JP6303523B2 - Molding materials and molded products - Google Patents

Description

  The present invention relates to a molding material, and more specifically, a molded article that has good dispersibility of reinforcing fibers in a polycarbonate resin at the time of molding and can exhibit excellent flame retardancy and mechanical properties can be obtained. It relates to molding materials.

  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 polyparaphenylene benzoxazole (PBO) fibers, and 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.

  The thermoplastic resin used as a matrix is highly demanded of polycarbonate resin because of its excellent mechanical properties such as impact resistance and thermal stability, and it is widely used in various fields such as electrical and electronic equipment casings and automotive parts. It is used. Here, in applications such as electronic device casings, further improvements in mechanical properties and high flame retardance are required in accordance with demands for further weight reduction and thickness reduction. However, the flame retardancy may be lowered by blending reinforcing fibers for improving the mechanical properties.

  In Patent Document 1, a composite in which a thermoplastic polymer having a phenol group having a lower melt viscosity than a thermoplastic resin serving as a matrix resin is attached to a continuous reinforcing fiber bundle is in contact with the thermoplastic resin. By arranging, a molding material is proposed in which the dispersion of the reinforcing fiber bundle is excellent in the molded product. However, it is difficult to say that the case where the polycarbonate resin is used as the matrix resin is sufficient, and the examination on the flame retardancy is also insufficient.

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

JP 2001-131418 A

  In view of the problems of the prior art, the present invention provides a molding material that has good dispersibility of carbon fibers in a polycarbonate resin at the time of molding and can obtain a molded product that can exhibit excellent flame retardancy and mechanical properties. The purpose is to do.

In order to solve the above problems, the present invention has the following configuration. That is,
A molding material containing 100 parts by weight of the following components (A) to (D) in total, and (E) a resin-impregnated reinforcing fiber bundle in which the following component (B) is melt-impregnated into the following component (A): ) And the following component (D).
(A) Carbon fiber to which sizing agent containing epoxy resin is attached in the range of 0.01 to 3.0% by weight 5 to 35 parts by weight (B) 1 to 15 parts by weight of phenol resin (( B) has a melting point of 120 ° C. O-cresol novolac resin, exceeding 150 ° C. and below)
(C) Polycarbonate resin 30-89 parts by weight (D) Phosphorus flame retardant 5-20 parts by weight

  The molding material of the present invention has good dispersibility of carbon fibers in a polycarbonate resin during molding, and a molded product excellent in flame retardancy and mechanical properties can be obtained. The molded product molded using the 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 casings.

It is the schematic which shows an example of the cross-sectional form of the (E) resin impregnation reinforcing fiber bundle in this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable longitudinal cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention. It is the schematic which shows an example of the preferable cross-sectional form of the molding material of this invention.

  The present invention will be described in detail. The molding material of the present invention comprises (A) a carbon fiber to which a sizing agent containing an epoxy resin is attached in an amount of 0.01 to 3.0% by weight, (B) a phenol resin, (C) a polycarbonate resin, (D) Consists of phosphorus-based flame retardants. 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.

  First, the carbon fiber to which the sizing agent containing the epoxy resin (A) used in the present invention is attached in the range of 0.01 to 3.0% by weight will be described. By including carbon fibers that are lightweight and have excellent strength and elastic modulus, a molding material with improved mechanical properties can be obtained. Moreover, it becomes easy to become familiar with a component (B) or a component (C) because the sizing agent containing an epoxy resin has adhered to 0.01 to 3.0 weight%, and dispersion | distribution of the carbon fiber to the polycarbonate resin at the time of shaping | molding Can be improved.

  The carbon fiber is not particularly limited, but carbon fibers such as PAN, pitch, and rayon are preferable from the viewpoint of 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 conductivity, carbon fibers coated with a metal such as nickel, copper or ytterbium can also be used.

  Furthermore, the surface oxygen concentration ratio [O / C], which is the ratio of the number of atoms of oxygen (O) and carbon (C) on the carbon fiber surface measured by X-ray photoelectron spectroscopy, is 0.05 to 0.5. Those are preferred. When the surface oxygen concentration ratio is 0.05 or more, the functional group amount on the surface of the carbon fiber can be secured, and (C) a polycarbonate resin described later can be more firmly bonded. 0.08 or more is more preferable, and 0.1 or more is more preferable. Moreover, although there is no restriction | limiting in particular in the upper limit of surface oxygen concentration ratio, Generally it can be illustrated to 0.5 or less from the balance of the handleability of carbon fiber, and productivity. 0.4 or less is more preferable, and 0.2 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, after cutting the carbon fiber bundle from which the sizing agent and the like adhering to the carbon fiber surface with a solvent was cut to 20 mm and spreading and arranging on a copper sample support base, using A1Kα1,2 as the X-ray source, 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 carbon fibers is not particularly limited, but is preferably in the range of 1 to 20 μm and preferably in the range of 3 to 15 μm from the viewpoint of the mechanical properties and surface appearance of the obtained molded product. More preferred.

  Moreover, there is no restriction | limiting in particular in the number of single fibers, It can use within the range of 100-350,000, It is preferable to use within the range of 1,000-250,000 especially. In addition, according to the present invention, even a reinforcing fiber bundle having a large number of single fibers can be used in the range of 20,000 to 100,000 because a molding material having good fiber dispersibility at the time of injection molding can be obtained. It is more preferable from the viewpoint of productivity.

  In addition, the carbon fiber used in the present invention is provided with a sizing agent, which improves bundling, bending resistance and scratch resistance, and can suppress the occurrence of fluff and yarn breakage in a high-order processing step. Higher processability can also be improved as a so-called paste or bundling agent, which is preferable. Furthermore, 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.

  As a component of the sizing agent used in the present invention, an epoxy resin is preferable because (C) the adhesive property with the polycarbonate resin is easily exhibited.

  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 improving mechanical properties. In general, when an epoxy resin has a large number of epoxy groups, the crosslinking density after the crosslinking reaction is increased, and thus the structure tends to have a low toughness. However, since an aliphatic epoxy resin has a flexible skeleton, the crosslinking density is low. Even if it is high, it tends to be a tough structure. For this reason, when the aliphatic epoxy resin is interposed between the carbon fiber and the matrix resin, it is soft and difficult to peel off.

  Examples of the aliphatic epoxy resin include diglycidyl ether compounds and polyglycidyl ether compounds. Specific examples of the diglycidyl ether compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol di Examples thereof include glycidyl ether, polytetramethylene glycol diglycidyl ether, and polyalkylene glycol diglycidyl ether. Specific examples of the polyglycidyl ether compound include glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ethers, sorbitol polyglycidyl ethers, arabitol polyglycidyl ethers, trimethylolpropane polyglycidyl ethers. , Trimethylolpropane 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. These 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 adhesiveness.

  The adhesion amount of the sizing agent is preferably 0.01 to 3.0% by weight with respect to 100% by weight of the total mass of the sizing agent and carbon fiber. If it is less than 0.01% by weight, the effect of improving the adhesiveness is hardly exhibited, and the carbon fiber may be poorly bundled during production. 0.03% by weight or more is more preferable. On the other hand, if the adhesion amount exceeds 3.0% by weight, the physical properties of the matrix resin may be lowered. More preferred is 2.5% by weight or less.

