JP2015048450A - Polycarbonate resin molding material and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin molding material that has good dispersibility of reinforcing fibers in a polycarbonate resin during molding, inhibits breakage of reinforcing fibers in the molded article and can exhibit excellent dynamic characteristics.SOLUTION: The polycarbonate resin molding material includes, based on 100 pts.wt. of [A] a polycarbonate resin, at least 10-250 pts.wt. of [D] a resin-impregnated reinforcing fiber produced by melting and impregnating [B] a reinforcing fiber bundle with [C] an epoxy resin and 1-150 pts.wt. of [E] a styrene-based resin, and/or, a copolymer of olefin and an alkyl (meth)acrylate. The weight ratio ([B]/[C]) of the component [B] to the component [C] contained in the component [D] is 87/13 to 50/50 and the component [D] is coated with a resin composition including at least the component [A].

Description

  The present invention relates to a molding material and a molded product. More specifically, the dispersibility of reinforcing fibers in a polycarbonate resin during molding is good, breakage of reinforcing fibers can be suppressed, and excellent mechanical properties can be expressed. The present invention relates to a polycarbonate resin molding material from which a molded product can be obtained and a molded product formed by molding the same.

  Molding materials containing reinforcing fibers and thermoplastic resins are lightweight and have excellent mechanical properties, and are therefore widely used in sports equipment applications, aerospace applications, general industrial applications, and the like. The reinforcing fibers used in these molding materials reinforce the molded product in various forms depending on the application. These reinforcing fibers include metal fibers such as aluminum fibers and stainless fibers, organic fibers such as aramid fibers and PBO (polyparaphenylene benzoxazole) fibers, inorganic fibers such as silicon carbide fibers, and carbon fibers. However, carbon fiber is preferable from the viewpoint of the balance of specific strength, specific rigidity, and lightness, and among them, polyacrylonitrile (PAN) carbon fiber is preferably used.

  As thermoplastic resins used as matrix resins, there is a great demand for polycarbonate resins due to their excellent mechanical properties such as impact resistance and thermal stability, especially in various fields such as electrical and electronic equipment casings and automotive parts. Widely used. Here, in applications such as electronic equipment casings, further improvements in mechanical properties are required in accordance with demands for further weight reduction and thickness reduction. However, the polycarbonate resin tends to have a relatively high melt viscosity, and the fluidity is low, or the reinforcing fibers may not be uniformly dispersed in the resin.

  As a polycarbonate resin composition excellent in dimensional stability, fluidity, and heat resistance, for example, a long fiber thermoplastic resin composition obtained by blending reinforcing fibers with a composition comprising a polycarbonate resin and a styrene resin has been proposed. (For example, refer to Patent Document 1). Also, polycarbonate resin, styrene resin and / or polyester resin, and organic phosphate ester are reinforced as a flame retardant resin composition that provides thin-walled molded products with excellent mechanical strength, heat resistance and flame retardancy. There has been proposed a flame retardant resin composition obtained by cutting a fiber that has been fused and adhered to a fiber (for example, see Patent Document 2). However, in both documents, there is a problem that the dispersibility of the reinforcing fibers at the time of molding is insufficient and the mechanical properties are also insufficient.

  Therefore, the present applicant has so far provided a method for producing a reinforcing fiber bundle that exhibits excellent dispersibility during molding, and a molding material by impregnating the reinforcing fiber bundle in a molten state with a compound having a bisphenol residue. It has been proposed (see, for example, Patent Document 3). Although this technique improves the dispersibility of reinforcing fibers in a molded product, there is a problem that mechanical properties such as impact resistance are still insufficient.

JP 2008-202012 A JP2013-121988A JP 2012-56232 A

  Under such circumstances, there has been a demand for the development of a polycarbonate resin molding material capable of obtaining a molded product that has good dispersibility of reinforcing fibers in the polycarbonate resin during molding and can exhibit excellent mechanical properties.

  In view of the problems of the prior art, the present invention provides a polycarbonate resin molding material that has good dispersibility of reinforcing fibers in a polycarbonate resin during molding, can suppress breakage of reinforcing fibers in a molded product, and can exhibit excellent mechanical properties. The purpose is to provide.

In order to solve the above problems, the present invention has the following configuration.
(1) 10 to 250 parts by weight of resin-impregnated reinforcing fiber [D] obtained by melt impregnating epoxy resin [C] into reinforcing fiber bundle [B] with respect to 100 parts by weight of polycarbonate resin [A], and styrene Resin and / or polycarbonate resin molding material containing 1-150 parts by weight of an olefin and (meth) acrylic acid alkyl ester copolymer [E], wherein the component [D] B] and the component [C] in a weight ratio ([B] / [C]) of 87/13 to 50/50, and the component [D] is a resin composition containing at least the component [A]. A polycarbonate resin molding material formed by coating.
(2) The polycarbonate resin molding material according to (1), wherein the component [D] is coated with a polycarbonate resin composition obtained by melt-kneading at least the component [A] and the component [E].
(3) The polycarbonate resin molding material according to (1) or (2), wherein the component [C] contains a bisphenol A type epoxy resin.
(4) The polycarbonate resin molding material according to any one of (1) to (3), wherein the component [E] includes a rubber-modified styrene resin.
(5) The polycarbonate resin molding material according to (4), wherein the rubber-modified styrene resin includes a styrene-ethylene-butylene-styrene copolymer (SEBS resin).
(6) The polycarbonate resin molding material according to any one of (1) to (3), wherein the component [E] includes a copolymer of ethylene and alkyl acrylate.
(7) The polycarbonate resin molding material according to any one of (1) to (6), further including 1 to 100 parts by weight of a flame retardant [F] with respect to 100 parts by weight of the component [A].
(8) The polycarbonate resin molding material according to (7), wherein the component [F] contains a phosphorus-based flame retardant.
(9) The polycarbonate resin molding material according to any one of (1) to (8), further including 0.1 to 100 parts by weight of a conductive filler [G] with respect to 100 parts by weight of the component [A].
(10) (i) dry blending a molding material containing at least the component [A] and the component [D], and (ii) a molding material containing at least the component [A] and the component [E]. The manufacturing method of the polycarbonate resin molding material in any one of 1)-(9).
(11) A molded product obtained by molding the polycarbonate resin molding material according to any one of (1) to (9).

  The polycarbonate resin molding material of the present invention has excellent dispersibility of reinforcing fibers in the polycarbonate resin at the time of molding, and is excellent in mechanical properties such as bending properties and impact resistance properties because the breakage of the reinforcing fibers is suppressed. A molded product can be obtained. Furthermore, when the reinforcing fiber has conductivity, the electromagnetic wave shielding property of the molded product is dramatically improved. The molded product molded using the polycarbonate resin molding material of the present invention is extremely useful for various parts and members such as electric / electronic devices, OA devices, home appliances, automobile parts, internal members, and housings.

It is the schematic which shows an example of the cross-sectional form of the resin impregnation reinforcement fiber [D] in this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the polycarbonate resin molding material of this invention. It is the schematic which shows an example (a) of a preferable longitudinal cross-sectional form of the polycarbonate resin molding material of this invention, and an example (b) of a cross-sectional form. It is the schematic which shows an example (a) of a preferable longitudinal cross-sectional form of the polycarbonate resin molding material of this invention, and an example (b) of a cross-sectional form. It is the schematic which shows an example (a) of a preferable longitudinal cross-sectional form of the polycarbonate resin molding material of this invention, and an example (b) of a cross-sectional form. It is the schematic which shows an example (a) of a preferable longitudinal cross-sectional form of the polycarbonate resin molding material of this invention, and an example (b) of a cross-sectional form. It is the schematic which shows an example of the preferable cross-sectional form of the polycarbonate resin molding material of this invention.

  The present invention will be described in detail. The polycarbonate resin molding material of the present invention comprises at least a polycarbonate resin [A], a resin-impregnated reinforcing fiber [D] obtained by melt-impregnating an epoxy resin [C] into a reinforcing fiber bundle [B], a styrenic resin, and / or Alternatively, a copolymer [E] of an olefin and an alkyl (meth) acrylate is included. First, these constituent components will be described in detail. In the present invention, the “molding material” means a raw material used when a molded product is molded by injection molding or the like.

  The polycarbonate resin [A] in the present invention is a resin having a good balance between mechanical properties, thermal stability, and flame retardancy, and the reinforcing effect by the reinforcing fiber and the flame retardancy improving effect by the flame retardant act more effectively. Therefore, it is preferably used. In the present invention, the polycarbonate resin [A] is a polymer having a carbonate ester structure in the main chain, and examples thereof include aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and aromatic polycarbonate. These may be used alone or in combination of two or more. An aromatic polycarbonate having a carbonate ester structure of 4,4'-dihydroxydiphenyl-2,2-propane (bisphenol A) is particularly preferably used from the viewpoint of superior impact resistance.

Further, the viscosity average molecular weight (M _v ) of the polycarbonate resin [A] is preferably 10,000 to 50,000. A viscosity average molecular weight (M _v ) of 10,000 or more is preferable because of excellent mechanical properties such as impact resistance. 15,000 or more is more preferable, and 18,000 or more is more preferable. On the other hand, when the viscosity average molecular weight (M _v ) is 50,000 or less, the fluidity during molding is excellent and the moldability is high, which is preferable. It is more preferably 40,000 or less, and further preferably 35,000 or less.

Here, the viscosity average molecular weight (M _v ) can be determined by the following method. First, with respect to a solution obtained by dissolving 0.7 g of polycarbonate resin [A] in 100 ml of methylene chloride at 20 ° C., the specific viscosity (η _SP ) calculated by the following formula is obtained at 20 ° C. using an Ostwald viscometer.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]

Subsequently, the viscosity average molecular weight M _v can be calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The method for obtaining the polycarbonate resin [A] is not particularly limited, and a known production method can be used, and examples thereof include a phosgene method, a transesterification method, and a solid phase polymerization method. In addition, “Iupilon” (registered trademark), “Novalex” (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd., “Panlite” (registered trademark) manufactured by Teijin Chemicals Ltd., “Taflon manufactured by Idemitsu Petrochemical Co., Ltd.” "(Registered trademark)" and the like can be obtained and used.

  In the present invention, the reinforcing fiber constituting the reinforcing fiber bundle [B] is not particularly limited, but for example, high strength and high strength such as carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, etc. Elastic modulus fibers can be used, and these may be used alone or in combination of two or more.

  The reinforcing fiber [B] in the present invention can improve mechanical properties due to the fiber reinforcing effect on the polycarbonate resin [A]. Furthermore, when the reinforcing fiber has inherent characteristics such as conductivity and thermal conductivity, those properties that cannot be achieved with the polycarbonate resin [A] alone can also be imparted. From such a viewpoint, among the reinforcing fibers, carbon fibers such as PAN, pitch, and rayon are preferable from the viewpoint of further improving mechanical properties and reducing the weight of the molded product. From the viewpoint of balance, PAN-based carbon fibers are more preferable. For the purpose of imparting electrical conductivity, reinforcing fibers coated with a metal such as nickel, copper or ytterbium are also preferably used.

  Further, as the carbon fiber, the surface oxygen concentration ratio [O / C] which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy is 0.05-0. .5 is preferred. When the surface oxygen concentration ratio is 0.05 or more, the amount of functional groups on the surface of the carbon fiber can be secured, stronger adhesion to the polycarbonate resin [A] can be obtained, and the strength of the molded product can be further improved. Can do. 0.08 or more is more preferable, and 0.1 or more is more preferable. On the other hand, the upper limit of the surface oxygen concentration ratio is not particularly limited, but it can be generally exemplified to be 0.5 or less in view of the balance of carbon fiber handleability and productivity. 0.4 or less is more preferable, and 0.3 or less is more preferable.

