JP2009185247A - Resin composition and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition and a molded article excellent in appearance and mechanical properties by reusing a reinforced resin molded article comprising a cycloolefin cured resin and carbon fibers. <P>SOLUTION: A resin composition containing a pulverized material of a reinforced resin molded article comprising a cycloolefin cured resin and carbon fibers, and a polymer material is used. The polymer material is preferably a hydrocarbon resin. The molded article obtained by molding the resin composition is excellent in appearance and mechanical properties. The resin composition is produced through a process for obtaining the pulverized material by pulverizing the reinforced resin molded article comprising the cycloolefin cured resin and the carbon fibers and a process for mixing the pulverized material and the polymer material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition in which a recovered product of a reinforced resin molded product containing a cycloolefin cured resin and carbon fiber is reused, and a molded product thereof.

  Fiber reinforced resin obtained by reinforcing cycloolefin cured resin such as dicyclopentadiene resin with carbon fiber, etc. is superior in mechanical properties, so it can be used for sports structures such as fishing rods and shafts for golf clubs, and for vehicle structures such as automobiles and aircraft. It is expected to be used in a wide range of applications from general industrial applications such as packaging, housing for home appliances, and building materials.

  On the other hand, the development of recycling technology for large-scale products has become a major issue in the industry, such as compliance with various laws such as the Containers and Packaging Recycling Law and the Home Appliance Recycling Law, and the improvement of the recycling ratio of automobile parts. However, the fiber reinforced resin using carbon fiber and the like whose market is rapidly expanding is very solid, and it is difficult to reuse waste products.

  As a method of reusing a dicyclopentadiene resin, Patent Document 1 discloses a composition comprising a thermosetting resin powder having active hydrogen capable of radical crosslinking, a polymer component imparting fluidity, and a radical initiator. A method for producing a crosslinked polymer molded article comprising pressure molding is disclosed. Specifically, a resin powder such as polydicyclopentadiene containing reinforcing glass is blended with about 10 to 27% by weight of a polymer component that imparts fluidity such as low molecular weight 1,2-polybutadiene. A hot-press molded product is illustrated. However, there is a problem that the appearance and mechanical strength of the molded product obtained by this method are not sufficient.

JP-A-5-209128

  An object of the present invention is to provide a resin composition and a molded product excellent in appearance and mechanical properties by reusing a reinforced resin molded product containing a cycloolefin cured resin and carbon fibers.

  In view of the above problems, the present inventors have intensively studied combinations of various reinforcing fibers and matrix resins in resin modification. As a result, carbon fiber reinforced resin molded products obtained by curing a cycloolefin polymer in carbon fiber reinforced fibers. It has been found that the pulverized product pulverized by a pulverizer or the like greatly improves the mechanical properties of resin molded products such as polyolefin and is excellent in appearance and the like. Based on these findings, the present inventors have completed the present invention.

Thus, according to the present invention, there is provided a resin composition comprising a pulverized product of a reinforced resin molded product containing a cycloolefin cured resin and carbon fibers and a polymer material.
The polymer material is preferably a hydrocarbon resin.
Moreover, according to this invention, the molded object formed by shape | molding the said resin composition is provided.
Furthermore, according to the present invention, a resin composition comprising a step of pulverizing a reinforced resin molded product containing a cycloolefin cured resin and carbon fiber to obtain a pulverized product, and a step of mixing the pulverized product with a polymer material A method is provided.

  According to the present invention, the mechanical properties of the resin can be easily modified using the pulverized product of the recovered carbon fiber reinforced resin molded product. In addition, since the molded article of the present invention is excellent in mechanical properties, it can be suitably used in fields such as automobiles and aircraft structures, sports, civil engineering, and architecture.

(Reinforced resin molded product)
The reinforced resin molded article used in the present invention contains a cycloolefin cured resin and carbon fiber. The manufacturing method, shape, etc. are not particularly limited. For example, after being used as a member such as a laminated body obtained by laminating and curing OA equipment, home appliances, vehicle structural members or prepregs molded by an injection molding method or the like. In addition, collected items and end products such as a spool runner generated when the member is molded are included.

