JP2013011049A - Composite reinforcement fiber bundle, method for producing the same, and molding material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite reinforcement fiber that has good impregnability of resin into a reinforcement fiber bundle and is capable of providing a molding having both excellent flame retardancy and weather resistance; a method for producing the same; and a molding material.SOLUTION: The composite reinforcement fiber bundle is formed by impregnating 100 pts.wt. of a reinforcement fiber bundle (A) with 10-100 pts.wt. of a halogen-based flame retardant (B) and 0.2-10 pts.wt. of a light stabilizer (C). The molding material is composed of the composite reinforcement fiber bundle and a thermoplastic resin composition (D). Also, the method for producing a composite reinforcement fiber bundle includes contacting the component (B) and the component (C) in a molten state at 100-320°C with the component (A) and further impregnating the component (A) with the component (B) and the component (C) in an amount of 80-100 wt.% of the supply amount by heating them.

Description

  The present invention relates to a composite reinforcing fiber bundle, a method for producing the same, and a molding material. More specifically, the present invention relates to a composite reinforcing fiber bundle that has good resin impregnation into a reinforcing fiber bundle and can impart flame retardancy and weather resistance during molding, a method for producing the same, and a molding material.

  Molding materials composed of reinforcing fibers and thermoplastic resins are widely used in sports equipment applications, aerospace applications and general industrial applications because they are lightweight and have excellent mechanical properties. The reinforcing fibers used in these molding materials reinforce the molded product in various forms depending on the usage. These reinforcing fibers include metal fibers such as aluminum fibers and stainless fibers, organic fibers such as aramid fibers and PBO fibers, inorganic fibers such as silicon carbide fibers, and carbon fibers. Carbon fibers are preferred from the viewpoint of the balance between rigidity and lightness, and among them, polyacrylonitrile-based carbon fibers are suitably used.

  However, in the process of producing a molding material, there is a problem in terms of economy and productivity in impregnating a continuous reinforcing fiber bundle with a thermoplastic resin, and it is not widely used at present. For example, it is well known that the higher the melt viscosity of the resin, the more difficult the impregnation of the reinforcing fiber bundle is. Thermoplastic resins with excellent mechanical properties such as toughness and elongation are high molecular weight polymers and require high process temperatures, making them unsuitable for producing molding materials easily and with high productivity. It was.

  In recent years, the demand for exterior materials such as structural parts of transport machinery is expanding, and high flame resistance and weather resistance are required. However, resins are generally vulnerable to heat and often do not have sufficient flame retardancy. In addition, it is sensitive to the action of light, which causes deterioration, that is, discoloration or lowering of mechanical strength, and molded products with resin as a matrix cannot withstand long-term use under conditions of significant light irradiation. It is known.

  Therefore, Patent Document 1 supports 10 to 30% by weight of an epoxy resin solid at room temperature and having a bromine content of at least 15% by weight, or an unmodified novolak phenol resin having a molecular weight of 2000 or less and solid at room temperature. The mesophase pitch carbon fiber chopped strand for direct injection molding is disclosed, and it is shown that the carbon fiber chopped strand has high bundling properties, is excellent in dispersibility and stability in the matrix resin, and exhibits a high reinforcing effect. Has been. However, when the resin is supported on the carbon fiber chopped strands, the solvent in which the resin is dissolved is impregnated with the carbon fiber chopped strands, so that the solvent tends to remain inside the reinforcing fiber bundle and voids inside the reinforcing fiber bundle are easily generated. There is a tendency. Furthermore, when it is used as a molding material with insufficient drying, it is not preferable because it may have a large amount of volatile components during molding or may cause defects in the molded product. Moreover, in order to perform sufficient drying, it is difficult to improve a line speed, and it may be inferior from the surface of economical efficiency and productivity. Further, no mention is made of flame retardancy and weather resistance.

  Under such circumstances, there has been a demand for a composite reinforcing fiber bundle that has good resin impregnation into the reinforcing fiber bundle and can impart flame retardancy and weather resistance during molding.

JP-A-8-60550

  In view of the problems of the prior art, the present invention provides a composite reinforcing fiber that has good resin impregnation into a reinforcing fiber bundle and can provide a molded product having excellent flame retardancy and weather resistance, and a method for producing the same And a molding material.