The surface oxygen concentration ratio of the carbon fiber is determined by X-ray photoelectron spectroscopy according to the following procedure. First, when a sizing agent or the like is attached to the surface of the carbon fiber, the carbon fiber bundle from which the sizing agent or the like attached to the surface of the carbon fiber is removed with a solvent is cut into 20 mm, and the sample support table made of copper is used. After expanding and arranging, A1Kα1 and 2 are used as X-ray sources, and the inside of the sample chamber is kept at 1 × 10 ⁻⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s is adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. Is obtained by drawing a straight base line in the range of 1191 to 1205 eV. O _1s peak area E. Is obtained by drawing a straight base line in the range of 947 to 959 eV.

Here, the surface oxygen concentration ratio is calculated as an atomic number ratio from the ratio of the O _1s peak area to the C _1s peak area using a sensitivity correction value unique to the apparatus. When the model ES-200 manufactured by Kokusai Electric Inc. is used as the X-ray photoelectron spectroscopy apparatus, the sensitivity correction value is set to 1.74.

  The means for controlling the surface oxygen concentration ratio [O / C] to 0.05 to 0.5 is not particularly limited. For example, techniques such as electrolytic oxidation, chemical oxidation, and vapor phase oxidation are used. Among them, electrolytic oxidation treatment is preferable.

  The average fiber diameter of the reinforcing fibers constituting the reinforcing fiber bundle [B] is not particularly limited, but is preferably in the range of 1 to 20 μm from the viewpoint of mechanical properties and surface appearance of the obtained molded product. More preferably, it is in the range of ˜15 μm.

  The number of single fibers of the reinforcing fiber bundle [B] is not particularly limited, and can be used within the range of 100 to 350,000, and particularly within the range of 1,000 to 250,000. Is preferred. Further, according to the present invention, since the resin-impregnated reinforcing fiber [D] sufficiently impregnated with the epoxy resin [C] can be obtained even in a reinforcing fiber bundle having a large number of single fibers, 20,000 to Use in the range of 100,000 is preferable from the viewpoint of productivity.

  Further, the reinforcing fiber bundle [B] used in the present invention is preferably provided with a sizing agent, and improves bundling property, bending resistance and scratch resistance, and fluff, yarn breakage in a higher processing step. Generation can be suppressed, and higher workability can be improved as a so-called paste or bundling agent. In particular, in the case of carbon fiber, by applying a sizing agent, it is possible to improve the adhesion and composite overall characteristics by adapting to the surface characteristics such as functional groups on the surface of the carbon fiber.

  The component of the sizing agent used in the present invention is not particularly limited, and examples thereof include an epoxy resin, a phenol resin, polyethylene glycol, polyurethane, polyester, an emulsifier, and a surfactant. Among these, the above-described polycarbonate resin, styrene-based resin described later, and / or an epoxy resin that easily exhibits adhesiveness with a matrix resin composed of a copolymer of olefin and (meth) acrylic acid alkyl ester are preferable. These may be used alone or in combination of two or more.

  Furthermore, examples of the epoxy resin used for the sizing agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic epoxy resin, phenol novolac type epoxy resin and the like. Of these, aliphatic epoxy resins are preferred from the viewpoint of further improving the mechanical properties. Normally, epoxy resins having a large number of epoxy groups tend to have a structure with low toughness because the crosslinking density after the crosslinking reaction increases, but aliphatic epoxy resins tend to have a crosslinking density due to their flexible skeleton. Even if it is high, it tends to be a structure with high toughness. For this reason, when an aliphatic epoxy resin is interposed between the reinforcing fiber and the matrix resin, it is soft and difficult to peel off.

  Specific examples of the aliphatic epoxy resin include diglycidyl ether compounds and polyglycidyl ether compounds. As the diglycidyl ether compound, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, Examples include polytetramethylene glycol diglycidyl ethers and polyalkylene glycol diglycidyl ethers. Polyglycidyl ether compounds include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ethers, arabitol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers, trimethylol Examples thereof include propane glycidyl ethers, pentaerythritol polyglycidyl ethers, polyglycidyl ethers of aliphatic polyhydric alcohols, and the like.

  Among the aliphatic epoxy resins, it is preferable to use a trifunctional or higher polyfunctional aliphatic epoxy resin, and it is more preferable to use an aliphatic polyglycidyl ether compound having three or more highly reactive glycidyl groups. . Among these, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ethers, and polypropylene glycol glycidyl ether are more preferable. Aliphatic polyglycidyl ether compounds are preferred because they have a good balance of flexibility, crosslink density, and compatibility with the matrix resin and effectively improve adhesion.

  Here, when using an epoxy resin for the sizing agent, it is not necessarily a different component from the epoxy resin [C] to be melt-impregnated into the reinforcing fiber bundle [B], but the epoxy equivalent of the epoxy resin used for the sizing agent is It is more preferable to select and use a component smaller than the epoxy equivalent of component [C]. Here, the small epoxy equivalent means that the number of epoxy groups per molecular weight is large. More specifically, the epoxy resin used for the sizing agent preferably has an epoxy equivalent of 100 g / eq or more and less than 300 g / eq, and the component [C] has an epoxy equivalent of 300 to 3000 g as described later. It is preferably in the range of / eq. In such a preferable range, the interfacial adhesiveness, fiber dispersibility, and mechanical properties can be improved in a balanced manner.

  Although the adhesion amount of a sizing agent is not specifically limited, 0.01-10 weight% is preferable in 100 weight% of reinforcing fiber bundles [B] containing a sizing agent and a reinforcing fiber. If the amount of sizing agent adhesion is 0.01% by weight or more, the effect of improving adhesiveness is sufficiently exhibited. 0.05 weight% or more is more preferable, and 0.1 weight% or more is further more preferable. On the other hand, if the sizing agent adhesion amount is 10% by weight or less, the physical properties of the polycarbonate resin [A] can be sufficiently maintained. 5% by weight or less is more preferable, and 2% by weight or less is more preferable.

  The means for applying the sizing agent is not particularly limited. For example, a sizing treatment liquid prepared by dissolving (including dispersion) a sizing agent in a solvent (including a dispersion medium in the case of dispersion) is prepared. In general, the sizing agent is applied to the reinforcing fiber by drying and vaporizing the solvent and removing the solvent after applying to the reinforcing fiber. Examples of a method for applying the sizing treatment liquid to the reinforcing fiber include a method of immersing the reinforcing fiber in the sizing treatment liquid via a roller, a method of contacting the reinforcing fiber with the roller to which the sizing treatment liquid is attached, There is a method of spraying on the reinforcing fiber. Moreover, although either a batch type or a continuous type may be sufficient, the continuous type which has good productivity and small variations is preferable. At this time, it is preferable to control the sizing solution concentration, temperature, yarn tension, and the like so that the amount of the sizing agent active component attached to the reinforcing fiber is uniformly attached within an appropriate range. Moreover, it is more preferable to vibrate the reinforcing fiber bundle [B] with ultrasonic waves when applying the sizing agent.

  The drying temperature and drying time should be adjusted according to the amount of the compound attached, but the time required for complete removal of the solvent used to apply the sizing agent and drying is shortened, while the thermal deterioration of the sizing agent is prevented and sizing is performed. From the viewpoint of preventing the treated reinforcing fiber bundle [B] from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower, and 180 ° C. or higher and 250 ° C. or lower. More preferably.

  Examples of the solvent used in the sizing treatment liquid include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone, and the like, but water is preferable from the viewpoint of easy handling and disaster prevention. Therefore, when using a compound insoluble or hardly soluble in water as a sizing agent, it is preferable to add an emulsifier and a surfactant and disperse in water. Specifically, as an emulsifier and a surfactant, styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, anionic emulsifier such as sodium polyacrylate, Nonionic emulsifiers such as cationic emulsifiers such as polyethyleneimine and polyvinylimidazoline, nonylphenol ethylene oxide adducts, polyvinyl alcohol, polyoxyethylene ether ester copolymers, sorbitan ester ethyl oxide adducts, etc. can be used. A nonionic emulsifier having a small size is preferable because it hardly inhibits the adhesive effect of the functional group contained in the sizing agent.

  In the present invention, the epoxy resin [C] is highly compatible with the polycarbonate resin [A], which is a matrix resin, and has an effect of improving the dispersibility of the reinforcing fiber bundle [B] in the resin. Here, the epoxy resin [C] used in the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, aliphatic epoxy resins, and phenol novolac type epoxy resins. Of these, bisphenol A type epoxy resins and bisphenol F type epoxy resins are more preferable, and bisphenol A type epoxy resins are more preferable from the viewpoint of excellent balance between viscosity and heat resistance. It is preferable to use such a resin because it is easy to be familiar with and impregnated with the reinforcing fibers, and the dispersibility of the reinforcing fiber bundle [B] in the polycarbonate resin [A] is easily improved.

  Moreover, in this invention, although the melt viscosity of epoxy resin [C] is not specifically limited, Preferably, the melt viscosity in 200 degreeC is 0.01-10 Pa.s. If the melt viscosity at 200 ° C. is 0.01 Pa · s or more, the fracture starting from the epoxy resin [C] can be reduced, and the mechanical properties of the molded product can be further improved. 0.05 Pa · s or more is more preferable, and 0.1 Pa · s or more is more preferable. On the other hand, when the melt viscosity at 200 ° C. is 10 Pa · s or less, the epoxy resin [C] is easily impregnated into the reinforcing fiber bundle [B]. Therefore, when the resin-impregnated reinforcing fiber [D] obtained in the present invention is used for molding or kneading, the epoxy resin [C] is converted into the polycarbonate resin [A], the reinforcing fiber bundle [B] and the epoxy resin [C]. C] can easily flow and move in the mixture, so that the dispersibility of the reinforcing fibers can be further improved. 5 Pa · s or less is more preferable, and 2 Pa · s or less is more preferable.

  As will be described later, when the reinforcing fiber bundle [B] is melt-impregnated with the epoxy resin [C] to form the resin-impregnated reinforcing fiber [D], the melting temperature (melting) when supplying the epoxy resin [C] The temperature in the bath is preferably 100 to 300 ° C. Therefore, in the present invention, attention was paid to the melt viscosity at 200 ° C. of the epoxy resin [C] as an index of the impregnation property of the epoxy resin [C] into the reinforcing fiber [B]. If the melt viscosity at 200 ° C. is in the above preferred range, in such a preferred melt temperature range, the impregnation property of the reinforcing fiber [B] is excellent, so that the dispersibility of the reinforcing fiber is further improved and the mechanical properties of the molded product are improved. It can be improved further.

In the present invention, the epoxy resin [C] preferably has a melt viscosity change rate of 2% or less after heating at 200 ° C. for 2 hours. Here, the melt viscosity change rate is obtained from the following equation.
(Change rate of melt viscosity) [%] = {(melt viscosity at 200 ° C. after heating at 200 ° C. for 2 hours) / (melt viscosity at 200 ° C. before heating at 200 ° C. for 2 hours)} × 100
As described above, when the reinforcing fiber bundle [B] is melt-impregnated with the epoxy resin [C] to form the resin-impregnated reinforcing fiber [D], the melting temperature when supplying the epoxy resin [C] (in the melting bath) Is preferably 100 to 300 ° C. Therefore, by making the rate of change in melt viscosity 2% or less, even when the resin-impregnated reinforcing fiber [D] is produced over a long period of time, uneven adhesion is suppressed and the resin-impregnated reinforcing fiber [D] is stabilized. Manufacturing can be secured. The rate of change in melt viscosity is more preferably 1.5% or less, still more preferably 1.3% or less.