  The means for applying the sizing agent is not particularly limited. For example, a sizing treatment solution in which the sizing agent is dissolved (including dispersion) in a solvent (including a dispersion medium in the case of dispersion) is prepared, and the treatment is performed. In general, a method of applying a sizing agent to carbon fiber by drying and vaporizing the solvent after removing the solution to the carbon fiber and removing it is generally used. Examples of the method of applying the sizing treatment liquid to the carbon fiber include, for example, a method of immersing the carbon fiber in the sizing treatment liquid via a roller, a method of contacting the carbon fiber with the roller to which the sizing treatment liquid is attached, and a sizing treatment liquid in a mist form There is a method of spraying on carbon 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 carbon fiber is uniformly attached within an appropriate range. Moreover, it is more preferable to vibrate the carbon fiber with ultrasonic waves when applying the sizing agent.

  The drying temperature and drying time should be adjusted according to the amount of sizing agent attached, but the complete removal of the solvent used to apply the sizing agent, shortening the time required for drying, while preventing thermal degradation of the sizing agent, From the viewpoint of preventing the sizing-treated carbon fibers 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 more preferably 180 ° C. or higher and 250 ° C. or lower.

  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 epoxy group contained in the sizing agent.

  The compounding amount of the carbon fiber (A) to which the sizing agent is adhered is 5 to 35 parts by weight with respect to 100 parts by weight of the total of the components (A) to (D). If it is less than 5 parts by weight, sufficient mechanical properties cannot be obtained. If it exceeds 35 parts by weight, fiber dispersibility during molding may be inferior, and fluidity and flame retardancy may be inferior.

  Next, in the present invention, the (B) phenol resin refers to a thermoplastic polymer having a phenol skeleton. Since the (B) phenol resin has a lower melt viscosity than the (C) polycarbonate resin, the fluidity can be improved during molding, and the dispersibility of the carbon fibers can be improved. Moreover, since it is radical-trapped by a phenol group, it is easy to improve a flame retardance. Furthermore, since the molding material of the present invention uses (B) a phenolic resin (A) resin impregnated reinforcing fiber bundle in which (A) carbon fiber is melt-impregnated, (B) the phenolic resin is (A) carbon fiber. It exists in the vicinity and can improve dispersibility and flame retardance more efficiently.

  The phenol skeleton may have a substituent, and may be cresol or naphthol. Specific examples of the (B) phenol resin include phenol novolak resins, o-cresol novolak resins, phenol aralkyl resins, naphthol novolak resins, and naphthol aralkyl resins. Among these, o-cresol novolac resin is excellent in the balance between heat resistance and handling properties such as melt viscosity, so that (E) the take-up speed of the resin-impregnated fiber bundle can be increased, and the flame retardancy can be maintained higher. Therefore, it is preferably used.

  Further, the melting point of the (B) phenol resin is not particularly limited, but it is preferably higher than 80 ° C. from the viewpoint of improving the heat resistance and handleability of the molding material and suppressing bleeding out during long-term storage of the molding material. More preferably, it is over 100 degreeC, and it is still more preferable over 120 degreeC. Although the upper limit of the melting point is not particularly limited, the molding material of the present invention uses (B) a resin-impregnated reinforcing fiber bundle in which (B) a phenol resin is melt-impregnated in the component (A). From the viewpoint, 200 ° C. or lower is preferable. More preferably, it is 180 degrees C or less, More preferably, it is 150 degrees C or less. By having a melting point of 120 to 150 ° C., the balance between heat resistance and handleability such as melt viscosity is excellent, so that (E) the take-up speed of the resin-impregnated fiber bundle can be increased and the flame retardancy can be maintained higher. Therefore, it is preferably used.

  In addition, melting | fusing point of (B) phenol resin can be calculated | required from DSC measurement. Specifically, it can be obtained from the value of the endothermic peak top measured under the condition of 40 ° C./minute temperature rise.

  The melt viscosity of the (B) phenol resin is not particularly limited, but (E) when obtaining a resin-impregnated reinforcing fiber bundle, it is easy to stably impregnate the inside of the carbon fiber bundle. From the viewpoint of easy flow to the resin, the melt viscosity at 190 ° C is preferably 0.1 to 100 Pa · s. If the melt viscosity of (B) phenolic resin at 190 ° C. is 0.1 Pa · s or more, the carbon fiber bundle can be stably impregnated by a general impregnation method. (E) Resin-impregnated fiber The take-up speed of the bundle can be increased. Moreover, since the viscosity difference with (C) polycarbonate resin is small, the fiber dispersibility at the time of injection molding can be improved more. 0.2 Pa · s or more is more preferable, and 0.5 Pa · s or more is more preferable. Moreover, if it is 10 Pa.s or less, the inside of a carbon fiber bundle can be easily impregnated, and the fiber dispersibility at the time of injection molding can be further improved. 10 Pa · s or less is more preferable, and 5 Pa · s or less is more preferable. Here, as an index of the melt viscosity of (E) the thermoplastic resin composition at the impregnation temperature, attention was focused on the melt viscosity at 190 ° C., but as described later, when (E) the thermoplastic resin composition is impregnated The temperature can be appropriately selected.

  (B) The melt viscosity of a phenol resin can be measured using a 40 mm parallel plate using a viscoelasticity measuring instrument under conditions of 0.5 Hz and 190 ° C.

  (B) The compounding quantity of a phenol resin is 1-15 weight part with respect to a total of 100 weight part of said component (A)-(D). If it is less than 1 part by weight, sufficient fluid dispersibility cannot be ensured due to poor fluidity, and flame retardancy may be poor. 2 parts by weight or more is preferable, and 3 parts by weight or more is more preferable. On the other hand, if it exceeds 15 parts by weight, flame retardancy may be inferior. 10 parts by weight or less is preferable, and 8 parts by weight or less is more preferable.

  Next, in the present invention, (C) polycarbonate resin is a polymer having a carbonate structure in the main chain, and examples thereof include aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and aromatic polycarbonate. Among thermoplastic resins, the polycarbonate resin is excellent in heat resistance, impact resistance and flame retardancy, and is amorphous, so that it has a low molding shrinkage and therefore has an excellent surface appearance. These may be used alone or in combination of two or more. In particular, 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 excellent impact resistance.

The viscosity average molecular weight (M _v ) of the (C) polycarbonate resin 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 bending strength and impact resistance. 15,000 or more is more preferable, and 25,000 or more is more preferable. Moreover, when the viscosity average molecular weight (M _v ) is 50,000 or less, it is preferable because the fluidity during molding is excellent and the moldability is high. It is more preferably 40,000 or less, and further preferably 35,000 or less.

Here, the viscosity average molecular weight (M _v ) of the (C) polycarbonate resin can be determined by the following method. First, from a solution obtained by dissolving 0.7 g of (C) polycarbonate resin in 100 ml of methylene chloride at 20 ° C., a specific viscosity (η _SP ) calculated by the following formula is obtained 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 _v ^0.83
c = 0.7.

  (C) The method for obtaining the polycarbonate resin 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, "Panlite" (registered trademark) manufactured by Teijin Chemicals Ltd., "Taflon" manufactured by Idemitsu Petrochemical Co., Ltd. "(Registered trademark)" etc. can be obtained and used.

  (C) As a compounding quantity of polycarbonate resin, it is 30-89 weight part with respect to a total of 100 weight part of said component (A)-(D). If it is less than 30 parts by weight, it may not flow during injection molding, which is not preferable. Moreover, when it exceeds 89 weight part, there are many ratios of (C) polycarbonate resin, mechanical characteristics may be insufficient, or a flame retardance may be insufficient.