  In order to solve the above problems, the present invention has the following configuration. That is, a composite reinforcing fiber bundle in which 10 to 100 parts by weight of a halogenated flame retardant (B) and 0.2 to 10 parts by weight of a light stabilizer (C) are impregnated with respect to 100 parts by weight of a reinforcing fiber bundle (A). is there.

  Further, as a result of intensive studies, the present inventors have invented the following method for producing a composite reinforcing fiber bundle that can solve the above-described problems. That is, the halogenated flame retardant (B) and the light stabilizer (C) are brought into contact with the reinforcing fiber bundle (A) in a molten state at 100 to 320 ° C. and further heated to be halogenated flame retardant (B) and the light stabilizer. It is a manufacturing method of the composite reinforcing fiber bundle in any one of Claims 1-6 which makes a reinforcing fiber bundle (A) impregnate 80 to 100 weight% of the supply amount of (C).

  Furthermore, as a result of intensive studies, the inventors have invented the following molding material capable of solving the above-described problems. That is, it is a molding material composed of the above-described composite reinforcing fiber bundle and the thermoplastic resin composition (D).

  By using the composite reinforcing fiber bundle and the molding material according to the present invention, a molded product having excellent flame retardancy and weather resistance can be obtained. In addition, the production method of the present invention provides a composite reinforcing fiber bundle having good impregnation into the reinforcing fiber bundle, less voids, and less volatile content during molding. The composite reinforcing fiber bundle according to the present invention and a molded product molded using a molding material are extremely suitable for various parts and members such as electrical / electronic equipment, OA equipment, home appliances, automobile parts, internal members, and casings. Useful.

It is the schematic which shows an example of the cross-sectional form of the composite reinforcing fiber bundle obtained by 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 present invention is a composite reinforcing fiber bundle composed of at least a reinforcing fiber bundle (A), a halogen-based flame retardant (B), and a light stabilizer (C). First, these components will be described. In the present invention, the composite reinforcing fiber bundle refers to a fiber obtained by impregnating a reinforcing fiber bundle (A) with a compound having affinity with a thermoplastic resin (hereinafter also referred to as an impregnated compound). It is suitably used in combination with a plastic resin.

  In the present invention, the reinforcing fiber (a) constituting the reinforcing fiber bundle (A) is not particularly limited, but, for example, a high fiber such as carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, etc. Strength and high modulus fibers can be used, and these may be used alone or in combination of two or more. Among these, PAN-based, pitch-based and rayon-based carbon fibers are preferable from the viewpoint of improving the mechanical properties and reducing the weight of the molded product, and from the viewpoint of the balance between the strength and elastic modulus of the molded product obtained. More preferred are fibers. For the purpose of imparting conductivity, reinforcing fibers coated with a metal such as nickel, copper, or ytterbium can also be 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 preferable, more preferably 0.08 to 0.4, and still more preferably 0.1 to 0.3. 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 a stronger adhesion to the thermoplastic resin can be obtained. 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.

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 maintained 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.

  Further, the average fiber diameter of the reinforcing fiber (a) constituting the reinforcing fiber bundle (A) used in the present invention is not particularly limited, but in the range of 1 to 20 μm from the viewpoint of the mechanical properties and surface appearance of the obtained molded product. Is preferably within the range of 3 to 15 μm.

  The number of single fibers of the reinforcing fiber bundle (A) is not particularly limited, and can be used within a range of 100 to 350,000, and particularly within a range of 1,000 to 250,000. Is preferred. Further, according to the present invention, even a reinforcing fiber bundle having a large number of single fibers can be obtained in a range of 20,000 to 100,000 since a sufficiently impregnated composite reinforcing fiber bundle can be obtained. It is also preferable from the viewpoint of productivity.

  Further, the reinforcing fiber bundle (A) used in the present invention is provided with a sizing agent (b), which improves the bundling property, bending resistance and scratch resistance, and in the higher processing step, fluff, yarn It is preferable because it can suppress the occurrence of cutting and can improve higher-order workability as a so-called paste or bundling agent. In particular, in the case of carbon fiber, by applying the sizing agent (b), 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 adhesion amount of the sizing agent (b) is not particularly limited, but is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, and 0.1 to 2% by weight based on the mass of the reinforcing fiber alone. % Is more preferable. If it is less than 0.01% by weight, the effect of improving adhesiveness is hardly exhibited, and if it is more than 10% by weight, the physical properties of the matrix resin may be lowered.