  The melt viscosity of the epoxy resin [C] can be determined by measurement using a viscoelasticity measuring device under conditions of 0.5 Hz and 200 ° C. using a 40 mm parallel plate. When calculating the rate of change in melt viscosity, the epoxy resin [C] is allowed to stand for 2 hours in a hot air dryer at 200 ° C., and then the melt viscosity measurement is similarly performed and calculated.

  In addition, the epoxy resin [C] preferably has a heating loss at 300 ° C. of 10 ° C./min (in air) of 5% by weight or less. When the loss on heating is 5% by weight or less, generation of decomposition gas during impregnation can be suppressed, and generation of voids inside the resin-impregnated reinforcing fiber [D] can be suppressed. Moreover, at the time of shaping | molding using the resin impregnated reinforcement fiber [D] obtained, a volatile matter can be reduced and the defect originating in the volatile matter inside a molded article can be suppressed. More preferably, it is 3% by weight or less.

In the present invention, “weight loss on heating” refers to the weight loss rate of the epoxy resin [C] before and after heating under the above heating conditions, where the weight of the epoxy resin [C] before heating is 100%. Can be sought.
(Weight loss on heating) [wt%] = {(weight before heating−weight after heating) / weight before heating} × 100

  Moreover, it is preferable that the epoxy equivalent of epoxy resin [C] is 300-3000 g / eq. When the epoxy equivalent is 300 g / eq or more, the reactivity is moderately suppressed, and the fiber dispersibility is further improved by suppressing the self-reaction and the reaction with the reinforcing fiber bundle [B] and the polycarbonate resin [A] during the molding process. Can be made. 500 g / eq or more is more preferable, and 800 g / eq or more is more preferable. On the other hand, when the epoxy equivalent is 3000 g / eq or less, the fiber dispersibility can be further improved during the molding process because it is easy to become familiar with and impregnated with the reinforcing fiber during the impregnation due to the interaction with the reinforcing fiber bundle. 2000 g / eq or less is more preferable, and 1500 g / eq or less is more preferable. In addition, the epoxy equivalent of epoxy resin [C] can be calculated | required based on JISK7236 test method.

  Moreover, it is preferable that the number average molecular weights of epoxy resin [C] are 500-5000. If the number average molecular weight is 500 or more, the mechanical properties of the molded product can be further improved. 800 or more is more preferable, and 1000 or more is more preferable. On the other hand, if the number average molecular weight is 5000 or less, the impregnation property can be further improved. 3000 or less is more preferable, and 2000 or less is more preferable. When the resin impregnated reinforcing fiber [D] in the present invention is used for molding or kneading, the epoxy resin [C] is made to have a number average molecular weight of 500 to 5,000 so that the epoxy resin [C] is a polycarbonate resin [C]. A], the reinforcing fiber bundle [B] and the epoxy resin [C] are more easily flowed and moved in the mixture. Furthermore, by setting the number average molecular weight of the epoxy resin [C] within such a range, the melt viscosity change rate and the heat loss of the epoxy resin [C] can be set within the above-mentioned preferable ranges, respectively. In addition, the number average molecular weight of epoxy resin [C] can be measured using a gel permeation chromatography (GPC).

  The reinforcing fiber bundle [B] is melt-impregnated with the epoxy resin [C] to form a resin-impregnated reinforcing fiber [D].

  In the present invention, the method for obtaining the resin-impregnated reinforcing fiber [D] by melt-impregnating the reinforcing fiber bundle [B] with the epoxy resin [C] is not particularly limited. C], the step (I) of bringing the epoxy resin [C] into contact with the reinforcing fiber bundle [B] in a molten state at 100 to 300 ° C., and the reinforcing fiber bundle [B] in contact with the epoxy resin [C] And the like, a method having a step (II) of impregnating by heating.

  In the step (I), the method of supplying the epoxy resin [C] and bringing it into contact with the reinforcing fiber bundle [B] is not particularly limited. For example, when an oil agent, a sizing agent, or a matrix resin is applied to the reinforcing fiber bundle. Any known method used can be used. Of these, dipping or coating is preferably used.

  Here, dipping refers to a method in which the epoxy resin [C] is supplied to the melting bath by a pump and the reinforcing fiber bundle [B] is passed through the melting bath. By immersing the reinforcing fiber bundle [B] in the molten bath of the epoxy resin [C], the epoxy resin [C] can be reliably attached to the reinforcing fiber bundle [B]. Further, the coating refers to a method of applying the epoxy resin [C] to the reinforcing fiber bundle [B] using a coating means such as a reverse roll, a normal rotation roll, a kiss roll, a spray, or a curtain. Here, the reverse roll, the forward rotation roll, and the kiss roll are a method in which an epoxy resin [C] melted by a pump is supplied to the roll and a melt of the epoxy resin [C] is applied to the reinforcing fiber bundle [B]. Say. Furthermore, the reverse roll is a method in which two rolls are rotated in opposite directions and a molten epoxy resin [C] is applied onto the roll. The forward roll is a roll in which the two rolls are rotated in the same direction. In this method, the molten epoxy resin [C] is applied onto a roll. Usually, in the reverse roll and the forward rotation roll, a method is used in which the reinforcing fiber bundle [B] is sandwiched, a roll is further installed, and the epoxy resin [C] is securely attached. On the other hand, the kiss roll is a method in which the epoxy resin [C] is adhered only by the contact between the reinforcing fiber bundle [B] and the roll. Therefore, the kiss roll is preferably used when the viscosity is relatively low, but with any roll method, a predetermined amount of the heated and melted epoxy resin [C] is applied and the reinforcing fiber bundle [B] is adhered. By running, a predetermined amount of epoxy resin [C] can be attached per unit length of the fiber bundle. The spray is a method that uses the principle of spraying, and is a method in which the molten epoxy resin [C] is sprayed onto the reinforcing fiber bundle [B] and the curtain is used to spray the molten epoxy resin [C] from a small hole. It is a method of applying by dropping naturally or a method of applying by dropping from a melting tank. Since it is easy to adjust the amount required for coating, loss of the epoxy resin [C] can be reduced.

  Moreover, as for the melting temperature (temperature in a fusion bath) at the time of supplying epoxy resin [C], 100-300 degreeC is preferable. If it is 100 degreeC or more, the viscosity of epoxy resin [C] can be suppressed moderately and adhesion nonuniformity can be suppressed. 150 degreeC or more is more preferable. On the other hand, if it is 300 degrees C or less, even when it manufactures over a long time, thermal decomposition of epoxy resin [C] can be suppressed. 250 degrees C or less is more preferable. The epoxy resin [C] can be stably supplied by contacting with the reinforcing fiber bundle [B] in a molten state at 100 to 300 ° C.

  Next, the step of heating and impregnating the reinforcing fiber bundle [B] in contact with the epoxy resin [C] obtained in the step (I) (step (II)) will be described. Specifically, for the reinforcing fiber bundle [B] in contact with the epoxy resin [C], at a temperature at which the epoxy resin [C] melts, tension is applied with a roll or bar, and widening and focusing are repeated. In this step, the epoxy resin [C] is impregnated into the reinforcing fiber bundle [B] by an operation such as applying pressure or vibration. As a more specific example, a method of performing widening by passing the reinforcing fiber bundle [B] in contact with the surface of a plurality of heated rolls and bars can be mentioned. A method of impregnation using a roll press or a double belt press is preferably used. Here, the squeezing base is a base whose diameter decreases toward the traveling direction, and at the same time scraping off the excessively adhered epoxy resin [C] while focusing the reinforcing fiber bundle [B], A base that promotes impregnation. The squeezing roll is a roller that promotes impregnation at the same time as scraping off the excessively adhered epoxy resin [C] by applying tension to the reinforcing fiber bundle [B] with a roller. The roll press is a device that continuously removes the air inside the reinforcing fiber bundle [B] by the pressure between the two rolls, and at the same time promotes impregnation. The double belt press refers to the reinforcing fiber bundle [B]. It is a device that promotes impregnation by pressing from above and below via a belt.

  In the step (II), it is preferable that 80 to 100% by weight of the supply amount of the epoxy resin [C] is impregnated in the reinforcing fiber bundle [B]. Since the yield is directly affected, the higher the amount of impregnation with respect to the supply amount, the better from the viewpoint of economy and productivity. More preferably, it is 85-100 weight%, More preferably, it is 90-100 weight%. Moreover, if it is 80 weight% or more, in addition to economical viewpoint, generation | occurrence | production of the volatile component resulting from the epoxy resin [C] in process (II) will be suppressed, and void generation | occurrence | production inside resin-impregnated reinforcement fiber [D] will be generated. Can be suppressed.

  Moreover, in process (II), it is preferable that the maximum temperature of epoxy resin [C] is 150-400 degreeC. When the maximum temperature is 150 ° C. or higher, the epoxy resin [C] can be sufficiently melted and impregnated more effectively. 180 degreeC or more is more preferable, and 200 degreeC or more is further more preferable. On the other hand, if the maximum temperature is 400 ° C. or lower, an undesirable side reaction such as a decomposition reaction of the epoxy resin [C] can be suppressed. 380 ° C. or lower is more preferable, and 350 ° C. or lower is further preferable.

  Although it does not specifically limit as a heating method in process (II), Specifically, the method of using a heated chamber, the method of performing a heating and pressurization simultaneously using a hot roller, etc. can be illustrated.

  Moreover, it is preferable to heat in non-oxidizing atmosphere from a viewpoint of suppressing generation | occurrence | production of undesirable side reactions, such as a crosslinking reaction and a decomposition reaction of epoxy resin [C]. Here, the non-oxidizing atmosphere is an atmosphere having an oxygen concentration of 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas atmosphere such as nitrogen, helium or argon. Of these, a nitrogen atmosphere is particularly preferred from the standpoints of economy and ease of handling.

In addition, the reinforcing fiber bundle [B] may be opened in advance before the steps (I) and (II). Opening is an operation for dividing the converged reinforcing fiber bundle [B], and an effect of further improving the impregnation property of the epoxy resin [C] can be expected. As a result of opening, the thickness of the reinforcing fiber bundle [B] is reduced, the width of the reinforcing fiber bundle [B] before opening is b ₁ (mm), the thickness is a ₁ (μm), and the components after opening (A ) Is b ₂ (mm) and the thickness is a ₂ (μm), it is preferable that the fiber opening ratio = (b ₂ / a ₂ ) / (b ₁ / a ₁ ) is 2.0 or more. And more preferably 2.5 or more.

  The method for opening the reinforcing fiber bundle [B] is not particularly limited. For example, a method of alternately passing uneven rolls, a method of using a drum-type roll, a method of applying tension fluctuation to axial vibration, and a reciprocating motion vertically. For example, a method of changing the tension of the reinforcing fiber bundle [B] by the two friction bodies, a method of blowing air to the reinforcing fiber bundle [B], and the like can be used.