  The molding material of the present invention contains (D) a phosphorus-based flame retardant. (D) The phosphorus-based flame retardant exhibits flame retardancy because a dense char is formed on the surface of the molded article due to the dehydration carbonization promoting action, blocking heat and oxygen and preventing flame propagation. (D) Phosphorus flame retardants include, for example, triphenyl phosphate, tricresyl phosphate, trimethyl phosphate, triethyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, and other aromatic phosphates And phosphoric acid ester compounds such as trisdichloropropyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, and other halogen-containing phosphoric acid ester compounds, condensed phosphoric acid ester compounds, polyphosphates, and red phosphorus compounds. . These may be used alone or in combination of two or more. Among them, the condensed phosphate ester compound has an excellent balance between heat resistance and flame retardancy, and its viscosity at the time of melting is lower than that of the (C) polycarbonate resin, so it can improve fluidity and help fiber dispersibility. Is preferable.

  The condensed phosphate ester compound is not particularly limited, and specific examples thereof include a reaction product of phosphorus oxychloride with a divalent phenol-based compound and phenol (or alkylphenol). More specifically, resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate and the like can be mentioned. Among them, bisphenol A bis-diphenyl phosphate is preferably used from the balance of flame retardancy and heat resistance, and specific examples thereof include “PX-200” manufactured by Daihachi Chemical Industry.

  (D) The compounding quantity of a phosphorus flame retardant is 5-20 weight part with respect to a total of 100 weight part of said component (A)-(D). If it is less than 5 parts by weight, sufficient flame retardancy may not be obtained when the molding material is molded. 7 parts by weight or more is preferable. On the other hand, if it exceeds 20 parts by weight, the mechanical properties of the obtained molded product may be inferior. 15 parts by weight or less is preferable.

  The molding material of the present invention may contain (F) a liquid crystalline resin and / or (G) a styrene resin in addition to the components (A) to (D), and can further improve flame retardancy.

  (F) Since the liquid crystalline resin forms a dense char on the surface of the molded product during combustion, the flame retardancy can be further improved. Furthermore, since the fluidity at the time of molding is excellent, the dispersibility of the carbon fiber is further improved, and the mechanical properties of the molded product can be further improved.

  The (F) liquid crystalline resin used in the present invention is a resin capable of forming an anisotropic molten phase, and examples thereof include liquid crystalline polyesters and liquid crystalline polyester amides. From the viewpoint of further improving the flame retardancy of the molded product, a wholly aromatic liquid crystalline polyester is preferable. Here, the wholly aromatic liquid crystalline polyester refers to those in which the structural units constituting the liquid crystalline polyester do not include aliphatic structural units and are all aromatic structural units.

  In the present invention, preferred liquid crystalline polyesters include, for example, a structural unit represented by the following formula (I) (hereinafter referred to as the structural unit (I)) and a structural unit represented by the following general formula (II) (hereinafter referred to as the structural unit (hereinafter referred to as structural unit)). , A structural unit (II)), a polyester comprising a structural unit represented by the following general formula (IV) (hereinafter referred to as structural unit (IV)), a structural unit (I), represented by the following formula (III) A structural unit (hereinafter referred to as structural unit (III)), a polyester composed of structural unit (IV), a structural unit (I), a structural unit (II), a structural unit (III), and a structural unit (IV). Examples include polyester. From the viewpoint of further improving the flame retardancy, structural unit (I), structural unit (II), polyester comprising structural unit (IV), structural unit (I), structural unit (II), structural unit (III), structure A polyester composed of the unit (IV) is more preferable, and a polyester composed of the structural unit (I), the structural unit (II), and the structural unit (IV) is more preferable.

(However, R ¹ in the general formula (II) represents one or more groups selected from the following (a) to (j), and R ² in the general formula (IV) represents the following (k) to (p And at least one group selected from the above formula (X) represents a hydrogen atom or a chlorine atom.

  The structural unit (I) is a structural unit generated from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-4,4. '-Dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'- A structural unit generated from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether, a structural unit (III) is a structural unit generated from ethylene glycol, a structural unit (IV) is terephthalic acid, isophthalic acid, 4, 4 '-Diphenyldicarboxylic acid, 2,6-naphthalene Rubonic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid Each of the structural units generated from one or more aromatic dicarboxylic acids selected from

Further, among these, it is particularly preferred that R ¹ is the above (a) and / or (c), and R ² is the above (k), (l) and / or (n).

  The amount of copolymerization of the structural units (I), (II), (III) and (IV) is arbitrary. However, the following copolymerization amount is preferable in order to further exhibit the characteristics of the present invention.

  That is, in the case of a copolymer composed of the structural units (I), (II), (III), and (IV), the total of the structural units (I) and (II) is the structural unit (I), (II ) And (III) is preferably 30 to 95 mol% from the viewpoint of heat resistance and moldability, and more preferably 40 to 90 mol%. Further, the structural unit (III) is preferably 5 to 70 mol% with respect to the total of the structural units (I), (II) and (III) from the viewpoint of long-term heat resistance, and 10 to 60 mol% is preferable. More preferred. The molar ratio [(I) / (II)] of the structural unit (I) to the structural unit (II) is preferably 75/25 to 95/5 from the viewpoint of the balance between heat resistance and moldability. More preferably, it is 78/22-93/7. The structural unit (IV) is preferably substantially equimolar to the total of the structural units (II) and (III).

  Moreover, in the case of the copolymer which does not contain the structural unit (III) and is composed of the structural units (I), (II) and (IV), the molar ratio of the structural unit (I) to the structural unit (II) [( I) / (II)] is preferably 75/25 to 95/5, more preferably 78/22 to 93/7, as described above. The structural unit (IV) is preferably substantially equimolar with the structural unit (II).

As for a copolymer which does not contain the structural unit (III) and is composed of the structural units (I), (II) and (IV), further preferred examples include that in the structural unit (II), R ¹ is the above (a). In the structural unit (IV), R ² is the above (k), including the structural unit II (which is the structural unit II ₁ ) and the above (c) (the structural unit II ₂ ). (Structural unit IV ₁ ) and (l) (Structural unit IV ₂ ) are included. Here, the structural unit (I) is a structural unit (I), the total of (II ₁₎ and (II _2), preferably 68 to 80 mol%. Further, the structural unit (II ₁ ) is preferably 55 to 75 mol% with respect to the total of the structural units (II ₁ ) and (II ₂ ). Further, the structural unit (IV ₁ ) is preferably 60 to 85 mol% with respect to the total of the structural units (IV ₁ ) and (IV ₂ ). Here, it is preferable that the total of the structural units (II ₁ ) and (II ₂ ) and the total of the structural units (IV ₁ ) and (IV ₂ ) are substantially equimolar.

  In the present invention, “substantially equimolar” means that the structural units constituting the polymer main chain excluding the terminal are equimolar. For this reason, the aspect which does not necessarily become equimolar when including the structural unit which comprises a terminal can satisfy the requirements of "substantially equimolar".

  The liquid crystalline polyester that can be preferably used includes aromatic dicarboxylic acids such as 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyldicarboxylic acid in addition to the components constituting the structural units (I) to (IV). Acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acid such as dodecanedioic acid, alicyclic dicarboxylic acid such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxy Aromatic diols such as diphenylsulfone, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxybenzophenone, 3,4′-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, Aliphatic diene such as neopentyl glycol , Cycloaliphatic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid Etc. can be further copolymerized within a range not impairing liquid crystallinity and flame retardancy.