  The reinforced resin molded product used in the present invention is composed of carbon fiber of reinforcing fiber and cycloolefin cured resin of matrix resin, and is very excellent in compatibility between carbon fiber and cycloolefin cured resin.

  The type of carbon fiber is not particularly limited, and for example, carbon fibers produced by various conventionally known methods such as acrylic, pitch, and rayon can be used. Among them, acrylic carbon fibers (PAN-based carbon fibers), which are carbon fibers manufactured using acrylic fibers (polyacrylonitrile fibers) as raw materials, are particularly excellent in compatibility with cycloolefin-cured resins, and are mechanically obtained. Properties such as strength and impact strength can be imparted to a high degree, which is preferable.

  The strength characteristics of the carbon fiber are not particularly limited and are appropriately selected according to the purpose of use. The tensile strength is a strand tensile strength measured according to JIS R7601, and is usually 0.5 to 50 GPa, preferably 1 to 10 GPa, more preferably 2 to 8 GPa. The tensile modulus is a strand tensile modulus measured according to JIS R7601, and is usually in the range of 100 to 1,000 GPa, preferably 200 to 800 GPa, more preferably 300 to 700 GPa. The elongation is a strand tensile elongation measured according to JIS R7601, and is usually 0.1 to 10%, preferably 0.5 to 5%, more preferably 1 to 3%. When the strength characteristics of the carbon fiber are within these ranges, characteristics such as the appearance and mechanical strength of the resulting molded body are highly balanced, which is preferable.

  The length of the carbon fiber is appropriately selected according to the purpose of use without any particular limitation, and both short fibers and long fibers can be used. However, when higher mechanical strength and toughness are desired, The length is 1 mm or more, preferably 2 mm or more, more preferably 3 mm or more, and most preferably continuous fiber.

  The form of the carbon fiber is not particularly limited, and can be appropriately selected from woven fabric, nonwoven fabric, mat, knit, braid, unidirectional strand, roving, chopped, and the like. Among these, in order to obtain a fiber reinforced resin base material having a higher level of mechanical strength and impact resistance, the fiber is preferably in the form of a continuous fiber such as a woven fabric, a unidirectional strand, or a roving. As the woven form, conventionally known ones can be used. For example, all of woven structures in which fibers such as plain weave, satin weave, twill weave, and triaxial weave are interlaced can be used. Moreover, as a woven fabric form, not only two-dimensional but also a stitch woven fabric and a three-dimensional woven fabric in which fibers are reinforced in the thickness direction of the woven fabric can be used.

  Carbon fibers are used as fiber bundle yarns when used in woven fabrics. In this case, the number of filaments in one fiber bundle yarn is not particularly limited, but is 1,000 to 100,000, preferably 2,000 to 20,000, more preferably 5,000 to 15. , 000.

  The carbon fiber content in the reinforced resin molded product is not particularly limited, but is usually 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and particularly preferably 30 to 70% by weight. % Range.

  The cycloolefin cured resin is not particularly limited as long as it is a cured cycloolefin polymer. As the cycloolefin polymer, a known polymer of cycloolefin monomer can be used without any particular limitation. Specific examples include a ring-opening polymer of a cycloolefin monomer, an addition polymer of a cycloolefin monomer, an addition copolymer of a cycloolefin monomer and a chain olefin, and a hydride thereof. A cycloolefin monomer is a compound having a ring structure formed of carbon atoms and having a carbon-carbon double bond in the ring. Examples thereof include norbornene monomers and monocyclic cycloolefins, and norbornene monomers are preferred. The norbornene-based monomer is a monomer containing a norbornene ring. The norbornene-based monomer is not particularly limited, and examples thereof include bicyclic compounds such as 2-norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydrodicyclopentadiene, tetracyclododecene, and ethylidenetetracyclododecene. , Tetracycles such as phenyltetracyclododecene, pentacycles such as tricyclopentadiene, heptacycles such as tetracyclopentadiene, and alkyl substituents thereof (methyl, ethyl, propyl, butyl substituents, etc.), alkylidene Substituted (eg, ethylidene substituted), aryl substituted (eg, phenyl, tolyl substituted), epoxy group, methacryl group, hydroxyl group, amino group, carboxyl group, cyano group, halogen group, ether group, ester bond contained Derivatives having polar groups such as It is. Examples of the monocyclic cycloolefin monomer include monocyclic cycloolefins such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and derivatives having a substituent.