  FIG. 1 is a schematic view showing an example of a cross-sectional form of a resin-impregnated reinforcing fiber [D] in the present invention. In the present invention, the transverse section means a section in a plane orthogonal to the axial direction. The resin-impregnated reinforcing fiber [D] used in the present invention is formed as a composite in which the reinforcing fiber bundle [B] is melt-impregnated with the epoxy resin [C] (hereinafter, the resin-impregnated reinforcing fiber [D] is combined). Also called the body). The form of this composite is as shown in FIG. 1, and the epoxy resin [C] 2 is filled between the single fibers 1 of the reinforcing fiber bundle [B]. That is, each single fiber 1 of the reinforcing fiber bundle [B] is dispersed like islands in the sea of the epoxy resin [C] 2.

  In the above composite, by making a composite in which the reinforcing fiber bundle [B] is satisfactorily impregnated with the epoxy resin [C], for example, when injection molding is performed together with the polycarbonate resin [A], it is melt-kneaded in a cylinder of an injection molding machine. The epoxy resin [C] thus diffused into the polycarbonate resin [A] helps to disperse the reinforcing fiber bundle [B] into the polycarbonate resin [A], and simultaneously diffuses into the polycarbonate resin [A] and the polycarbonate resin [A]. ] In the reinforcing fiber bundle [B] and has a role as a so-called impregnation aid / dispersion aid that helps the polycarbonate resin [A] penetrate into and impregnate the reinforcing fiber bundle [B].

  The weight ratio ([B] / [C]) of the reinforcing fiber bundle [B] and the epoxy resin [C] contained in the composite is 87/13 to 50/50. When the weight ratio of the reinforcing fiber bundle [B] and the epoxy resin [C] is less than 50 and the weight ratio of the epoxy resin [C] exceeds 50, the resulting molded product is obtained. The mechanical properties of are insufficient. Moreover, the flame retardance which polycarbonate resin originally has may be reduced. The weight ratio of the reinforcing fiber bundle [B] is preferably 60 or more, and the weight ratio of the epoxy resin [C] is preferably 40 or less, the weight ratio of the reinforcing fiber bundle [B] is 70 or more, and the weight of the epoxy resin [C]. The ratio is more preferably 30 or less. On the other hand, when the weight ratio of the reinforcing fiber [B] is more than 87 and the weight ratio of the epoxy resin [C] is less than 13, it is dispersible with respect to the polycarbonate resin [A] and flows during molding such as injection molding. Sex is reduced. The weight ratio of the reinforcing fiber bundle [B] is preferably 85 or less, the weight ratio of the epoxy resin [C] is preferably 15 or more, the weight ratio of the reinforcing fiber bundle [B] is 83 or more, and the weight of the epoxy resin [C]. The ratio is more preferably 17 or more.

  Here, when an epoxy resin is applied as a sizing agent to the reinforcing fiber [B], the epoxy resin [C] does not include an epoxy resin as a sizing agent, and the entire reinforcing fiber to which the sizing agent is applied is reinforced fiber. From the viewpoint of manifestation of interfacial adhesion and fiber dispersibility, it is preferable to obtain a composite by melting and impregnating the epoxy resin [C] so that the weight ratio is the bundle [B].

  Moreover, when a sizing agent is provided to the reinforcing fiber bundle [B], the weight ratio between the sizing agent and the epoxy resin [C] is preferably 0.001 to 0.5 / 1. More preferably, it is 0.005-0.1 / 1, More preferably, it is 0.01-0.05 / 1. It is preferable to use each component within such a range because the interfacial adhesion, fiber dispersibility, and mechanical properties can be improved in a more balanced manner.

  Further, the reinforcing fiber bundle [B] may be melt impregnated with the epoxy resin [C] with another additive as long as the object of the present invention is not impaired. Examples of additives include the flame retardant [F] and conductive filler [G] described below, the above-mentioned polycarbonate resin [A], a styrene-based resin described later, an olefin, and an alkyl (meth) acrylate. Thermosetting resins and thermoplastic resins other than the copolymer [E], inorganic fillers, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insecticides, deodorants, and coloring inhibitors , Heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, coupling agents and the like. At this time, the weight ratio of the reinforcing fiber bundle [B] and the epoxy resin [C] contained in the composite is preferably maintained within the above range.

In the composite, it is desirable that the reinforcing fiber bundle [B] is completely impregnated with the epoxy resin [C]. However, in reality, this is difficult, and the composite has a certain amount of voids (reinforcing fiber bundles). There is a portion where neither [B] nor epoxy resin [C] exists. In particular, when the content of the reinforcing fiber bundle [B] is large, the number of voids increases, but even when a certain amount of voids exist, the effect of promoting impregnation and fiber dispersion of the present invention is shown. From the viewpoint of further improving the impregnation / fiber dispersion promoting effect, the porosity is preferably less than 40%. A more preferable range of the porosity is 20% or less. The porosity is measured by measuring the composite according to the ASTM D2734 (1997) test method, or in the cross section of the composite, the total area of the composite portion formed by the reinforcing fiber bundle [B] and the epoxy resin [C] and the void It can be calculated using the following formula from the total area of the part.
(Void ratio) [%] = {(total area of the void) / (total area of the composite portion + total area of the void)} × 100

  Furthermore, the smaller the volatile content of the obtained composite, the smaller the volatile content during molding, which is preferable. The weight loss rate after drying at 200 ° C. for 2 hours is preferably less than 5%, more preferably less than 3%, and even more preferably less than 1%. For example, it is preferable that the volatile content of the composite is increased by setting the adhesion amount of the sizing agent applied to the reinforcing fiber [B], the drying temperature, and the heating loss of the impregnated epoxy resin [C] within the above-described preferable range. Can range.

  In the present invention, the resin-impregnated reinforcing fiber [D] contained in the polycarbonate resin molding material is 10 to 250 parts by weight with respect to 100 parts by weight of the polycarbonate resin [A] constituting the polycarbonate resin molding material. When the resin-impregnated reinforcing fiber [D] is less than 5 parts by weight, the reinforcing effect by the reinforcing fiber cannot be obtained, and sufficient mechanical properties are not exhibited. 15 parts by weight or more is preferable. On the other hand, when the resin-impregnated reinforcing fiber [D] is more than 250 parts by weight, the fluidity at the time of molding is remarkably lowered, so that the dispersibility of the reinforcing fiber bundle [B] is lowered and a molded product may not be obtained. is there. Moreover, even when a molded product is obtained, fiber breakage is promoted by the collision and entanglement of the fibers, and sufficient mechanical properties are not exhibited. 200 parts by weight or less is preferable, and 150 parts by weight or less is more preferable. In the above preferred range, the content of the resin-impregnated reinforcing fiber [D] and other components can be adjusted so that the weight content Wf of the reinforcing fiber in the molded product is 3 to 40% by weight. From the viewpoint of the mechanical properties of the molded product and the balance of moldability, it is more preferable to adjust to 5 to 30% by weight.

  The polycarbonate resin molding material of the present invention further contains a styrene resin and / or a copolymer [E] of an olefin and a (meth) acrylic acid alkyl ester. The copolymer [E] of a styrene resin or olefin and an alkyl (meth) acrylate is dispersed in the polycarbonate resin [A], so that the flowability and impact characteristics of the matrix resin during molding are reduced. There is an effect of improving. Furthermore, in this invention, the effect which suppresses the fiber breakage of the reinforced fiber at the time of a shaping | molding expresses by including the copolymer [E] of a styrene resin and / or an olefin, and the (meth) acrylic-acid alkylester. I found out. Although the details of the cause of the effect are not clear, it is estimated as follows. That is, the reinforcing fiber bundle [B] impregnated with the epoxy resin [C] has excellent fiber dispersibility because the epoxy resin [C] has good compatibility with the polycarbonate resin [A] as described above. Here, the polycarbonate resin [A] present at the interface with the reinforcing fiber is compatible with the epoxy resin [C] and becomes a polycarbonate resin / epoxy resin mixed molten resin. On the other hand, the copolymer [E] of styrene resin or olefin and (meth) acrylic acid alkyl ester is finely dispersed in the polycarbonate resin [A], but the styrene resin or olefin and (meth) acrylic acid. Compared with the affinity between the copolymer [E] with the alkyl ester and the polycarbonate resin [A], the copolymer [E] with the styrene resin or olefin and the alkyl (meth) acrylate and the polycarbonate resin / epoxy Because of the higher affinity with the resin-mixed molten resin, the copolymer [E] of styrene resin or olefin and (meth) acrylic acid alkyl ester dispersed in the vicinity of the reinforcing fiber is the interface with the reinforcing fiber. It is thought that it has aggregated. At this time, a copolymer [E] of styrene resin or olefin and (meth) acrylic acid alkyl ester works as a lubricant, and in order to reduce the influence of shear between reinforcing fiber and polycarbonate resin, and friction between fibers, It is considered that a breakage suppressing effect is achieved. The effect of suppressing breakage of such reinforcing fibers is not manifested until the epoxy resin [C] and the styrene resin and / or the copolymer [E] of olefin and alkyl (meth) acrylate are aligned. When the epoxy resin [C] is not present, the dispersibility of the reinforcing fiber bundle [B] is lowered, and in addition, the copolymer [E of styrene resin or olefin and (meth) acrylic acid alkyl ester] ] Does not occur, it is presumed that the effect of suppressing breakage that reduces shear during molding and friction between fibers is not exhibited. Further, when the styrene resin and / or the copolymer [E] of olefin and (meth) acrylic acid alkyl ester is not present, a lubricant effect cannot be expected. These fiber breakage suppressing effects can be obtained when a styrene resin or a copolymer of olefin and (meth) acrylic acid alkyl ester is used as component [E], or when styrene resin, olefin and (meth) acrylic acid are used. It is expressed in any case where a copolymer with an alkyl ester is used in combination.

  The styrene resin in the present invention contains an aromatic vinyl monomer as a polymerization component, and is a copolymer of an aromatic vinyl monomer and another component copolymerizable therewith. May be. Examples of other components include vinyl monomers other than aromatics and rubber components. The mode of copolymerization is not particularly limited, and known ones can be used, and examples thereof include random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization. Two or more of these may be used in combination. Moreover, as a mode of the styrene resin, a single styrene resin may be used, but other components and the styrene resin may form a so-called core-shell structure. When forming the core-shell structure, a structure in which another resin is covered with a styrenic resin is preferable, and since the styrenic resin is present in the shell layer of the outer shell, the aggregation effect due to the above-mentioned affinity is exhibited, and the core The properties of the layer components can be expressed simultaneously.

  Specific examples of the aromatic vinyl monomer include, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o, p- Examples include dichlorostyrene. Two or more of these may be used in combination. In particular, styrene and α-methylstyrene are preferably used.

  In addition, it is preferable to copolymerize other vinyl monomers that can be copolymerized with the aromatic vinyl monomer, and by selecting a copolymer component, such as chemical resistance, heat resistance, impact resistance, etc. Desired characteristics can be further improved. Specific examples of other copolymerizable vinyl monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, ( N-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, chloromethyl (meth) acrylate, glycidyl (meth) acrylate, Examples thereof include maleic anhydride, itaconic anhydride, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like. Two or more of these may be used in combination. In particular, acrylonitrile is preferably used.

  More preferably, the styrenic resin includes a rubber-modified styrenic resin that is a copolymer of a rubber component copolymerizable with an aromatic vinyl monomer. Since the soft segment composed of the rubber component relaxes the external force applied to the reinforcing fiber during molding, a larger fiber breakage effect can be expected, and the impact resistance can be further improved. Specific examples of rubber components copolymerizable with aromatic vinyl monomers include polybutadiene rubber, styrene-butadiene copolymer, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene copolymer, butyl acrylate, Examples thereof include a butadiene copolymer and isoprene rubber. Two or more of these may be used in combination. Of these, diene rubbers such as polybutadiene and styrene-butadiene copolymer are preferred.