  Here, although melting | fusing point of (F) liquid crystalline resin is not specifically limited, 220-350 degreeC is preferable, More preferably, it is 270 degreeC-340 degreeC.

  In addition, the melt viscosity of the (F) liquid crystalline resin is not particularly limited, but is preferably 1 to 200 Pa · s, more preferably 10 to 200 Pa · s, from the viewpoint of dispersibility in the (C) polycarbonate resin. Preferably, 10 to 100 Pa · s is more preferable. In the present invention, the melt viscosity of (F) liquid crystalline resin is measured by a Koka flow tester under the condition of (F) melting point of liquid crystalline resin + 10 ° C. and shear rate of 1,000 / sec. Value.

There is no restriction | limiting in particular in the manufacturing method of the said liquid crystalline polyester used in this invention, It can manufacture according to the well-known polyester polycondensation method. Specifically, for example, the following production method is preferable.
(1) Diacylated products of p-acetoxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid The method of manufacturing from a deacetic acid polycondensation reaction from.
(2) Reacting p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid with acetic anhydride. The method of producing by deacetic acid polycondensation reaction after acylating a phenolic hydroxyl group.
(3) Phenyl ester of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method of producing from a phenol decondensation polycondensation reaction.
(4) After reacting p-hydroxybenzoic acid and aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and the like with a predetermined amount of diphenyl carbonate to obtain diphenyl ester, 4,4 ′ -A method of adding an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone and producing it by dephenol polycondensation reaction.
(5) Manufactured by the method (1) or (2) in the presence of a polyester polymer such as polyethylene terephthalate, an oligomer, or a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate. how to.

  The polycondensation reaction of the liquid crystalline polyester proceeds even without catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate, sodium acetate, antimony trioxide, and magnesium metal can also be used as a catalyst.

  In this invention, when (F) liquid crystalline resin is included in a molding material, the content is 1-30 weight part with respect to 100 weight part of component (A)-(D). (F) If the compounding quantity of liquid crystalline resin is 1 weight part or more, the flame retardance of a molded article can be improved more. 3 parts by weight or more is more preferable, and 5 parts by weight or more is more preferable. On the other hand, if the content of (F) liquid crystalline resin is 30 parts by weight or less, the mechanical properties of the molded product can be maintained at a higher level. 25 parts by weight or less is more preferable, and 20 parts by weight or less is more preferable.

  In the present invention, (F) the liquid crystalline resin may be contained in any of the molding materials, but (C) the inclusion of the liquid crystalline resin in the molding material in a melt-kneaded form in the polycarbonate resin is stable. This is preferable because the obtained flame retardancy is obtained. Specifically, for example, it is preferably contained as a so-called polycarbonate resin composition obtained by melt-kneading (C) a polycarbonate resin and (F) a liquid crystalline resin.

  (G) Since the styrenic resin has an aromatic ring, it is easy to form char on the surface of the molded product during combustion. Further, since it can be copolymerized with various other components as will be described later, a flexible skeleton can be introduced and impact strength can be improved. For this reason, the balance between flame retardancy and impact resistance can be further improved.

  The (G) styrene resin in the present invention is obtained by polymerizing an aromatic vinyl monomer, and is a copolymer of the aromatic vinyl monomer and another component copolymerizable therewith. It may be a polymer. 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. In addition, as an aspect 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 a core-shell structure, a structure in which another resin is covered with a styrene resin is preferable, and since the styrene resin is present in the shell layer of the outer shell, the aggregation effect due to the above-described affinity is exhibited, and the core The properties of the layer components can be expressed simultaneously.

  Examples of aromatic vinyl monomers include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, and o, p-dichlorostyrene. Is mentioned. 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 carbon fiber at the time of 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., “Clayton” manufactured by Kraton Polymer Japan Co., Ltd. ( Registered trademark).

  In this invention, when (G) styrene resin is included in a molding material, it is preferable that the content is 1-15 weight part with respect to 100 weight part of component (A)-(D). (G) If content of a styrene-type resin is 1 weight part or more, the impact resistance characteristic of a molded article can be improved more. 2 parts by weight or more is more preferable, and 3 parts by weight or more is more preferable. On the other hand, if the content of (G) the styrene resin is 15 parts by weight or less, the flame retardancy of the molded product can be further improved. 12 parts by weight or less is more preferable, and 9 parts by weight or less is more preferable.

  In the present invention, (G) the styrenic resin may be contained in any of the molding materials, but (C) it is stable to be contained in the molding material in the form of being melt-kneaded in the polycarbonate resin. This is preferable because the obtained impact resistance characteristics can be obtained. Specifically, for example, it is preferably contained as a so-called polycarbonate resin composition obtained by melt-kneading (C) a polycarbonate resin and (G) a styrene resin.

  The molding material of the present invention may further contain other components as necessary.

  The molding material of the present invention comprises (E) a resin-impregnated reinforcing fiber bundle obtained by melt-impregnating the (B) phenol resin with the carbon fiber (A) to which the sizing agent is adhered, the (C) polycarbonate resin and the (D) It is coated with a phosphorus flame retardant. In the present invention, the method of obtaining the (E) resin-impregnated reinforcing fiber bundle by melt-impregnating the component (A) with the (B) phenol resin is not particularly limited, but the following methods can be exemplified.

  That is, the step (I) of supplying the component (A) with the (B) phenol resin and bringing the (B) phenol resin into contact with the component (A) in a molten state at 100 to 300 ° C., and (B) contacting with the phenol resin The method which has process (II) which heats and impregnates the component (A) currently performed is mentioned.

  Although it does not specifically limit in process (I), The well-known manufacturing method which provides an oil agent, a sizing agent, and matrix resin to a carbon fiber bundle can be used. Among them, dipping or coating is preferable, and as a specific coating, a reverse roll, a normal rotation roll, a kiss roll, a spray, and a curtain are preferably used.

  Here, dipping refers to a method in which (B) the phenol resin is supplied to the melting bath by a pump and the component (A) is passed through the melting bath. By immersing the component (A) in the (E) phenol resin melting bath, the (B) phenol resin can be reliably attached to the component (A). Moreover, a reverse roll, a normal rotation roll, and a kiss roll mean the method of supplying the (B) phenol resin fuse | melted with the pump to a roll, and apply | coating the melt of (B) phenol resin to a component (A). Further, the reverse roll is a method in which two rolls are rotated in opposite directions and a molten (B) phenol resin is applied on the roll, and the positive roll is obtained by rotating the two rolls in the same direction. And (B) a phenol resin melted on a roll. Usually, in the reverse roll and the forward rotation roll, a method is used in which the component (A) is sandwiched, and a roll is further installed, and (B) the phenol resin is reliably adhered. On the other hand, the kiss roll is a method in which the component (A) and the roll are in contact, and (B) the phenol resin is adhered. Therefore, the kiss roll is preferably used when the viscosity is relatively low. However, even if any roll is used, a predetermined amount of the (B) phenol resin heated and melted is applied, and the component (A) is allowed to run while being adhered. Thus, a predetermined amount of (B) phenol resin can be adhered per unit length of the fiber bundle. Spray is a method that uses the principle of spraying, and is a method in which molten (B) phenolic resin is sprayed and sprayed onto component (A). Curtains spontaneously drop molten (B) phenolic resin from small holes. And a method of applying by overflowing from the melting tank. Since it is easy to adjust the amount required for coating, the loss of (B) phenol resin can be reduced.