  The cycloolefin cured resin is obtained by curing the cycloolefin polymer, and is defined by not dissolving in a solvent. On the other hand, the uncured cycloolefin polymer is usually dissolved in a solvent. The solvent used in the dissolution test is appropriately selected from solvents such as aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether and tetrahydrofuran, and halogenated hydrocarbons such as dichloromethane and chloroform. In addition, as a method for curing the cycloolefin polymer, any known method such as radical crosslinking or ionic crosslinking can be employed, and radical crosslinking is preferred.

  The reinforced resin molded product used in the present invention contains the carbon fiber and the cycloolefin cured resin as essential components, and may contain other compounding agents as necessary. Other compounding agents are appropriately selected depending on the purpose of use, but include elastomer materials, fillers, anti-aging agents, flame retardants, colorants, light stabilizers, pigments, foaming agents, polymer modifiers, etc. Can be mentioned.

  The reinforced resin molded product used in the present invention is used as a pulverized product. The pulverization method is not particularly limited, but a pulverized product of the reinforced resin molded product is produced by fragmentation using a crusher or a pulverizer. Various methods such as a shearing type, an impact type, and a cutting type can be adopted for the crusher and the crusher.

  Specifically, it is usually crushed to a particle size of about 10 mm by a crusher, and then used as a powder having a particle size of 1 to 500 μm, preferably 5 to 250 μm, more preferably 10 to 100 μm. it can. Specific examples of the crusher and crusher include, for example, a crusher such as a shreter, a joke crusher, a gyre crusher, a cone crusher, a hammer crusher, an impact crusher, a roll crusher, a roll mill, a stamp mill, and an edge runner. And crushers such as a grinder, a cutter mill, a rod mill, etc., a grinder, an Elofold mill, a cascade mill, and the like.

  The pulverized product of the reinforced resin molded product used in the present invention can be used after being sieved. For screening, for example, by airflow classification, etc., usually only powders of 500 μm or less, preferably 250 μm or less, more preferably 100 μm or less are screened, and powders having a larger particle size are pulverized again by a crusher or a pulverizer. The

  The pulverized product of the reinforced resin molded product used in the present invention is preferably used separately based on the specific gravity. For example, the specific gravity of carbon fiber is 1.8 and the specific gravity of dicyclopentadiene resin is 1.0, so that it can be used separately from a pulverized product with a lot of carbon fibers and a pulverized product with a lot of resin components. Separation by specific gravity can be performed by a separation method using a liquid or a method using a centrifugal separation method. Centrifugal separation is performed by putting a pulverized material on a rotating plate and rotating the rotating plate to such an extent that a predetermined centrifugal force is generated, and the pulverized material scattered from the rotating plate has a large specific gravity. The crushed material remaining on the top is separated as having a small specific gravity. Moreover, it can also carry out using the centrifugation method by a cyclone.

  The specific gravity of the pulverized product of the reinforced resin molded product used in the present invention is appropriately selected depending on the purpose of use, but is usually 1.10 to 1.70, preferably 1.20 to 1.75, more preferably 1. It is in the range of 30 to 1.70.

  The pulverized product of the reinforced resin molded product used in the present invention is usually used with a water content of 0.1% by weight or less. Moreover, it is preferable to use what pulverized material of the reinforced resin molded product used for this invention removed the metal foreign material using the magnet etc.

  These pulverized products of reinforced resin molded products can be used alone or in combination of two or more.