  Specific examples of the styrene resin include polystyrene (PS resin), high impact polystyrene (HIPS resin), styrene-acrylonitrile copolymer resin (AS resin), modified AS resin, acrylonitrile-acrylic acid ester-styrene copolymer. (AAS resin), acrylonitrile-ethylene-styrene copolymer (AES resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methacrylate-butadiene-styrene copolymer (MBS resin), styrene-butadiene copolymer Polymer (SBR resin), styrene-butadiene-styrene copolymer (SBS resin), styrene-ethylene-butylene-styrene copolymer (SEBS resin), styrene-isoprene-styrene copolymer (SIS resin), etc. It is done. From the viewpoint of further improving the impact resistance and the effect of suppressing breakage of the reinforcing fiber, MBS resin, SBS resin, and SEBS resin, which are rubber-modified styrene resins, are preferably used, and among them, SEBS resin is particularly preferable.

  Here, the SEBS resin is not particularly limited, but a hydrogenated block copolymer obtained by hydrogenating a styrene-butadiene block copolymer is more preferable. Examples of commercially available SEBS resins include “Tuftec” (registered trademark) manufactured by Asahi Kasei Chemicals Corporation, “Septon” (registered trademark) manufactured by Kuraray Co., Ltd., and “Clayton” manufactured by Kraton Polymer Japan Co., Ltd. ( Registered trademark).

  The copolymer of olefin and (meth) acrylic acid alkyl ester in the present invention is a copolymer of at least olefin and (meth) acrylic acid alkyl ester, and further copolymerized with other components. There may be. Copolymers of olefins and (meth) acrylic acid alkyl esters can be polymerized using various known polymerization methods that are generally known. For example, there is a method of radical polymerization of one or more olefins and one or more (meth) acrylic acid alkyl esters in the presence of a radical initiator. The form of the copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

  The olefin preferably has 1 to 8 carbon atoms, and specific examples thereof include ethylene, propylene, 1-butene, 1-pentene and the like. These may be used alone or in combination of two or more. Of these, ethylene is particularly preferred from the viewpoint of moldability and dispersibility.

  As the (meth) acrylic acid alkyl ester, an alkyl ester having 1 to 15 carbon atoms of (meth) acrylic acid is preferable, and specific examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, Alkyl acrylates such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t- Examples thereof include alkyl methacrylates such as butyl methacrylate, 2-ethylhexyl methacrylate and stearyl methacrylate. Among these, an alkyl ester having 1 to 10 carbon atoms of (meth) acrylic acid is preferable, and excellent dispersibility is easily exhibited during molding. An alkyl ester having 8 or less carbon atoms is more preferable, and an alkyl ester having 6 or less carbon atoms is more preferable. These may be used alone or in combination of two or more. Particularly preferred are methyl acrylate and ethyl acrylate.

  In the present invention, the styrene resin and / or the copolymer [E] of olefin and alkyl (meth) acrylate contained in the polycarbonate resin molding material is a polycarbonate resin [ A] It is 1-150 weight part with respect to 100 weight part. In addition, when it contains either a styrene resin or a copolymer of olefin and (meth) acrylic acid alkyl ester, the content of both styrene resin and olefin and (meth) acrylic acid alkyl ester When it contains, the total content needs to exist in the said range. If the copolymer [E] of the styrene resin and / or olefin and (meth) acrylic acid alkyl ester is less than 1 part by weight, a sufficient fiber breakage suppressing effect may not be obtained during molding. The impact resistance of the product is reduced. 3 parts by weight or more is preferable, and 5 parts by weight or more is more preferable. On the other hand, when the amount of the styrene resin and / or copolymer [E] of olefin and (meth) acrylic acid alkyl ester is more than 150 parts by weight, the rigidity and flame retardancy of the molded product are lowered. 80 parts by weight or less is preferable, and 50 parts by weight or less is more preferable.

  In the present invention, the styrene resin and / or the copolymer [E] of olefin and (meth) acrylic acid alkyl ester is contained as a polycarbonate resin molding material in any of the raw materials used during molding. From the viewpoint of efficiently expressing the effect of the styrene resin and / or the copolymer [E] of the olefin and the alkyl (meth) acrylate, the polycarbonate resin [A] and the styrene resin And / or a so-called polycarbonate resin composition in which a copolymer [E] of an olefin and an alkyl (meth) acrylate is melt-kneaded, is contained in the resin covering the resin-impregnated reinforcing fiber [D]. It is preferable. In the preferable range described above, the weight content of the styrene resin and / or the copolymer [E] of the olefin and the alkyl (meth) acrylate in the molded article is 1 to 40% by weight. Furthermore, it is preferable to adjust the content of each component from the balance of mechanical properties of the molded product and flame retardancy. More preferably, it is adjusted to 3 to 30% by weight, and more preferably 3 to 20% by weight.

  In this invention, when high flame retardance is required, it is preferable to contain a flame retardant [F] further. The content of the flame retardant [F] is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin [A] constituting the polycarbonate resin molding material. When the content of the flame retardant [F] is 1 part by weight or more, sufficient flame retardancy can be imparted to a molded product obtained from the polycarbonate resin molding material. On the other hand, if the content of the flame retardant [F] is 100 parts by weight or less, the mechanical properties of the molded product can be maintained at a higher level, and an increase in specific gravity can be suppressed. 50 parts by weight or less is more preferable, and 30 parts by weight or less is more preferable. In the above preferred range, adjusting the content of each component so that the weight content of the flame retardant [F] in the molded product is 1 to 40% by weight, From the balance of flame retardancy, it is preferable. More preferably, it is adjusted to 3 to 30% by weight, and more preferably 3 to 20% by weight.

  The flame retardant [F] used in the present invention is not particularly limited, and examples thereof include a halogen flame retardant, a phosphorus flame retardant, and a metal salt flame retardant. In the present invention, among these various flame retardants, the development of flame retardancy, the presence or absence of concern about the generation of toxic gases, the increase in specific gravity due to the addition of the flame retardant, the phase of the polycarbonate resin [A] and the flame retardant [F] From the viewpoint of solubility, it is more preferable to use a phosphorus-based flame retardant. Furthermore, when a phosphorus flame retardant is used, an effect of further improving the strength of the molded product may be seen. Although this cause is not clear, it is considered that the polycarbonate flame retardant [A], which is a matrix, is plasticized by the phosphorus-based flame retardant, thereby improving the elongation at break of the molded article and accompanyingly increasing the breaking stress. This effect is particularly remarkable in the range of the preferable content of the flame retardant [F] described above.

  Typical halogen flame retardants include decabromodiphenyl ether, tetrabromobisphenol A, tetrabromobisphenol S, 1,2-bis (2 ′, 3 ′, 4 ′, 5 ′, 6′-pentabromophenyl. ) Ethane, 1,2-bis (2,4,6-tribromophenoxy) ethane, 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, 2, 6- or 2,4-dibromophenol, brominated polystyrene, ethylenebistetrabromophthalimide, hexabromocyclododecane, hexabromobenzene, pentabromobenzyl acrylate, 2,2-bis [4 ′ (2 ″, 3 ″ -Dibromopropoxy)-, 3 ', 5'-dibromophenyl] -propane, bis (3,5-dibromo, 4-dibromopro Brominated flame retardants containing bromine-containing compounds such as xylphenyl) sulfone and tris (2,3-dibromopropyl) isocyanurate, chlorinated paraffin, chlorinated polyethylene, chlorinated polypropylene, perchloropentacyclodecane, dodecachlorododecahydrodi Examples include chlorine-based flame retardants including chlorine-containing compounds such as methanodibenzocyclooctene and dodecachlorooctahydrodimethanodibenzofuran. These may be used alone or in combination of two or more. Here, polycarbonate oligomers of tetrabromobisphenol A are particularly preferred from the viewpoint of thermal stability and balance of mechanical properties of the molded product. The halogen-based flame retardant decomposes in a molded article and exhibits flame retardancy by stabilizing active H radicals and OH radicals in a combustion field by a radical trap effect.

  Representative examples of phosphorus flame retardants include triphenyl phosphate, tricresyl phosphate, trimethyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and other aromatic phosphorus. Phosphate ester compounds such as acid esters, halogen-containing phosphate ester compounds such as trisdichloropropyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, condensed phosphate ester compounds, polyphosphates, red phosphorus compounds, etc. Can be mentioned. These may be used alone or in combination of two or more. The phosphorus-based flame retardant promotes dehydration carbonization to form a dense char on the surface of the molded article, blocks heat and oxygen, and prevents flame propagation. Moreover, flame retardance is expressed by stabilizing H radicals and OH radicals active in the combustion field by radical trap effect against radical chain reaction in thermal decomposition.

  As metal salt flame retardants, some inorganic salts typified by antimony trioxide and antimony pentoxide are used in combination with halogen flame retardants, which are used as flame retardant aids, and organic sulfonates. And organic alkali metal salts. When the former antimony oxide is used in combination with a halogen-based flame retardant, it exhibits flame retardancy due to the surface shielding effect of oxyhalide of antimony and the effect of preventing thermal decomposition reaction in the air layer. The latter organic alkali metal salt undergoes intermolecular transesterification and isomerization rearrangement reaction during combustion, and the polycarbonate molecules are diversified to promote carbonization and exhibit flame retardancy.

  In the present invention, when the flame retardant [F] is used, the flame retardant [F] may be contained as a polycarbonate resin molding material in any of the raw materials used during molding. Here, in this invention, when the preferable example contained in either of raw materials is specifically mentioned, what is called a polycarbonate resin composition formed by melt-kneading polycarbonate resin [A] and a flame retardant [F], for example. In the aspect of being included in the resin covering the resin-impregnated reinforcing fiber [D] together with the styrene resin [E], or in the step of obtaining the resin-impregnated reinforcing fiber [D], the reinforcing fiber bundle [B] Examples include an embodiment in which a flame retardant [F] is melt-impregnated together with an epoxy resin [C] and contained in the resin-impregnated reinforcing fiber [D]. Also, a molding material made of a so-called polycarbonate resin composition obtained by melting and kneading a resin impregnated reinforcing fiber [D] with a polycarbonate resin [A] and a polycarbonate resin [A] and a flame retardant [F]. An embodiment in which a polycarbonate resin molding material mixture is obtained by dry blending is also preferable because the amount of reinforcing fibers and flame retardant contained in the molded product can be easily adjusted before molding. Here, in the present invention, dry blending is different from melt-kneading, and means that the two materials are stirred and mixed at a temperature at which the resin component does not melt to make a substantially uniform state, mainly injection molding. It is preferably used when a pellet-shaped material is used during extrusion molding or the like.

