one item.   A molded article obtained by the production method according to any one of claims 1 to 4.