  Furthermore, when the sizing agent (b) is applied to the reinforcing fiber bundle (A) used in the present invention, the weight ratio (b) / (B) of the sizing agent (b) and the halogenated flame retardant (B). Is preferably 0.01 / 1 to 0.5 / 1. More preferably, it is 0.04 / 1-0.4 / 1, More preferably, it is 0.08-0.3 / 1. It is preferable to use each component within such a range because interfacial adhesion, fiber dispersibility, mechanical properties, and flame retardancy can be improved in a well-balanced manner. In addition, although it does not specifically limit as a method of making weight ratio (b) / (B) of a sizing agent (b) and a halogenated flame retardant (B) into a preferable range, For example, a certain halogenated flame retardant (B ) For adjusting the amount of sizing agent (b) attached to the amount of impregnated), or for adjusting the amount of halogenated flame retardant (B) impregnated for a certain amount of sizing agent (b) attached, etc. Is preferable from the viewpoint of process control. The weight ratio (b) / (B) between the sizing agent (b) and the halogen-based flame retardant (B) is the adhesiveness or flame retardant that is caused by the sizing agent (b) or the halogen-based flame retardant (B). It is preferable to adjust in consideration of the balance of sex.

The weight ratio (b) / (B) between the sizing agent (b) and the halogen-based flame retardant (B) can be obtained by the following equation.
Weight ratio of sizing agent (b) to halogenated flame retardant (B) (b) / (B) = W _Sz / W _B
Here, W _Sz represents the adhesion amount of the sizing agent (b) in the reinforcing fiber bundle (A), the weighed value w ₁ (g) of the reinforcing fiber bundle (A), and the weighed reinforcing fiber bundle (A). Can be obtained by the following formula from the weighed value w ₂ (g) after heating at 450 ° C. for 15 minutes in a nitrogen atmosphere.
W _Sz (unit: weight%) = {(w ₁ −w ₂ ) / w ₁ } × 100
W _B represents the amount of the halogen flame retardant (B), the impregnation amount W _BC of the halogen flame retardant (B) and the light stabilizer (C), the halogen flame retardant (B) and the light stabilizer (C ) In the following formula: r _B : r _C
W _B (unit:% by weight) = W _BC × {r _B / (r _B + r _C )}
Here, the impregnation amount W _BC of the halogen-based flame retardant (B) and the light stabilizer (C) is the measured value W ₁ (g) of the composite reinforcing fiber bundle and the weighed composite reinforcing fiber bundle at 450 ° C. in a nitrogen atmosphere. From the measured value W ₂ (g) after heating for 15 minutes, the following formula can be used.
W _BC (unit:% by weight) = {(W ₁ −W ₂ ) / W ₁ } × 100
When the sizing agent (b) is added to the reinforcing fiber bundle (A) in the composite reinforcing fiber bundle, the impregnation amount W _BC of the halogen-based flame retardant (B) and the light stabilizer (C) is expressed by the following formula: It can ask for.
W _BC (unit:% by weight) = {(W ₁ −W ₂ −w _Sz ) / W ₁ } × 100
Here, w _Sz is an adhesion weight (g) of the sizing agent (b) in the composite reinforcing fiber bundle represented by the following formula.
w _Sz (unit: g) = W _Sz W ₂ / (100−W _Sz )

  Moreover, it does not specifically limit as a sizing agent (b) used in this invention, An epoxy resin, a phenol resin, polyethyleneglycol, a polyurethane, polyester, an emulsifier, or surfactant etc. are mentioned. Among these, an epoxy resin that easily exhibits adhesiveness with the matrix resin is preferable. These may be used alone or in combination of two or more.