  In this invention, it is preferable to contain a conductive filler [G] for the purpose of imparting conductivity. The conductive filler [G] in the present invention itself has conductivity, and can be improved in the conductive properties of the molded product by being dispersed in the molded product without impairing the effects of the present invention. If it is, it will not be specifically limited. Specifically, for example, carbon black, metal powder represented by gold, silver, nickel, copper, aluminum and the like, reinforcing fiber such as carbon fiber and conductive metal fiber, and the like can be given. From the viewpoint of further improving the dispersibility of the resin-impregnated reinforcing fiber [D] in the polycarbonate resin [A], the preferred form of the conductive filler [G] is a fine powder or a flaky granular solid. Carbon black is preferable from the viewpoint of the balance between the property improvement effect and the specific gravity. In the present invention, when a conductive fiber such as carbon fiber or metal fiber is used as the reinforcing fiber, the molded product exhibits conductivity, but the conductive filler [ G] is preferably used. In particular, in the present invention, the styrenic resin [E] may aggregate at the reinforcing fiber interface during molding, and a so-called conductive path formed by contact between the conductive fibers may be difficult to form. Therefore, even when a conductive fiber is used as the reinforcing fiber, it is more preferable to contain a conductive filler [G] when high conductivity is required.

  The content of the conductive filler [G] is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polycarbonate resin [A] constituting the polycarbonate resin molding material. If content of electroconductive filler [G] is 0.1 weight part or more, the electroconductivity improvement effect will fully express. On the other hand, if it is 20 parts by weight or less, the mechanical properties can be maintained at a higher level, and an increase in the specific gravity of the molded product can be suppressed. 10 parts by weight or less is more preferable, and 5 parts by weight or less is more preferable. Moreover, in said preferable range, it is shaping | molding to adjust content of each structural component so that the weight content rate which the electroconductive filler [G] in a molded article occupies may be 0.1 to 10 weight%. It is preferable from the balance of the mechanical properties of the product and the improvement of conductivity. More preferably, it is adjusted to 0.1 to 5% by weight, and more preferably 0.1 to 3% by weight.

  Next, the polycarbonate resin molding material in the present invention will be described in detail.

  In the present invention, the polycarbonate resin molding material preferably has a structure in which the resin-impregnated reinforcing fiber [D] (composite) is coated with at least the polycarbonate resin [A]. Here, in the present invention, the “coated structure” means that the composite obtained as described above is appropriately disposed and adhered to the polycarbonate resin [A]. A method of arranging the molten polycarbonate resin [A] in contact with the composite, and cooling and solidifying it is preferable. The method is not particularly limited, but more specifically, by using an extruder and a coating die for a wire coating method, the composite is continuously arranged so as to cover the polycarbonate resin [A]. And a method of arranging a film-like polycarbonate resin [A] melted by using an extruder and a T die from one side or both sides of a composite flattened by a roll or the like and integrating them by a roll or the like. it can.

  FIG. 2 is a schematic view showing an example of a preferred longitudinal sectional form of the polycarbonate resin molding material of the present invention. In the present invention, the longitudinal section means a section in a plane including the axial direction. As an example of the polycarbonate resin molding material of the present invention, as shown in FIG. 2, the individual fibers 1 of the reinforcing fiber bundle [B] are arranged substantially parallel to the axial direction of the molding material, and the reinforcing fiber bundle [B]. The length of is substantially the same as the length of the molding material.

  Here, “arranged substantially parallel” means that the long axis of the reinforcing fiber bundle [B] and the long axis of the polycarbonate resin molding material are oriented in the same direction. The angle formed between the axes is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. The “substantially the same length” means, for example, in a pellet-shaped molding material, the reinforcing fiber bundle [B] is cut in the middle of the pellet, or the reinforcing fiber bundle [B ] Is not substantially included. In particular, the amount of the reinforcing fiber bundle [B] shorter than the entire length of the pellet is not specified, but the content of the reinforcing fiber bundle [B] having a length of 50% or less of the total length of the pellet is 30% by mass or less. If it is, it is evaluated that the reinforcing fiber bundle [B] significantly shorter than the entire length of the pellet is substantially not contained. Furthermore, the content of the reinforcing fiber bundle [B] having a length of 50% or less of the total length of the pellet is preferably 20% by mass or less. In addition, pellet total length is the length of the reinforcing fiber bundle [B] orientation direction in a pellet. Since the reinforcing fiber bundle [B] has a length equivalent to that of the molding material, the reinforcing fiber length in the molded product can be increased, so that excellent mechanical properties can be obtained.

  3a, 4a, 5a, and 6a each schematically show an example of a longitudinal cross-sectional shape of the polycarbonate resin molding material of the present invention. FIGS. 3b, 4b, 5b, and 6b are respectively shown in FIGS. 1 schematically represents an example of a cross-sectional form of a polycarbonate resin molding material corresponding to the above.

  The cross-sectional form of the polycarbonate resin molding material is limited to that shown in the figure as long as the polycarbonate resin [A] is disposed so as to adhere to the composite composed of the reinforcing fiber bundle [B] and the epoxy resin [C]. However, preferably, as shown in the longitudinal cross-sectional forms of FIGS. 3a to 5a, a structure in which the composite body is a core material and is sandwiched between polycarbonate resins [A] is preferable.

  Moreover, as shown in the cross-sectional form of FIGS. 3b to 5b, a configuration in which the composite is disposed as a core structure and arranged in a core-sheath structure in which the periphery thereof is covered with a polycarbonate resin [A] is preferable. Moreover, when arrange | positioning so that a polycarbonate resin [A] may coat | cover the some composite_body | complex as shown in FIG. 7, the number of composite_body | complexes about 2-6 is desirable.

  The boundary between the composite and the polycarbonate resin [A] is bonded, and the polycarbonate resin [A] partially enters the composite near the boundary and is compatible with the epoxy resin [C] constituting the composite. It may be in such a state that it is impregnated in a reinforcing fiber.

  The polycarbonate resin molding material of the present invention is kneaded by a technique such as injection molding or press molding to form a molded product. From the viewpoint of the handling property of the molding material, it is preferable that the composite and the polycarbonate resin [A] are kept in the shape as described above without being separated while being bonded until molding is performed. The composite and the polycarbonate resin [A] are completely different in shape (size, aspect ratio), specific gravity, and mass, so they are classified at the time of transportation and handling of materials until molding, and at the time of material transfer in the molding process. If the arrangement of the core-sheath structure as illustrated in FIGS. 3b to 5b is used, the polycarbonate may be used. Resin [A] constrains the composite, and a stronger composite can be achieved. In addition, as to which of the core-sheath structure as illustrated in FIGS. 3b to 5b or the layered arrangement as illustrated in FIG. 6b is advantageous, it is easy to manufacture and handle the material. From the viewpoint of ease, a core-sheath structure is more preferable.

  The polycarbonate resin molding material of the present invention may be continuous as long as it has substantially the same cross-sectional shape in the axial direction, and depending on the molding method, a continuous material may be cut into a certain length. It may be. It is preferable that it is cut into a length in the range of 1 to 50 mm. By adjusting to such a length, the fluidity and handleability during molding can be sufficiently enhanced. A particularly preferred embodiment of the molding material cut into an appropriate length in this way can be exemplified by long fiber pellets for injection molding.

  Further, the polycarbonate resin molding material of the present invention can be used depending on the molding method even if it is continuous or long. For example, a thermoplastic yarn prepreg can be wound around a mandrel while heating to obtain a roll-shaped molded product. Examples of such molded products include liquefied natural gas tanks. Moreover, it is also possible to produce a unidirectional thermoplastic prepreg by heating and fusing a plurality of molding materials of the present invention in a continuous manner while keeping them continuous. Such a prepreg can be applied to fields where lightness, high strength, elastic modulus, and impact resistance are required, such as automobile members.

  In the present invention, the polycarbonate resin molding material does not necessarily need to be composed of a single molding material. In a mixture of several molding materials, mixing is performed so that the content of various components falls within the scope of the present invention. May be.

  In the present invention, preferable examples of the method for producing a polycarbonate resin molding material include: (i) resin impregnated reinforcement in which at least polycarbonate resin [A] and reinforcing fiber bundle [B] are melt impregnated with epoxy resin [C]. Molding material containing fiber [D] (referred to as blend component 1), and (ii) at least polycarbonate resin [A], styrene resin, and / or olefin and (meth) acrylic acid alkyl ester A method of dry blending a molding material (referred to as blend component 2) made of a resin composition obtained by melt-kneading the coalescence [E] so that the content of each component is in the above range can be mentioned.

  Here, a preferable mixing ratio of the blend components 1 and 2 is [blend component 1 / blend component 2] = 75/25 to 25/75 (weight ratio), more preferably 70/30 to 30/70, Preferably it is 67 / 33-33 / 67. By making the mixing ratio within this range, the reinforcing fiber bundle [B] and the styrene resin and / or the copolymer [E] composed of olefin and alkyl (meth) acrylate are more uniformly dispersed during molding. Can be made. In the polycarbonate resin molding material mixture obtained by dry blending in such a preferred range, the composition of blend components 1 and 2 is preferably adjusted so that the content of various components is within the preferred range.

  The molding method of the polycarbonate resin molding material obtained in the present invention is not particularly limited, and examples thereof include molding methods having excellent productivity such as injection molding, autoclave molding, press molding, filament winding molding, and stamping molding. A combination of these can also be used. It can also be applied to integrated molding such as insert molding and outsert molding. Furthermore, it is possible to utilize an adhesive method having excellent productivity such as a correction treatment by heating, heat welding, vibration welding, ultrasonic welding, etc. after molding.

  Examples of uses of molded products obtained by the above molding method include instrument panels, door beams, under covers, lamp housings, pedal housings, radiator supports, spare tire covers, front end and other various modules, cylinder head covers, bearing retainers, Automotive parts such as intake manifolds, pedals, parts and skins, landing gear pods, winglets, spoilers, edges, ladders, failings, ribs, and other aircraft related parts, parts and skins, tools such as monkeys, wrenches, Examples include home and office electrical product parts such as telephones, facsimiles, VTRs, copiers, televisions, microwave ovens, audio equipment, toiletries, laser discs (registered trademarks), refrigerators, and air conditioners. In addition, there are also housings used for personal computers, digital cameras, mobile phones, etc., and members for electrical and electronic devices such as keyboard supports that are members that support keyboards inside personal computers. It is done. In the present invention, when a carbon fiber having conductivity is used as the reinforcing fiber bundle [B], such a member for electrical / electronic equipment is more preferable because it imparts electromagnetic wave shielding properties.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the following Example does not limit this invention.

[Method for evaluating molded products]
(1) Fiber dispersibility of molded product A molded product of 80 mm x 80 mm (3 mm thickness) was molded, and the number of undispersed reinforcing fiber bundles present on the front and back surfaces was counted visually. Evaluation was performed on 50 molded articles, and fiber dispersibility was determined for the total number based on the following criteria (AC passed).
A: 1 or less of undispersed reinforcing fiber bundles B: 1 or more and less than 5 undispersed reinforcing fiber bundles C: 5 or more and less than 10 undispersed reinforcing fiber bundles D: 10 or more undispersed reinforcing fiber bundles .

(2) Fiber length in the molded product The center part of the molded ISO-type tensile dumbbell test piece is cut into 20 mm × 10 mm (4 mm thickness), ashed at 500 ° C. for 2 hours, and the carbon fiber in the test piece is taken out. It was. This carbon fiber was put into a beaker together with 3 L of water, and the carbon fiber was uniformly dispersed in water using an ultrasonic cleaner. 1 mL of dispersed water in which carbon fibers are uniformly dispersed with a dropper having a tip diameter of 8 mm was sucked and sampled in a petri dish having a 10 mm × 10 mm recess, and then dried. The carbon fibers after drying were observed with an optical microscope (50 to 200 times), and the length of 1000 randomly selected was measured. In each example, common reinforcing fibers are used, and the density and diameter of the reinforcing fibers are the same. Therefore, the weight average fiber length was calculated from the following formula.
Weight average fiber length = Σ (Mi ² × Ni) / Σ (Mi × Ni)
Mi: Fiber length (mm)
Ni: The number of fibers having a fiber length Mi.