  Moreover, as a melting temperature of the phenol resin in a melting bath at the time of supplying (B) a phenol resin to a component (A), 100-300 degreeC is preferable. If it is 100 degreeC or more, the viscosity of (B) phenol resin can be suppressed moderately, and adhesion nonuniformity can be suppressed. 150 degreeC or more is more preferable. Moreover, if it is 300 degrees C or less, the thermal decomposition of (B) phenol resin can be suppressed. 250 degrees C or less is more preferable.

  Next, as step (II), (B) component (A) in contact with the phenol resin obtained in step (I) is heated and impregnated. Specifically, (B) component (A) in contact with the phenolic resin is subjected to (B) tension with a roll or bar at a temperature at which the phenolic resin is melted, repeated widening and focusing, pressure and This is a step of impregnating the component (A) with the (B) phenol resin by an operation such as applying vibration. As a more specific example, there can be mentioned a method of performing widening by passing a fiber bundle in contact with the surfaces of a plurality of heated rolls or bars. Among these, a method of impregnation using a squeezing die, a squeezing roll, a roll press, or a double belt press is preferably used. Here, the squeezing base is a base whose diameter decreases in the direction of travel. While concentrating the component (A), the excessively adhering (B) phenol resin is scraped and impregnated. It is a mouthpiece to encourage. Further, the squeeze roll is a roller that urges impregnation at the same time as scraping off the excessively adhering (B) phenol resin by applying tension to the component (A) with a roller. The roll press is a device that promotes impregnation at the same time that the air inside the component (A) is continuously removed by the pressure between the two rolls, and the double belt press is from above and below the component (A). It is a device that promotes impregnation by pressing through a belt.

  Moreover, in the step (II), it is preferable that 80 to 100% by weight of the supply amount of the (B) phenol resin is impregnated in the component (A). 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. Moreover, if the impregnation amount of (B) phenol resin is 80% by weight or more of the supply amount, (E) voids inside the resin impregnated reinforcing fiber bundle due to generation of volatile components in step (II) can be suppressed. it can. More preferably, it is 85-100 weight%, More preferably, it is 90-100 weight%.

  Moreover, in process (II), it is preferable that the highest temperature of the (B) phenol resin heated is 150-400 degreeC. If it is 150 degreeC or more, (B) phenol resin can fully be melted and an impregnation to a reinforcing fiber bundle can be advanced more effectively. 180 degreeC or more is more preferable, and 200 degreeC or more is further more preferable. On the other hand, if it is 400 degrees C or less, side reactions, such as the decomposition reaction of (B) phenol resin, 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 and the method of heating and pressurizing simultaneously using a hot roller can be illustrated.

  Moreover, it is preferable to heat in non-oxidizing atmosphere from a viewpoint of suppressing generation | occurrence | production of unfavorable side reactions, such as the crosslinking reaction of a (B) phenol resin, and a decomposition reaction. 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. Among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling.

In addition, the component (A) may be opened in advance before the steps (I) and (II). Opening is an operation of separating the converged component (A), and (B) an effect of further enhancing the impregnation property of the phenol resin can be expected. With the opening, the thickness of the component (A) is reduced, the width of the component (A) before opening is b ₁ (mm), the thickness is a ₁ (μm), and the width of the component (A) after opening is When b ₂ (mm) and the thickness are a ₂ (μm), it is preferable that the fiber opening ratio = (b ₂ / a ₂ ) / (b ₁ / a ₁ ) is 2.0 or more, 2.5 More preferably, the above is used.

  The method for opening component (A) is not particularly limited. For example, a method in which concavo-convex rolls are alternately passed, a method in which drum rolls are used, a method in which tension variation is applied to axial vibration, and a reciprocating motion in vertical direction 2 A method of changing the tension of the component (A) by individual friction bodies, a method of blowing air to the component (A), and the like can be used.

  FIG. 1 is a schematic view showing an example of a cross-sectional form of the (E) resin-impregnated reinforcing fiber bundle in the present invention. In the present invention, the transverse section means a section in a plane orthogonal to the axial direction. The (E) resin-impregnated reinforcing fiber bundle obtained in the present invention is formed as a composite obtained by applying and impregnating the component (A) with (B) phenol resin (hereinafter referred to as (E) resin-impregnated reinforcing fiber bundle. Also called complex). The form of this composite is as shown in FIG. 1, and the (B) phenol resin 2 is filled between each single fiber of the component (A). That is, (B) In the sea of the phenol resin 2, each single fiber 1 of the component (A) is dispersed like an island.

  In the above composite, (B) a composite in which the phenol resin is satisfactorily impregnated with the component (A) is melt-kneaded in a cylinder of an injection molding machine when, for example, (C) polycarbonate resin is injection molded. (B) The phenol resin diffuses into the (C) polycarbonate resin and helps the component (A) to disperse in the (C) polycarbonate resin, and at the same time the (C) polycarbonate resin replaces and impregnates the component (A). It has a role as a so-called impregnation aid / dispersion aid.

Further, in the composite, it is desirable that the component (A) is completely impregnated with the (B) phenol resin. However, in reality, this is difficult, and the composite has a certain amount of voids (component (A)). (B) a portion where no phenol resin is present). In particular, when the content of component (A) is large, the number of voids increases, but even when a certain amount of voids are present, the effect of promoting impregnation and fiber dispersion of the present invention is shown. However, if the porosity exceeds 40%, the effect of promoting impregnation and fiber dispersion is remarkably reduced, so the porosity is preferably less than 40%. A more preferable range of the porosity is 20% or less. The porosity is determined 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 formed by components (A) and (B) phenolic resin and It can be calculated from the total area using the following formula.
(Void ratio) [%] = (total area of void) / (total area of composite portion + total area of 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 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%.

  In the present invention, the molding material has a structure in which (E) a resin-impregnated reinforcing fiber bundle (composite) is coated with (C) a polycarbonate resin and (D) a phosphorus flame retardant. In addition to (C) polycarbonate resin and (D) phosphorus flame retardant, (F) liquid crystalline resin and / or styrene resin or a composition containing other components may be coated. Here, in the present invention, the “coated structure” means, for example, in the case of a structure coated with (C) a polycarbonate resin and (D) a phosphorus flame retardant, the composite obtained as described above is ( It is preferable that the resin is suitably disposed and bonded to C) polycarbonate resin and (D) phosphorus flame retardant, and examples of the bonding method include molten (C) polycarbonate resin and (D) phosphorus-based flame retardant. For example, a method in which a flame retardant is disposed in contact with the composite, and cooled and solidified. The method is not particularly limited, but more specifically, (C) a polycarbonate resin and (D) a phosphorus flame retardant continuously around the composite using an extruder and a coating die for a wire coating method. (C) Polycarbonate resin and (D) Phosphorus-based difficulty that are melted by using an extruder and a T-die from one or both sides of a composite flattened with a roll or the like. An example is a method in which a flame retardant is disposed and integrated with a roll or the like.

  FIG. 2 is a schematic view showing an example of a preferred longitudinal sectional form of the molding material produced in 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 molding material of the present invention, as shown in FIG. 2, the single fibers 1 of the component (A) are arranged substantially parallel to the axial direction of the molding material, and the length of the component (A) is the same as that of the molding material. The length is substantially the same as the length.