  Examples of the epoxy resin 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. Normally, epoxy resins with a large number of epoxy groups tend to have a low toughness structure because the crosslinking density after the crosslinking reaction is high, and even if they are interposed between the reinforcing fibers and the matrix resin, they are peeled off because they are brittle. It is easy to do, and the strength improvement effect by fiber reinforcement may not appear. On the other hand, since the aliphatic epoxy resin has a flexible skeleton, it tends to have a high toughness structure even if the crosslinking density is high. When it 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, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-diglycidyl ether compound, and 1,4- Examples include butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, and polyalkylene glycol diglycidyl ether. Also, in the polyglycidyl ether compound, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane Examples thereof include 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, polyglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, 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.

  The means for applying the sizing agent (b) is not particularly limited. For example, a method of immersing in a sizing solution through a roller, a method of contacting a roller to which the sizing solution is attached, and a method of spraying the sizing solution in a mist form and so on. 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 active component of the sizing agent (b) attached to the reinforcing fiber bundle (A) is uniformly attached within an appropriate range. Moreover, it is more preferable to vibrate the reinforcing fiber bundle (A) with ultrasonic waves when applying the sizing agent (b).

  The drying temperature and drying time should be adjusted according to the amount of the compound attached, but the complete removal of the solvent used for the application of the sizing agent (b) and the time required for drying are shortened, while the heat of the sizing agent (b) is reduced. From the viewpoint of preventing deterioration and preventing the sizing-treated reinforcing fiber bundle (A) from becoming hard and deteriorating the spreadability of the bundle, the drying temperature is preferably 150 ° C. or higher and 350 ° C. or lower, 180 It is more preferable that the temperature is not lower than 250 ° C and not higher than 250 ° C.

  Examples of the solvent used for the sizing agent (b) include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone and the like, but water is preferable from the viewpoint of easy handling and disaster prevention. Accordingly, when a compound insoluble or hardly soluble in water is used 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 polyfunctional compound.

  A well-known thing can be used as a halogen-type flame retardant (B) used for this invention. Typical examples thereof 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-dibromopropoxy) Brominated flame retardants containing bromine-containing compounds, such as phenyl) sulfone, tris (2,3-dibromopropyl) isocyanurate, or chlorinated paraffin, chlorinated polyethylene, chlorinated polypropylene, perchloropentacyclodecane, Examples include chlorine-based flame retardants containing chlorine-containing compounds such as dodecachlorododecahydrodimethanodibenzocyclooctene and dodecachlorooctahydrodimethanodibenzofuran. These may be used alone or in combination of two or more. These halogen-based flame retardants (B) are decomposed in the molded article and exhibit flame retardancy by stabilizing active H radicals and OH radicals in the combustion field by a radical trap effect.

  In the present invention, the amount of the halogen-based flame retardant (B) impregnated in the composite reinforcing fiber bundle is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the reinforcing fiber bundle (A). From the balance between mechanical properties and flame retardancy, the amount is more preferably 15 to 80 parts by weight, still more preferably 20 to 60 parts by weight. When the blending amount of the halogen-based flame retardant (B) is less than 10 parts by weight, a sufficient flame retardant effect may not be obtained, and when it exceeds 100 parts by weight, the mechanical properties are reduced, the specific gravity of the molded product is increased, Since the halogen flame retardant (B) may bleed out from the surface of the molded product, it is not preferable.

  The light stabilizer (C) used in the present invention refers to an ultraviolet absorber that converts external light energy into harmless heat energy for the matrix resin, a radical scavenger that traps radicals generated by photooxidation, and the like. .

  The ultraviolet absorber has the effect of stabilizing the light resistance of the halogen-based flame retardant (B), that is, suppressing the generation of halogen radicals and suppressing the light deterioration of the flame retardant. In addition, the radical scavenger suppresses the reaction between the radical and oxygen by scavenging radicals generated by cutting the polymer main chain of the matrix resin in the combustion process, so that the halogen-based flame retardant (B) is used alone. Moreover, flame retardance can be further improved by using these light stabilizers (C) in combination.

  In the present invention, known light stabilizers (C) can be used, for example, UV absorbers such as benzotriazole, cyanoacrylate, triazine, benzophenone, and oxalic anilide, hindered amine, and benzoate. And radical scavengers of the system. These may be used alone or in combination of two or more. In particular, since a hindered amine radical scavenger exhibits a high synergistic effect with an ultraviolet absorber, it is more preferable to use these simultaneously.