(Polymer polymer)
The polymer material used in the present invention is not particularly limited, and examples thereof include a thermoplastic resin, a thermosetting resin, and an elastomer.

  Examples of the thermoplastic resin include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and liquid crystal polyester; polyolefins such as polyethylene, polypropylene, polybutylene, and polycycloolefin; polystyrene, polyoxymethylene, polyamide, polycarbonate, and polymethylene. Methacrylate, polyimide, polyetherimide, polyetherketone, polyetheretherketone, polysulfone and the like can be mentioned, and hydrocarbon resins such as polyolefin and polystyrene are preferable, and polyolefin is more preferable.

  Examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, phenol resin, benzoxazine resin, vinyl ester resin, polybutadiene resin, cycloolefin cured resin such as dicyclopentadiene resin, and the like. Among these, a cycloolefin cured resin is preferable.

  Examples of the elastomer material include natural rubber, polyisoprene, polybutadiene, styrene-butadiene copolymer, chloroprene, acrylonitrile-butadiene copolymer, styrene-isoprene-styrene block copolymer, and styrene-butadiene-styrene block copolymer. , Ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-vinyl acetate copolymer, and hydrogenated products thereof.

  These polymer materials can be used alone or in combination of two or more. The use ratio of the pulverized product of the reinforced resin molded product and the polymer material is appropriately selected according to the purpose of use. It is -90/10, Preferably it is the range of 10 / 90-60 / 40, Preferably it is the range of 10 / 90-40 / 60.

(Resin composition and molded body)
In the resin composition of the present invention, the pulverized product of the reinforced resin molded product and the polymer material are essential components, and other components can be blended as necessary. Examples of other components include reinforcing fibers, anti-aging agents, fillers, flame retardants, colorants, light stabilizers, pigments, foaming agents, and polymer modifiers.

  The reinforcing fiber is not particularly limited. For example, organic fibers such as PET (polyethylene terephthalate) fiber, aramid fiber, ultra-high molecular polyethylene fiber, polyamide (nylon) fiber, liquid crystal polyester fiber; glass fiber, carbon fiber, Examples thereof include inorganic fibers such as alumina fibers, tungsten fibers, molybdenum fibers, butene fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers. Among these, organic fiber, glass fiber, and carbon fiber are preferable, and carbon fiber is more preferable.

  As the anti-aging agent, at least one anti-aging agent selected from the group consisting of phenol-based anti-aging agents, amine-based anti-aging agents, phosphorus-based anti-aging agents and sulfur-based anti-aging agents is particularly suitable. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is particularly preferable. The filler is not particularly limited as long as it is generally used industrially, and any of inorganic fillers and organic fillers can be used. Examples of the flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a halogen flame retardant, a metal hydroxide flame retardant such as aluminum hydroxide, and an antimony compound such as antimony trioxide. As the colorant, dyes, pigments and the like are used. There are various kinds of dyes, and known ones may be appropriately selected and used.

  These other components can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.

  The resin composition of the present invention can be produced by mixing the above components, and the mixing method and the resin composition shape are appropriately selected according to the type of the polymer material.

  When the polymer material is a thermoplastic resin, the mixing method and the resin composition shape may be in accordance with the conventional method of thermoplastic resin, and usually melt and knead using an extruder to produce a linear strand, which is solidified. And then used as pellets cut to a predetermined length. Although the length of a pellet is suitably selected according to the intended purpose, it is 1-50 mm normally, Preferably it is 2-40 mm, More preferably, it is the range of 3-30 mm.

  When the polymer material is a thermosetting resin, the mixing method and the resin composition shape may be in accordance with ordinary methods, may be cured in a mold, or used as a prepreg. In the case of a prepreg, each component can be impregnated in a reinforced resin or the like, and a thermosetting resin can be polymerized and used. The impregnation method of each component is applied to the reinforcing fiber by a known method such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, or a slit coating method, and if necessary, a protective film thereon Can be carried out by stacking and pressing with a roller or the like from above. After impregnating each component into the reinforcing fiber, the polymerizable composition can be bulk polymerized by heating the impregnated product to a predetermined temperature, whereby a sheet-like or film-like prepreg is obtained. The polymerization method can be performed according to each thermosetting resin.