(3) Bending strength / flexural modulus In accordance with ISO 178, the fulcrum distance is set to 64 mm using a three-point bending test jig (indenter radius 5 mm), and the bending strength and bending are tested under the test conditions of 2 mm / min. The elastic modulus was measured. As a testing machine, “Instron” (registered trademark) universal testing machine 5566 type (manufactured by Instron) was used.

(4) Charpy impact strength with notch Based on ISO179-1, the Charpy impact strength with a notch was measured using a 1.0 J hammer. In addition, the test piece used what shape | molded the 80 mm x 10 mm (4mm thickness) molded article, and gave the notch process of notch angle 45 degrees and depth 2mm based on ISO2818.

(5) Electromagnetic shielding properties Using an evaluation device manufactured by Microwave Factory, the electromagnetic shielding properties at a near electric field of 1 GHz were measured according to the KEC method. In addition, electromagnetic wave shielding property was computed by the following formula. For the test piece, a conductive paste (Dotite manufactured by Fujikura Kasei Co., Ltd.) was applied to four sides of a 150 mm × 150 mm (3 mm thick) square plate, and the conductive paste was sufficiently dried.
_{SE = 20 × logE 0 / E} X
SE: Electromagnetic shielding (dB)
E ₀ : Spatial electric field strength when there is no shielding material E _X : Spatial electric field strength when there is a shielding material

(6) Flame retardance A molded product (test piece) of 125 mm × 13 mm (3 mm thickness) was molded, and flame retardancy evaluation was performed in accordance with UL-94. Specifically, a burner flame was applied to the lower end of the vertically supported test piece and kept for 10 seconds, and then the burner flame was separated from the test piece. After the flame disappeared, the burner flame was applied again and the same operation was performed. The determination was made based on the flaming combustion duration after the completion of the first flame contact, the sum of the second flaming combustion duration and the flameless combustion duration, and the presence or absence of combustion fallen objects. The standards for each grade in UL94 are as follows.
V-0: The first and second flammable combustion durations are within 10 seconds each, and the total of the first and second flammable combustion durations of five test pieces is within 50 seconds. Second flammable combustion The total of the duration and the flameless combustion duration was within 30 seconds, and there were no burning fallen objects.
V-1: The first and second flammable combustion durations are more than 10 seconds each and within 30 seconds, and the total of the first and second flammable combustion durations of five test pieces is within 250 seconds. The total of the flammable combustion duration and the flameless combustion duration was more than 30 seconds and within 60 seconds, and there were no burning fallen objects.
V-2: First and second flammable combustion durations each exceeding 10 seconds within 30 seconds, and total of the first and second flammable combustion durations of five test pieces within 250 seconds The total of the flammable combustion duration and the flameless combustion duration was more than 30 seconds and within 60 seconds, and there were burning fallen objects.

(Reference Example 1) Production of carbon fiber Spinning, firing treatment and surface oxidation treatment were carried out from a copolymer mainly composed of polyacrylonitrile, the total number of single yarns was 24,000, the single fiber diameter was 7 μm, and the mass per unit length. A homogeneous carbon fiber having a specific gravity of 1.6 g / m, a specific gravity of 1.8 g / cm ³ and a surface oxygen concentration [O / C] of 0.12 was obtained. The carbon fiber had a strand tensile strength of 4880 MPa and a strand tensile modulus of 225 GPa.

Here, the surface oxygen concentration ratio was determined according to the following procedure by X-ray photoelectron spectroscopy using the carbon fiber after the surface oxidation treatment. First, the carbon fiber bundle was cut to 20 mm, spread and arranged on a copper sample support, and then A1Kα1 and 2 were used as X-ray sources, and the inside of the sample chamber was kept at 1 × 10 ⁻⁸ Torr. The kinetic energy value (KE) of the main peak of C _1s was adjusted to 1202 eV as a peak correction value associated with charging during measurement. C _1s peak area E. As a linear base line in the range of 1191 to 1205 eV. O _1s peak area E. As a linear base line in the range of 947 to 959 eV. The atomic ratio was calculated from the ratio of the O _1s peak area to the C _1s peak area using the sensitivity correction value unique to the apparatus. As an X-ray photoelectron spectroscopy apparatus, Kokusai Denki Co., Ltd. model ES-200 was used, and the sensitivity correction value was set to 1.74.

(Reference Example 2) Application of sizing agent A sizing solution in which polyglycerol polyglycidyl ether (epoxy equivalent: 140 g / eq) was dissolved in water so as to be 2% by weight was prepared as a sizing agent. A sizing agent was applied to the carbon fiber by a dipping method so as to be 0.0% by weight, followed by drying at 230 ° C.

Reference Example 3 Production of Resin-impregnated Reinforcing Fibers [D] and [d] A liquid film in which epoxy resin [C] or terpene phenol polymer [c] is heated and melted is formed on a roll heated to a coating temperature. I let you. A reverse roll was used to form a film having a constant thickness on the roll. An epoxy resin [C] or a terpene phenol polymer [c] was adhered by passing a continuous reinforcing fiber bundle [B] on the roll while contacting. Next, it passed between 5 sets of 50 mm diameter roll presses in a chamber heated to the impregnation temperature in a nitrogen atmosphere. By this operation, epoxy resin [C] or terpene phenol polymer [c] was impregnated into the reinforcing fiber bundle to form resin-impregnated reinforcing fiber [D] or [d] having a predetermined blending amount.

Reference Example 4 Production of Polycarbonate Resin Composition Using a TEX-30α twin screw extruder (screw diameter 30 mm, die diameter 5 mm, barrel temperature 290 ° C., screw rotation speed 150 rpm) manufactured by JSW, polycarbonate resin [A], Supply a dry blend of styrene resin [E] from the main hopper, discharge the molten resin from the die port while degassing from the downstream vacuum vent, cool the resulting strand, and cut it with a cutter. Thus, a melt-kneaded pellet of the polycarbonate resin composition was obtained.

[Raw materials]
・ Polycarbonate resin [A]
[A-1] An aromatic polycarbonate resin “Taflon” (registered trademark) A2600 (viscosity average molecular weight: 26500) having a carbonate ester structure of bisphenol A manufactured by Idemitsu Co., Ltd. was used.
・ Reinforcing fiber [B]
[B-1] Carbon fibers provided with a sizing agent obtained according to Reference Example 1 and Reference Example 2 were used.
-Epoxy resin [C], terpene phenol polymer [c]
[C-1] Bisphenol A type epoxy resin “jER1003” manufactured by Mitsubishi Chemical Corporation (melt viscosity: 0.5 Pa · s, loss on heating: 2%, epoxy equivalent: 700 g / eq, number average molecular weight: 1300, melt Viscosity change rate: 1.1%) was used.
[C-2] Bisphenol A type epoxy resin “jER1004AF” manufactured by Mitsubishi Chemical Corporation (melt viscosity: 1 Pa · s, loss on heating: 1%, epoxy equivalent: 900 g / eq, number average molecular weight: 1700, change in melt viscosity Rate: 1.1%).
[C-3] Bisphenol A type epoxy resin “jER1006FS” manufactured by Mitsubishi Chemical Corporation (melt viscosity: 9 Pa · s, loss on heating: 0.5%, epoxy equivalent: 1300 g / eq, number average molecular weight: 2300, melt Viscosity change rate: 1.1%) was used.
[C-4] Bisphenol F type epoxy resin “jER4005P” manufactured by Mitsubishi Chemical Corporation (melt viscosity: 0.9 Pa · s, loss on heating: 2%, epoxy equivalent: 1050 g / eq, number average molecular weight: 1800, melt Viscosity change rate: 1.2%).
[C-5] Terpene phenol polymer “YP90L” (non-epoxy resin) manufactured by Yasuhara Chemical Co., Ltd. was used.
・ Resin impregnated reinforcing fiber [D], [d]
[D-1] According to Reference Example 3, the resin-impregnated reinforcing fiber obtained by impregnating the component [B-1] with the component [C-1] at an application temperature of 150 ° C. and an impregnation temperature of 250 ° C. is used. It was.
[D-2] According to Reference Example 3, the resin-impregnated reinforcing fiber obtained by impregnating the component [B-1] with the component [C-2] at an application temperature of 150 ° C. and an impregnation temperature of 250 ° C. is used. It was.
[D-3] Resin-impregnated reinforcing fiber obtained by impregnating the above component [B-1] with the above component [C-3] at a coating temperature of 150 ° C. and an impregnation temperature of 250 ° C. according to Reference Example 3 was used. It was.
[D-4] According to Reference Example 3, the resin-impregnated reinforcing fiber obtained by impregnating the component [B-1] with the component [C-4] at an application temperature of 150 ° C. and an impregnation temperature of 250 ° C. is used. It was.
[D-5] According to Reference Example 3, the resin-impregnated reinforcing fiber obtained by impregnating the component [B-1] with the component [c-5] at an application temperature of 150 ° C. and an impregnation temperature of 250 ° C. is used. It was.
-Styrenic resin and / or copolymer [E], [e] consisting of olefin and (meth) acrylic acid alkyl ester
[E-1] Hydrogenated styrene / butadiene block copolymer (SEBS resin) “Tuftec” (registered trademark) M1913 manufactured by Asahi Kasei Chemicals Corporation was used.
[E-2] Hydrogenated styrene / butadiene block copolymer (SEBS resin) “Tuftec” M1943 manufactured by Asahi Kasei Chemicals Corporation was used.
[E-3] Kaneka Corporation MBS resin “Kane Ace” (registered trademark) M-511 was used.
[E-4] Acrylonitrile-styrene / silicone / acrylic core-shell type composite rubber “METABREN” (registered trademark) SRK200A manufactured by Mitsubishi Rayon Co., Ltd. was used.
[E-5] Ethylene / acrylic acid ester terpolymer "Elvalloy" (registered trademark) HP4051 manufactured by Mitsui DuPont Polychemical Co., Ltd. was used.
[E-6] Hydrogenated styrene / butadiene block copolymer (SEBS resin) “Tuftec” (registered trademark) M1913 manufactured by Asahi Kasei Chemicals Co., Ltd. and ethylene / acrylic acid ester 3D manufactured by Mitsui DuPont Polychemical Co., Ltd. A mixture of the copolymer “Elvalloy” (registered trademark) HP4051 at a weight ratio of 50/50 was used.
・ Flame retardant [F]
[F-1] A condensed phosphate ester flame retardant “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. was used.
[F-2] A mixture of brominated polycarbonate “Fireguard” (registered trademark) FG850012 by Teijin Chemicals Ltd. and antimony trioxide “FCP-AT3” by Suzuhiro Chemical Co., Ltd. 3 parts by weight is used. It was.
・ Conductive filler [G]
[G-1] Carbon black “# 3050B” manufactured by Mitsubishi Chemical Corporation was used.

(Example 1)
In the combination of the reinforcing fiber bundle [B] and the epoxy resin [C] shown in Table 1, the weight ratio [B] / [C] of the component [B] and the epoxy resin [C] is the value shown in the table. The impregnation amount was adjusted as described above, and a resin-impregnated reinforcing fiber [D] was obtained according to Reference Example 3.