  Here, “arranged substantially in parallel” means that the major axis of the component (A) and the major axis of the molding material are oriented in the same direction. The angle deviation is preferably 20 ° or less, more preferably 10 ° or less, and further preferably 5 ° or less. In addition, “substantially the same length” means that, for example, in a pellet-shaped molding material, the component (A) is cut in the middle of the pellet, or the component (A) significantly shorter than the total length of the pellet is substantially Is not included. In particular, the amount of the component (A) shorter than the total length of the pellet is not specified, but the content of the component (A) having a length of 50% or less of the total length of the pellet is 30% by mass or less. Evaluates that the component (A) significantly shorter than the whole pellet length is substantially not contained. Furthermore, the content of the component (A) having a length of 50% or less of the total length of the pellet is preferably 20% by mass or less. In addition, a pellet full length is the length of the orientation direction of the component (A) in a pellet. Since the component (A) has a length equivalent to that of the molding material, the length of the reinforcing fiber in the molded product can be increased, so that excellent mechanical properties can be obtained.

  3 to 6 each schematically show an example of the longitudinal cross-sectional form of the molding material of the present invention. FIGS. 7 to 10 are cross-sectional views of the molding material of the present invention shown in FIGS. FIG. 11 schematically illustrates an example of a cross-sectional shape of the molding material of the present invention.

  If the cross-sectional form of the molding material is arranged so that the composition containing (C) polycarbonate resin and (D) phosphorus flame retardant adheres to the composite composed of components (A) and (B) phenolic resin Although not limited to what is shown in the figure, preferably, as shown in FIGS. 3 to 5, the composite becomes a core material and is sandwiched in layers with a composition containing (C) polycarbonate resin and (D) phosphorus flame retardant. A configuration in which these are arranged is preferable.

  Also, as shown in FIGS. 7 to 9, the composite is arranged in a core-sheath structure in which the core structure is covered with a composition containing (C) a polycarbonate resin and (D) a phosphorus-based flame retardant. The configuration is preferable. Moreover, when arrange | positioning so that the composition containing (C) polycarbonate resin and (D) phosphorus flame retardant may coat | cover several composites as shown in FIG. 11, the number of composites is about 2-6. desirable.

  The boundary between the composite and the composition containing (C) the polycarbonate resin and (D) the phosphorus-based flame retardant is adhered, and the composition containing (C) the polycarbonate resin and (D) the phosphorus-based flame retardant is partially formed in the vicinity of the boundary. It may enter a part of the composite and be in a state where it is compatible with the (B) phenol resin constituting the composite, or impregnated with the component (A).

  The 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 point of handling of the molding material, the composite and the composition containing (C) polycarbonate resin and (D) phosphorus-based flame retardant do not separate and remain bonded until molding is performed. It is preferable to keep. In the composition containing the composite and (C) polycarbonate resin and (D) phosphorus flame retardant, the shape (size, aspect ratio), specific gravity, and mass are completely different. The material is classified at the time of material transfer, and there are cases where the mechanical properties of the molded product vary, the fluidity is lowered and the mold is clogged, or blocking in the molding process is exemplified in FIGS. With such an arrangement of the core-sheath structure, the composition containing (C) the polycarbonate resin and (D) the phosphorus-based flame retardant restrains the composite, and a stronger composite can be achieved. In addition, as to which of the core-sheath structure as illustrated in FIGS. 7 to 9 or the layered arrangement as illustrated in FIG. From the viewpoint of ease, a core-sheath structure is more preferable.

  The 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. Good. It is preferable to be cut to a length in the range of 1 to 50 mm. By adjusting to this 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.

  A molded article can be obtained by molding the molding material of the present invention. Examples of the molding method include injection molding. Also, integrated molding such as insert molding and outsert molding can be easily performed. 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.

  Molded products include instrument panels, door beams, under covers, lamp housings, pedal housings, radiator supports, spare tire covers, front end and other modules, cylinder head covers, bearing retainers, intake manifolds, pedals and other automotive parts and components. Aircraft parts such as outer panels, landing gear pods, winglets, spoilers, edges, ladders, failings, ribs, members and outer panels, monkeys, wrenches, telephones, facsimiles, VTRs, copiers, televisions , Household and office electrical product parts such as microwave ovens, audio equipment, toiletries, laser discs (registered trademark), refrigerators and air conditioners. Further, there are also cases for electrical and electronic equipment typified by a case used for personal computers, mobile phones, etc., and a keyboard support that is a member for supporting a keyboard inside the personal computer. Especially, since the molding material of this invention uses carbon fiber, it is excellent in electromagnetic wave shielding, and since it can obtain a flame retardance, it is preferably used for the member for electrical / electronic devices.

  Moreover, it is preferable that the weight average fiber length of the carbon fiber contained in the molded article of this invention is 0.5-3 mm. If the weight average fiber length of the carbon fiber is 0.5 mm or more, the mechanical properties and electromagnetic wave shielding properties are further improved. 0.8 mm or more is more preferable. On the other hand, if the weight average fiber length of the carbon fiber is 3 mm or less, the fiber dispersibility is excellent and the surface appearance is improved. More preferably, it is 1.5 mm or less.

  Further, a method for obtaining a molded product having the above-mentioned weight average fiber length is not particularly limited, and a method using so-called long fiber pellets in which fibers remain in the pellets during injection molding can be mentioned. Although it does not specifically limit as length of the carbon fiber contained in a long fiber pellet, 3-20 mm is preferable, More preferably, it is 4-15 mm.

Here, the “weight average fiber length” in the present invention refers to the following formula that considers the contribution of the fiber length instead of simply taking the number average by applying the calculation method of the weight average molecular weight to the calculation of the fiber length. The average fiber length calculated from However, the following formula is applied when the fiber diameter and density of the carbon fiber are constant.
Weight average fiber length = Σ (Mi ² × Ni) / Σ (Mi × Ni)
Mi: Fiber length (mm)
Ni: The number of carbon fibers having a fiber length Mi.

  The weight average fiber length can be measured by the following method. The molded product is incinerated at 500 ° C. for 2 hours, the carbon fiber in the molded product is taken out, and the carbon fiber is uniformly dispersed in water. The dispersed water in which carbon fibers are uniformly dispersed is sampled in a petri dish, dried, and observed with an optical microscope (50 to 200 times). The length of 1000 randomly selected carbon fibers is measured, and the weight average fiber length is calculated from the above formula.

  In addition, the molded article of the present invention preferably has a flame retardancy of V-1 or higher in a UL-94 flame retardant test at a thickness of 1/32 inch (about 0.8 mm). More preferably, it is V-0. From the viewpoint of safety when the molded product is used for, for example, a member for an electric / electronic device, flame retardancy particularly in a molded product as thin as 1/32 inch is important. By using the molding material within the scope of the present invention, the weight-average fiber length is 0.5 to 1.5 mm due to the so-called auxiliary combustion effect that assists the flame retardancy effect by the phosphorus flame retardant and the flame retardancy by the phenol resin. Even if it exists, a flame retardance can be hold | maintained.