  When the polymer material is an elastomer material, the mixing method and the resin composition shape may be in accordance with conventional methods, and can usually be performed using a kneader such as a roll, a kneader, or a Banbury.

(Molded body)
The molded body of the present invention is formed by molding the above resin composition. The molding method is appropriately selected according to the type of polymer material according to a conventional method.

  The polymer material molded body blended with the pulverized product of the reinforced resin molded product containing the cycloolefin cured resin and carbon fiber of the present invention is excellent in appearance and mechanical properties. For example, for example, OA and AV equipment, automobiles and railways. It is suitably used for sports applications such as golf shafts and fishing rods, and other general industrial applications such as automotive structural materials, aircraft interior parts, and the like. Specific applications include, for example, sports applications such as fishing rods, golf club shafts, tennis rackets, and skistocks; displays, FDD carriages, chassis, HDD, MO, motor brush holders, parabolic antennas, notebook computers, mobile phones, Electric / electronic devices such as digital still cameras, PDAs, portable MDs, liquid crystal displays, plasma displays; telephones, facsimiles, VTRs, photocopiers, televisions, irons, hair dryers, rice cookers, microwave ovens, audio equipment, vacuum cleaners, toiletries Supplies, leather discs, compact discs, lighting, refrigerators, air conditioners, typewriters, word processors, office automation equipment and household appliances; undercovers, scuff plates, pillar trims, professionals Automobiles such as rubber shafts, drive shafts, wheels, wheel covers, fenders, door mirrors, room mirrors, feshers, bumpers, bumper beams, bonnets, trunk hoods, aero parts, platforms, cowl louvers, roofs, instrument panels, spirals and various modules Parts; aircraft parts such as landing gear pods, wing reds, spoilers, edges, ladders, and failings; and building materials such as panels.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In the examples and comparative examples, “part” and “%” are based on weight unless otherwise specified.

Each characteristic in an Example and a comparative example was measured and evaluated according to the following method.
(1) Appearance evaluation: The appearance of the obtained molded product was observed and evaluated according to the following criteria.
◎: Shape collapse, powder fall off, etc. are not observed. Δ: Shape collapse, powder fall off, etc. are slightly observed. X: Shape collapse, powder fall off, etc. are severely observed.

(2) Evaluation of mechanical properties of molded article: Izod impact strength test of molded article was carried out with a swing angle of 127 degrees using Ushima UF Impact Test, Comparative Example 1 (resin blank molded article) was set to 100, and the following criteria Judged.
A: More than 110 Δ: More than 100, 110 or less ×: 100 or less

Production Example 1 (Production of reinforced resin molded product A)
A catalyst solution was prepared by dissolving 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine in 952 parts of toluene. Separately, 100 parts of dicyclopentadiene (DCP), 0.74 parts of allyl methacrylate as a chain transfer agent, 1.2 parts of di-t-butyl peroxide (186 ° C., 1 minute half-life temperature), phenolic As an anti-aging agent, 1.0 part of 3,5-di-t-butyl-4-hydroxyanisole was added and mixed to prepare a monomer solution. The above catalyst solution was added thereto at a rate of 0.12 ml per 100 g of cycloolefin monomer and stirred to prepare a polymerizable composition.

On the other hand, a stack of six carbon fibers (fiber basis weight: 190 g / m ² , fiber tensile strength 4,900 MPa, fiber tensile elastic modulus: 294 GPa, thickness 0.1 mm) is placed in a mold and clamped. It was. Then, the prepared polymerizable composition was poured into a mold and cured at 200 ° C. for 15 minutes to obtain a reinforced resin molded product A (carbon fiber content 71%).