  Among the hindered amine light stabilizers, it is particularly preferable to use an amino ether type hindered amine light stabilizer. The amino ether type hindered amine light stabilizer refers to a hindered amine light stabilizer having a structure represented by the following structural formula (1) in the compound, and representative examples thereof include Tinuvin 123 and Tinuvin 152 manufactured by BASF Japan Ltd. Tinuvin NOR 371 FF, Tinuvin XT850 FF, Tinuvin XT855 FF, Flamestab NOR 116 FF, ADEKA Corporation ADEKA STAB LA-81, and the like. These may be used alone or in combination of two or more.

(Wherein R ¹ represents an arbitrary structure other than hydrogen, R ² represents at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, an alkylcarbonyl group and a cycloalkylcarbonyl group. Preferred carbon number of R ² Is 5-12.)

  Amino ether type hindered amine light stabilizers are oxidized by oxygen, ultraviolet rays, etc. to generate nitrooxide radicals, capture the radicals generated in the matrix resin, take the structure of amino ether (-NOR), and further alkyl radicals And it retains the weather resistance by capturing peroxide radicals.

  Further, it is known that in the process of burning the resin composition, thermal decomposition that causes generation of combustible gas is a chain reaction involving active radicals. Here, the nitrooxide radical as described above is generated during combustion from the amino ether type hindered amine light stabilizer, and this captures and lowers the active radical, and exhibits flame retardancy. The flame retardancy at this time is synergistically improved by using it together with a halogen-based flame retardant. The cause of this mechanism is not always clear, but nitrooxide radicals derived from aminoether-type hindered amine light stabilizers promote the radical trapping effect of halogenated flame retardants, and perform the same function as so-called flame retardant aids. Estimated to do.

  On the other hand, the non-amino ether type hindered amine light stabilizer having an NH or NR (R: alkyl group) structure is an amine compound, and thus has a neutralizing reaction when attacked by an acid and has an effect of weather resistance. May decrease. Therefore, when the halogen-based flame retardant (B) is used in combination as in the present invention, the inherent improvement in weather resistance may not be sufficiently exhibited. In addition, it is more preferable to use an amino ether type hindered amine light stabilizer because there are cases where it takes time to generate a nitrooxide radical due to the structure and the peroxide radical cannot be captured in the matrix resin.

  In the present invention, the amount of the light stabilizer (C) impregnated in the composite reinforcing fiber bundle is preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the reinforcing fiber bundle (A). If the light stabilizer (C) is less than 0.2 parts by weight, sufficient weather resistance and flame retardancy may not be obtained. If the light stabilizer (C) exceeds 10 parts by weight, the light stabilizer itself becomes a generation source of decomposition gas, and the flame retardant It is not preferable because the properties may be lowered.

  In the manufacturing method of the composite reinforcement fiber bundle in this invention, it has a process which makes a halogenated flame retardant (B) and a light stabilizer (C) contact a reinforcement fiber bundle (A) in a 100-320 degreeC molten state. Preferably it is 100-250 degreeC, More preferably, it is 100-200 degreeC. At this time, in consideration of the melting point of the halogen-based flame retardant (B) and the light stabilizer (C) to be supplied and the melt viscosity described later, it is preferable to adjust the temperature range to an appropriate temperature. Here, when the temperature is lower than 100 ° C., the viscosity of the halogen-based flame retardant (B) and the light stabilizer (C) is increased, and uneven adhesion may occur during the supply. Moreover, when it exceeds 320 degreeC, when manufactured over a long time, a halogenated flame retardant (B) and a light stabilizer (C) may thermally decompose. By contacting the reinforcing fiber bundle (A) in a molten state at 100 to 320 ° C., the halogen-based flame retardant (B) and the light stabilizer (C) can be stably supplied and impregnated.

  Reinforce the halogenated flame retardant (B) and light stabilizer (C) for the method of controlling the temperature when the halogenated flame retardant (B) and light stabilizer (C) are brought into contact with the reinforcing fiber bundle (A). An appropriate method may be selected according to the method of contacting with the fiber bundle (A). For example, the temperature of the melting bath for melting the halogen flame retardant (B) and the light stabilizer (C), the coating roll A method for adjusting the surface temperature can be mentioned.