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

The following materials were used as starting materials for each example and comparative example.
(B) Phenol resin (B-1) Phenol novolac resin “Phenolite” (registered trademark) TD-2131 manufactured by DIC Corporation: Melting viscosity at 190 ° C. and melting point 0.4 Pa · s at 190 ° C.
(B-2) o-cresol novolak resin “Phenolite” (registered trademark) KA-1165 manufactured by DIC Corporation: Melting viscosity of 1.2 Pa · s at a melting point of 125 ° C. and 190 ° C.
(C) Polycarbonate resin (C-1) Polycarbonate resin “Panlite” (registered trademark) L-1225L manufactured by Teijin Chemicals Ltd .: Viscosity average molecular weight 19,500, having a carbonate structure of bisphenol A (C-2) Polycarbonate resin “Taflon” (registered trademark) A2600 manufactured by Idemitsu Kosan Co., Ltd .: (D) Phosphorus flame retardant having a viscosity average molecular weight of 26,000 and a carbonate ester structure of bisphenol A (D-1) Phosphorus Chemical Industries, Ltd. Red phosphorus flame retardant “NOBARRETT 120”
(D-2) Condensed phosphate ester flame retardant “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.
(G) Styrenic resin (G-1) Hydrogenated styrene / butadiene block copolymer (SEBS resin) “Tuftec” (registered trademark) M1913 manufactured by Asahi Kasei Chemicals Corporation
(G-2) Kaneka Corporation MBS resin “Kane Ace” (registered trademark) M-511
(G-3) Acrylonitrile-styrene / silicone / acrylic core-shell type composite rubber “METABREN” (registered trademark) SRK200A manufactured by Mitsubishi Rayon Co., Ltd.

  Evaluation in each example and comparative example was performed by the following method.

(1) Production of molded product (test specimen for evaluation) The pellet-shaped molding material obtained in each example and comparative example was injected using a SE75DUZ-C250 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. A molded article (evaluation specimen) was molded by injection molding at 10 seconds, holding pressure: molding lower limit pressure + 10 MPa, holding pressure time: 10 seconds, cylinder temperature: 290 ° C., mold temperature: 90 ° C. Here, the cylinder temperature indicates the temperature of the portion where the molding material of the injection molding machine is heated and melted, and the mold temperature indicates the temperature of the mold for injecting a resin for forming a predetermined shape. The obtained molded product was allowed to stand for 24 hours in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH, and then subjected to evaluation described below.

(2) Fiber dispersibility A 100 mm × 100 mm (3 mmt) molded product was formed by the method described in (1) above, and the number of undispersed reinforcing fiber bundles present on the front and back surfaces was counted visually. Evaluation was performed on 50 molded products, and fiber dispersibility was determined for the total number based on the following criteria. A to C were judged acceptable.
A: Less than 1 undispersed CF bundle B: 1 or more and less than 5 undispersed CF bundles C: 5 or more and less than 10 undispersed CF bundles D: 10 or more undispersed CF bundles

(3) Flame retardancy By the method described in (1) above, a molded product of 125 mm × 13 mm (thickness 1/32 inch: about 0.8 mm) is molded, and flame retardancy evaluation is performed according to UL-94. Carried out. Specifically, a burner flame was applied to the lower end of the vertically supported molded product and kept for 10 seconds, and then the burner flame was separated from the molded product. 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. In addition, when it burned exceeding the following range, it was set to V-out.
V-0: The duration of the first flammable combustion was within 10 seconds, and the sum of the second flammable combustion duration and the flameless combustion duration was within 30 seconds, and there were no burning fallen objects.
V-1: The duration of the first flammable combustion is more than 10 seconds within 30 seconds and the total of the second flammable combustion duration and the flameless combustion duration is more than 30 seconds and within 60 seconds, There wasn't.
V-2: The duration of the first flammable combustion is over 10 seconds within 30 seconds, and the total of the second flammable combustion duration and the flameless combustion duration is over 30 seconds within 60 seconds, there were.

(4) Weight average fiber length By the method described in (1) above, a molded product of 125 mm × 13 mm (thickness 1/32 inch: about 0.8 mm) is molded, and the molded product is incinerated at 500 ° C. for 2 hours. The carbon fiber in the molded product was taken out, the carbon fiber was uniformly dispersed in water, the dispersed water in which the carbon fiber was uniformly dispersed was sampled in a petri dish, dried, and observed with an optical microscope (50 times). . The length of 1000 carbon fibers selected at random was measured, and 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 carbon fibers having a fiber length Mi.

(5) Bending strength By the method described in (1) above, a bending test specimen (width 10 mm, thickness 4 mm) is formed, and in accordance with ISO 178, a three-point bending test jig (indenter radius 5 mm) is used. The fulcrum distance was set to 64 mm, and the bending strength was measured under test conditions of a test speed of 2 mm / min. As a testing machine, “Instron” (registered trademark) universal testing machine 5566 type (manufactured by Instron) was used.

(6) Charpy impact strength with notch By the method described in (1) above, a test piece for Charpy impact test (width 10 mm, thickness 4 mm) was molded, and a 1.0 J hammer was applied according to ISO 179-1. Used to measure the notched Charpy impact strength. In addition, in accordance with ISO 2818, a notch with a notch angle of 45 ° and a depth of 2 mm was used as a specimen for Charpy impact test.

(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 carbon fiber having 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 Using the carbon fiber produced in Reference Example 1, polyglycerol polyglycidyl ether (epoxy equivalent: 140 g / eq) as a sizing agent was dissolved in water so as to be 2% by weight. A sizing treatment liquid was prepared, and a sizing agent was applied to the reinforcing fiber bundle by an immersion method so that the adhesion amount was 0.5% by weight, followed by drying at 230 ° C. to produce carbon fiber-1.

Reference Example 3 (F-1) Preparation of liquid crystalline resin (1)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 932 parts by weight of p-hydroxybenzoic acid, 251 parts by weight of 4,4′-dihydroxybiphenyl, 99 parts by weight of hydroquinone, 284 parts by weight of terephthalic acid, 90 parts by weight of isophthalic acid And 1252 parts by weight of acetic anhydride (1.09 equivalents of total phenolic hydroxyl groups) were allowed to react at 145 ° C. for 1 hour with stirring in a nitrogen gas atmosphere, and the jacket temperature was increased from 145 ° C. to 270 ° C. on average. The temperature was increased at a temperature rate of 0.68 ° C./min, and the temperature was increased from 270 ° C. to 350 ° C. at an average temperature increase rate of 1.4 ° C./min. The temperature raising time was 4 hours. Thereafter, the polymerization temperature was maintained at 350 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter. (F-1) A liquid crystalline resin (melting point = 330 ° C.) was obtained.

50 mg of the obtained (F-1) liquid crystalline resin was weighed into an NMR sample tube, and a solvent (pentafluorophenol / 1,1,2,2-tetrachloroethane-d ₂ = 65/35 (weight ratio) mixed solvent). ¹ H-NMR measurement was performed at an observation frequency of 500 MHz and a temperature of 80 ° C. using a UNITY INOVA 500 type NMR apparatus (manufactured by Varian). When the composition was analyzed from the peak area ratio derived from each structural unit observed in the vicinity of 7 to 9.5 ppm, the structural unit derived from p-hydroxybenzoic acid (I-1) and the structure derived from 4,4′-dihydroxybiphenyl proportion of units _(II 1 -1) and hydroquinone-derived structural units _(II 2 -1) structural units to the total of (I-1) was 75 mol%. In addition, the ratio of the structural unit (II ₁ -1) to the total of the structural unit (II ₁ -1) and the structural unit (II ₂ -1) was 60 mol%. Furthermore, the ratio of the structural unit (IV ₁ -1) to the total of the structural unit derived from terephthalic acid (IV ₁ -1) and the structural unit derived from isophthalic acid (IV ₂ -1) was 76 mol%. The total of the structural unit (II ₁ -1) and the structural unit (II ₂ -1) and the total of the structural unit (IV ₁ -1) and the structural unit (IV ₂ -1) are substantially equimolar. there were.