  Next, according to Reference Example 4, a polycarbonate resin composition was obtained using a dry blend of polycarbonate resin [A] and styrene resin [E] shown in Table 1. At this time, the mixing ratio at the time of dry blending of each of the above components is the predetermined amount shown in Table 1 with respect to the blending amount of the above components [A] and [E] in the polycarbonate resin molding material and the weight content in the molded product. It adjusted so that it might become the value of.

  The resin-reinforced fiber [D] obtained above is a coating die for a wire coating method installed at the tip of a TEX-30α type twin screw extruder (screw diameter 30 mm, L / D = 32) The polycarbonate resin composition was discharged from the extruder into the die in a molten state, and continuously disposed so as to cover the periphery of the resin-impregnated reinforcing fiber [D]. Here, in the step of coating the periphery of the resin-impregnated reinforcing fiber [D] with the polycarbonate resin composition, the compounding amount of the resin-impregnated reinforcing fiber [D] in the polycarbonate resin molding material and the weight content of the reinforcing fiber in the molded product The discharge amount of the polycarbonate resin composition was adjusted so that the rate Wf was a predetermined value shown in Table 1. The obtained continuous molding material was cooled and then cut with a cutter to obtain a 7 mm long fiber pellet-shaped polycarbonate resin molding material.

  Using the SE75DUZ-C250 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., the obtained polycarbonate resin molding material in the form of long fiber pellets was injected for 10 seconds, holding pressure: molding lower limit pressure +10 MPa, holding pressure time: 10 A test piece for characteristic evaluation (molded product) was molded by injection molding under the conditions of second, cylinder temperature: 300 ° C., mold temperature: 80 ° C. The obtained test piece was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then evaluated according to the injection molded product evaluation method shown in the above (1) to (6). The evaluation results are summarized in Table 1.

(Example 2)
The resin impregnated reinforcing fiber [D] obtained in the same manner as in Example 1 was passed through a coating die for electric wire coating method installed at the tip of a TEX-30α type twin screw extruder of Nippon Steel Works, Ltd., and an extruder The polycarbonate resin [A] was melted and discharged into the die in a molten state, and continuously disposed so as to cover the periphery of the resin-impregnated reinforcing fiber [D]. At this time, the amount of the resin-impregnated reinforcing fiber [D] and the amount of the polycarbonate resin [A] and the resin-impregnated reinforcing fiber [D] in the obtained polycarbonate resin molding material are adjusted so that the weight ratio is 100/34. The discharge amount of A] was adjusted. The obtained continuous molding material was cooled and then cut with a cutter to obtain a 7 mm long fiber pellet-shaped polycarbonate resin molding material.

  Next, according to Reference Example 4, a polycarbonate resin composition was obtained using a dry blend of polycarbonate resin [A] and styrene resin [E] shown in Table 1. At this time, the blending ratio during dry blending was adjusted so that the weight ratio of the polycarbonate resin [A] and the styrene resin [E] in the polycarbonate resin composition was 100/26.

  The obtained polycarbonate resin molding material in the form of long fiber pellets and the above polycarbonate resin composition have the composition of polycarbonate resin [A], resin-impregnated reinforcing fiber [D], and styrene resin [E] as shown in Table 1. The mixture ratio was adjusted and dry blended, and a test piece for characteristic evaluation (molded product) was molded under the same conditions as in Example 1 using a SE75DUZ-C250 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. . The obtained test piece was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then evaluated according to the injection molded product evaluation method shown in the above (1) to (6). The evaluation results are summarized in Table 1.

(Examples 3 to 18, Comparative Examples 1 to 5, Comparative Examples 7 and 8)
The value shown in the table for the weight ratio [B] / [C] of the component [B] and the epoxy resin [C] in the combination of the reinforcing fiber bundle [B] and the epoxy resin [C] shown in Tables 1-3. The amount of impregnation was adjusted so that the resin-impregnated reinforcing fiber [D] was obtained in the same manner as in Example 1. Then, in Reference Example 4, the polycarbonate resin [A] shown in Tables 1 to 3, the styrenic resin, and In addition to the copolymer [E] composed of an olefin and an alkyl (meth) acrylate, a polycarbonate resin composition was obtained using a dry blend of a flame retardant [F]. In the same manner as in Example 1, a polycarbonate resin molding material in the form of long fiber pellets was obtained from the resin-impregnated reinforcing fiber [D] and the polycarbonate resin composition obtained here. Here, the mixing ratio of each component at the time of preparing the polycarbonate resin composition and the discharge amount of the polycarbonate resin composition were adjusted so that the composition of each component became the values shown in Tables 1 to 3.

  Using the SE75DUZ-C250 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a test piece for property evaluation (molded product) is molded under the same conditions as in Example 1 using the obtained polycarbonate resin molding material in the form of long fiber pellet did. The obtained test piece was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then evaluated according to the injection molded product evaluation method shown in the above (1) to (6). The evaluation results are summarized in Tables 1 to 3.

(Example 19)
After obtaining the resin-impregnated reinforcing fiber [D] in the same manner as in Example 1, in Reference Example 4, in addition to the polycarbonate resin [A] and the styrene resin [E] shown in Table 2, the flame retardant [F], A polycarbonate resin composition was obtained using a dry blend of conductive filler [G]. In the same manner as in Example 1, a polycarbonate resin molding material in the form of long fiber pellets was obtained from the resin-impregnated reinforcing fiber [D] and the polycarbonate resin composition obtained here. Here, the mixing ratio of each component at the time of preparing the polycarbonate resin composition and the discharge amount of the polycarbonate resin composition were adjusted so that the composition of each component became the value shown in Table 2.

  Using the SE75DUZ-C250 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a test piece for property evaluation (molded product) is molded under the same conditions as in Example 1 using the obtained polycarbonate resin molding material in the form of long fiber pellets. did. The obtained test piece was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then evaluated according to the injection molded product evaluation method shown in the above (1) to (6). The evaluation results are summarized in Table 2.

(Comparative Example 6)
After obtaining the resin-impregnated reinforcing fiber [D] in the same manner as in Example 1, the polycarbonate resin [A] and the flame retardant [F] shown in Table 3 were added without adding the styrenic resin [E] in Reference Example 4. A polycarbonate resin composition was obtained using the dry blend. In the same manner as in Example 1, a polycarbonate resin molding material in the form of long fiber pellets was obtained from the resin-impregnated reinforcing fiber [D] and the polycarbonate resin composition obtained here. Here, the mixing ratio of each component at the time of preparing the polycarbonate resin composition and the discharge amount of the polycarbonate resin composition were adjusted so that the composition of each component became the value shown in Table 3.

  Using the SE75DUZ-C250 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a test piece for property evaluation (molded product) is molded under the same conditions as in Example 1 using the obtained polycarbonate resin molding material in the form of long fiber pellets. did. The obtained test piece was allowed to stand in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours, and then evaluated according to the injection molded product evaluation method shown in the above (1) to (6). The evaluation results are summarized in Table 3.

  The materials of Examples 1 to 19 all showed excellent dispersibility, mechanical properties, and electromagnetic shielding properties. In particular, for the examples where the flame retardant [F] was added, the effect of improving flame retardancy could also be confirmed. What changed the kind of epoxy resin [C] like Examples 10-12, and the copolymer of a styrene resin and / or an olefin, and the (meth) acrylic-acid alkylester like Examples 13-17 [ The same excellent characteristics were exhibited for those obtained by changing the type of E] and those obtained by changing the type of flame retardant [F] as in Example 18. Moreover, as shown in Example 19, the improvement effect of the electromagnetic wave shielding property by addition of electroconductive filler [G] was also confirmed.

  On the other hand, in Comparative Example 1, since the epoxy resin [C] was not impregnated, the dispersibility of the reinforcing fiber bundle [B] was poor, and a molded product worthy of evaluation could not be obtained.

  In Comparative Example 2, since the impregnation amount of the epoxy resin [C] was small, the dispersibility of the reinforcing fiber bundle [B] was lowered. In Comparative Example 3, since the amount of the epoxy resin [C] impregnated was too large, the mechanical properties were lowered, and further, the viscosity of the matrix resin was lowered, so that drip was observed.

  In Comparative Example 4, the amount of the reinforcing fiber bundle [B] was small, so that sufficient mechanical properties were not expressed. In Comparative Example 5, the amount of the reinforcing fiber bundle [B] was too large, so The mold could not be filled sufficiently and a molded product could not be obtained.

  In Comparative Example 6, since the copolymer [E] of styrene resin or olefin and (meth) acrylic acid alkyl ester was not added, fiber breakage was observed, and sufficient impact strength was not exhibited. In No. 7, since there was too much quantity of styrene resin [E], the bending elastic modulus and the remarkable flame retardance were seen.

  In Comparative Example 8, since the terpene phenol polymer was used instead of the epoxy resin [C], the reinforcing fiber bundle [B] was not sufficiently dispersed, and satisfactory mechanical properties were not obtained.

  The polycarbonate resin molding material of the present invention has excellent dispersibility of reinforcing fibers in the polycarbonate resin at the time of molding and suppresses breakage of the reinforcing fibers, so that the molded product has excellent mechanical properties such as bending properties and impact resistance properties. Can be obtained and developed for various applications. It is particularly suitable for various parts / members such as electrical / electronic equipment, OA equipment, home appliances, automobile parts, internal members, and housings.

1: Each single fiber of reinforcing fiber bundle [B] 2: Epoxy resin [C]
3: Resin-impregnated reinforcing fiber [D]
4: Polycarbonate resin [A]

Claims (11)

With respect to 100 parts by weight of the polycarbonate resin [A], at least 10 to 250 parts by weight of the resin-impregnated reinforcing fiber [D] obtained by melt-impregnating the epoxy resin [C] into the reinforcing fiber bundle [B], and a styrenic resin, And / or a polycarbonate resin molding material containing 1 to 150 parts by weight of a copolymer [E] of an olefin and an alkyl (meth) acrylate, wherein the component [B] contained in the component [D] The component [C] has a weight ratio ([B] / [C]) of 87/13 to 50/50, and the component [D] is coated with a resin composition containing at least the component [A]. Polycarbonate resin molding material. The polycarbonate resin molding material according to claim 1, wherein the component [D] is coated with a polycarbonate resin composition obtained by melt-kneading at least the component [A] and the component [E]. The polycarbonate resin molding material of Claim 1 or 2 in which the said component [C] contains a bisphenol A type epoxy resin. The polycarbonate resin molding material in any one of Claims 1-3 in which the said component [E] contains a rubber modification styrene resin. The polycarbonate resin molding material according to claim 4, wherein the rubber-modified styrene resin includes a styrene-ethylene-butylene-styrene copolymer (SEBS resin). The polycarbonate resin molding material in any one of Claims 1-3 in which the said component [E] contains the copolymer of ethylene and an alkyl acrylate ester. The polycarbonate resin molding material according to any one of claims 1 to 6, further comprising 1 to 100 parts by weight of a flame retardant [F] with respect to 100 parts by weight of the component [A]. The polycarbonate resin molding material according to claim 7, wherein the component [F] contains a phosphorus-based flame retardant. The polycarbonate resin molding material according to any one of claims 1 to 8, further comprising 0.1 to 20 parts by weight of a conductive filler [G] with respect to 100 parts by weight of the component [A]. A dry blend of (i) a molding material comprising at least the component [A] and the component [D], and (ii) a molding material comprising at least the component [A] and the component [E]. The method for producing a polycarbonate resin molding material according to any one of 9. A molded article formed by molding the polycarbonate resin molding material according to claim 1.

Images