Production Example 2 (Production of reinforced resin molded product B)
Except having changed the magnitude | size of the metal mold | die, it carried out similarly to manufacture example 1, and obtained the carbon fiber reinforced resin molded product B with a carbon fiber content of 66%.

Example 1
The reinforced resin molded product A obtained in Production Example 1 was crushed with a uniaxial impact crusher (consumption energy 700 kJ / kg) and then pulverized with a grinder (particle size # 80) to obtain a pulverized product. The particle size of the obtained pulverized product was 20 μm.

  Subsequently, 40 parts of the pulverized product was mixed with 100 parts of polypropylene to obtain a resin composition. This was injection-molded at 150 ° C. for 90 seconds to obtain a molded body having a 10 cm square and a thickness of 3 mm. The appearance and mechanical properties of the obtained molded body were evaluated, and the results are shown in Table 1.

Example 2
The resin molded product B obtained in Production Example 2 was crushed with a uniaxial impact crusher (energy consumption: 700 kJ / kg), and then pulverized with a grinder (particle size # 80) to obtain a pulverized product. The particle size of the obtained pulverized product was 20 μm. A molded product was obtained in the same manner as in Example 1 except that 40 parts of the pulverized product was used as the pulverized product. Each characteristic was evaluated and the results are shown in Table 1.

Comparative Example 1
This was carried out in the same manner as in Example 1 except that the pulverized resin molded product was not used, and a blank molded body was obtained. Each characteristic was evaluated, and the results are shown in Table 1.

Example 3
A catalyst solution was prepared by dissolving 51 parts of benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride and 79 parts of triphenylphosphine in 952 parts of toluene. Separately, 100 parts of dicyclopentadiene (DCPD) is added as a cycloolefin monomer, and 1.2 parts of di-t-butyl peroxide (1 minute half-life temperature 186 ° C.) is used as a crosslinking agent. 20 parts of m-diisopropenylbenzene, 1.0 part of 3,5-di-tert-butyl-4-hydroxyanisole as a phenolic antioxidant, 0.74 part of allyl methacrylate as a chain transfer agent, and production examples The reinforced resin molded product A prepared in 1 was crushed with a uniaxial impact crusher (consumption energy 700 kJ / kg), and then pulverized with a grinder (particle size # 80) and 50 parts of a pulverized product with a particle size of 20 μm was added. Thereafter, the catalyst solution was added at a rate of 0.12 ml per 100 g of cycloolefin monomer and stirred to prepare a polymerizable composition.

  Next, 100 parts of the obtained polymerizable composition was cast on a polyethylene naphthalate film (thickness: 75 μm), an acrylic carbon fiber was laid thereon, and 80 parts of the polymerizable composition was further added thereon. After casting, a polyethylene naphthalate film was further covered thereon, and the polymerizable composition was impregnated into the carbon fiber using a roller. Subsequently, this was subjected to a polymerization reaction at 120 ° C. for 5 minutes to obtain a prepreg having a thickness of 0.13 mm.

  This prepreg was cut into a size having a width of 80 mm and a length of 1000 mm, and the polyethylene naphthalate film was peeled off. Then, 6 sheets of the prepreg were stacked and placed in an oven at 200 ° C. for 15 minutes to cure the resin, thereby producing a laminate. Each characteristic of the obtained laminate was evaluated, and the results are shown in Table 1.

  As is clear from the above results, it can be seen that when the resin composition of the present invention is used, molded articles having excellent appearance and mechanical properties can be obtained (Examples 1 to 3).

Claims (4)

A resin composition comprising a pulverized product of a reinforced resin molded article containing a cycloolefin cured resin and carbon fiber, and a polymer material. The resin composition according to claim 1, wherein the polymer material is a hydrocarbon resin. The molded object formed by shape | molding the resin composition of Claim 1 or 2. A method for producing a resin composition comprising a step of pulverizing a reinforced resin molded article containing a cycloolefin cured resin and carbon fiber to obtain a pulverized product, and a step of mixing the pulverized product and a polymer material.