  Moreover, about the obtained (F-1) liquid crystalline resin, using Koka type flow tester CFT-500D (orifice 0.5φ × 10 mm) (manufactured by Shimadzu Corporation), temperature: melting point of liquid crystalline polyester + 10 ° C., When the melt viscosity was measured under the condition of shear rate: 1000 / sec, it was 28 Pa · s.

Reference Example 4 (F-2) Preparation of liquid crystalline resin (2)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 995 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl / g The mixture was charged with 216 parts by weight of polyethylene terephthalate and 969 parts by weight of acetic anhydride, reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere, and then heated to 325 ° C. over 4 hours. Thereafter, the polymerization temperature was maintained at 325 ° C., nitrogen was pressurized to 0.1 MPa, and the mixture was heated and stirred for 20 minutes. Thereafter, the pressure was released, the pressure was reduced to 133 Pa in 1.0 hour, and the reaction was continued for another 120 minutes. When the torque reached 12 kg · cm, the polycondensation was completed. Next, the inside of the reaction vessel is pressurized to 0.1 MPa, the polymer is discharged to a strand through a die having a circular discharge port having a diameter of 10 mm, pelletized by a cutter, and (F-2) liquid crystalline A resin (melting point = 314 ° C.) was obtained.

  The obtained (F-2) liquid crystalline resin was subjected to composition analysis in the same manner as in Reference Example 3 above. As a result, structural unit (I-2) derived from p-hydroxybenzoic acid, derived from 4,4′-dihydroxybiphenyl The total of the structural unit (I-2) and the structural unit (II-2) is 80 mol% with respect to the total of the structural unit (II-2) and the ethylenedioxy unit (III-2) derived from polyethylene terephthalate, Structural unit (III-2) is 12.5 mol% with respect to the sum total of structural units (I-2), (II-2) and (III-2), and the structure of structural unit (I-2) The molar ratio [(I) / (II)] to the unit (II-2) is 91.5 / 8.5, and the aromatic dicarboxylic acid unit (IV-2) derived from terephthalic acid and polyethylene terephthalate is a structural unit. (II-2) Totaled equimolar Beauty (III-2).

  Further, when the melt viscosity of the obtained (F-2) liquid crystalline resin was measured in the same manner as in Reference Example 3, it was 12 Pa · s.

Reference example A
On the roll heated to the coating temperature, a liquid film in which (B) the phenol resin (B-1) was heated and melted was formed. A reverse roll was used to form a film having a constant thickness on the roll. The continuous carbon fiber-1 obtained in Reference Example 2 was passed through this roll while being in contact therewith, and (B) the phenol resin (B-1) was adhered. Next, in a chamber heated to the impregnation temperature (maximum temperature: 250 ° C.), (B) the carbon fiber-1 to which the phenol resin (B-1) was attached was placed between five sets of 50 mm diameter roll presses. Was passed. By this operation, (B) a phenol resin was impregnated to the inside of the carbon fiber bundle, and (E) a resin-impregnated reinforcing fiber bundle having a predetermined blending amount was formed. Moreover, as a result of calculating the adhesion amount from the coating amount and the impregnation amount at this time, it was 85% by weight. In addition, it adjusted so that it might become a desired compounding quantity from the input amount of carbon fiber-1 and the thickness on the roll of (B) phenol resin (B-1).

  On the other hand, a TEX-30α type twin screw extruder (screw diameter 30 mm, die diameter 5 mm, barrel temperature 290 ° C., screw rotation speed 150 rpm) manufactured by JSW was used and (C) polycarbonate resin (C-1 ) And (D) a dry blend of phosphorus-based flame retardant (D-1) was supplied from the main hopper, and the molten resin was discharged from the die port while degassing from the downstream vacuum vent. The obtained strand was cooled and then cut with a cutter to obtain a melt-kneaded pellet of a polycarbonate resin composition.

  A wire coating method in which the (E) resin impregnated reinforcing fiber bundle obtained by the above method is installed at the tip of a Nippon Steel Works TEX-30α type twin screw extruder (screw diameter 30 mm, L / D = 32) The melt-kneaded pellets of the polycarbonate resin composition obtained by the above method are discharged from the extruder into the die in a molten state so as to cover the periphery of the (E) resin-impregnated reinforcing fiber bundle. Arranged continuously. At this time, the amount of the (E) resin-impregnated reinforcing fiber bundle and the discharge amount of the polycarbonate resin composition were adjusted so that each component had the blending amount 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 molding material. Table 1 shows the results of evaluation by the method described above.

Reference Examples AG, Examples 7 , 9-20, Comparative Examples 1-5
Long fiber pellets were produced in the same manner as in Reference Example A , except that the types and amounts of each component were changed as shown in Tables 1, 2 and 3. The evaluation results are summarized in Table 1, Table 2, and Table 3. Here, in the example which mix | blended (F) liquid crystalline resin or (G) styrene-type resin, as a melt-kneaded pellet of the polycarbonate resin composition which mix | blended these with (C) polycarbonate resin and (D) phosphorus flame retardant Using.

As described above, in Examples 7 and 9 to 20, molded articles having excellent fiber dispersibility and good flame retardancy and bending strength were obtained. On the other hand, in Comparative Examples 1-5, only the molding material with inferior fiber dispersibility and flame retardance was obtained.

  The molding material of the present invention has good flame retardancy and excellent dispersibility of carbon fibers in the polycarbonate resin at the time of molding, so that a molded product having excellent mechanical properties such as bending properties and impact resistance properties can be obtained. It can be used for various purposes. It is particularly suitable for various parts / members such as electrical / electronic equipment, OA equipment, home appliances, automobile parts, internal members, and housings.

DESCRIPTION OF SYMBOLS 1 Monofilament of component (A) 2 (B) Phenolic resin 3 (E) Resin-impregnated reinforcing fiber bundle 4 (C) Composition containing polycarbonate resin and (D) phosphorus flame retardant

Claims (8)

A molding material containing 100 parts by weight of the following components (A) to (D) in total, and (E) a resin-impregnated reinforcing fiber bundle in which the following component (B) is melt-impregnated into the following component (A): ) And the following component (D).
(A) Carbon fiber to which sizing agent containing epoxy resin is attached in the range of 0.01 to 3.0% by weight 5 to 35 parts by weight (B) 1 to 15 parts by weight of phenol resin (( B) has a melting point of 120 ° C. O-cresol novolac resin, exceeding 150 ° C. and below)
(C) Polycarbonate resin 30-89 parts by weight (D) Phosphorus flame retardant 5-20 parts by weight The molding material according to claim 1, wherein the component (D) is a condensed phosphate ester compound. The molding material of Claim 1 or 2 whose melt viscosity in 190 degreeC of the said component (B) is 0.2-10 Pa.s. The molding material according to any one of claims 1 to 3 , wherein the surface oxygen concentration ratio [O / C] of the carbon fiber used in the component (A) is 0.1 to 0.2. The molding material according to any one of claims 1 to 4 , wherein the sizing agent in the component (A) is a tri- or higher functional aliphatic epoxy resin. The molding material according to any one of claims 1 to 5 , wherein the component (C) has a viscosity average molecular weight of 25,000 to 35,000. The molding material according to any one of claims 1 to 6 , comprising (F) a liquid crystalline resin and / or (G) a styrene-based resin in addition to the components (A) to (D). A molded product obtained by injection molding the molding material according to any one of claims 1 to 7 , wherein a weight average fiber length of carbon fibers contained in the molded product is 0.5 to 1.5 mm, and the molded product. A molded product having a flame retardancy of UL-94 of V-1 or more at a thickness of 1/32 inch.

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