  In the present invention, in the step of bringing the halogen flame retardant (B) and the light stabilizer (C) into contact with the reinforcing fiber bundle (A) in a molten state, the halogen flame retardant (B) and the light stabilizer (C). The melt viscosity of is preferably 0.01 to 10 Pa · s. More preferably, it is 0.05-5 Pa.s, More preferably, it is 0.1-2 Pa.s. In such a range, the halogen flame retardant (B) and the light stabilizer (C) can be stably supplied. Further, when contacting with the reinforcing fiber bundle (A), the halogen-based flame retardant (B) and the light stabilizer (C) permeate appropriately into the reinforcing fiber bundle (A). In the step of impregnating the reinforcing fiber bundle (A) with 80 to 100% by weight of the supply amount of the system flame retardant (B) and the light stabilizer (C), it becomes easy to impregnate the amount in a uniform and preferable range. Therefore, it is preferable.

  In the present invention, as a method for controlling the melt viscosity, a method of adjusting the temperature from the temperature range of 100 to 320 ° C. so that the melt viscosity is in a preferable range can be mentioned. Other methods include a method of adding a melt viscosity modifier within a range not impairing the effects of the present invention. The melt viscosity modifier in this invention is not specifically limited, An epoxy resin, a phenol resin, polyethyleneglycol, a polyurethane, polyester, a plasticizer etc. can be illustrated. Among these, an epoxy resin that can also exhibit adhesiveness with the matrix resin is more preferable.

  In addition, the melt viscosity in this invention can be calculated | required by measuring on 0.5 Hz conditions using a 40-mm parallel plate using a viscoelasticity measuring device.

  Moreover, although there is no limitation in particular about the method of supplying a halogen-type flame retardant (B) and a light stabilizer (C), and making it contact with a reinforced fiber bundle (A), an oil agent, a sizing agent, and matrix resin are provided to a fiber bundle. Such a known production method 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. Two or more of these methods may be combined.

  Here, dipping refers to a method in which a halogen-based flame retardant (B) and a light stabilizer (C) are supplied to a melting bath with a pump, and the reinforcing fiber bundle (A) is passed through the melting bath. By immersing the reinforcing fiber bundle (A) in a molten bath of the halogen-based flame retardant (B) and the light stabilizer (C), the halogen-based flame retardant (B) and the light stabilizer (C) are surely added to the reinforcing fiber bundle ( A) can be attached. The reverse roll, the positive rotation roll, and the kiss roll are supplied with a halogen-based flame retardant (B) and a light stabilizer (C) melted by a pump, and a halogen-based flame retardant (A) is added to the reinforcing fiber bundle (A). A method of applying a melt of B) and a light stabilizer (C). Further, the reverse roll is a method in which two rolls rotate in opposite directions to each other, and a molten halogen flame retardant (B) and a light stabilizer (C) are applied onto the roll. This is a method in which the roll of the book rotates in the same direction and the halogenated flame retardant (B) and the light stabilizer (C) melted on the roll. Usually, in the reverse roll and the positive rotation roll, a method is used in which the reinforcing fiber bundle (A) is sandwiched and a roll is further installed to securely attach the halogen flame retardant (B) and the light stabilizer (C). On the other hand, the kiss roll is a method of attaching the halogen-based flame retardant (B) and the light stabilizer (C) only by contacting the reinforcing fiber bundle (A) and the roll. Therefore, the kiss roll is preferably used when the viscosity is relatively low, but any roll method is used to apply a predetermined amount of the heat-melted halogen flame retardant (B) and light stabilizer (C) to strengthen By running while adhering the fiber bundle (A), a predetermined amount of the halogenated flame retardant (B) and the light stabilizer (C) can be adhered per unit length of the fiber bundle. Spraying uses the principle of spraying, and is a method of spraying molten halogen flame retardant (B) and light stabilizer (C) in the form of a mist onto the reinforcing fiber bundle (A), and the curtain is melted This is a method in which the halogen-based flame retardant (B) and the light stabilizer (C) are naturally dropped from a small hole and applied, or by overflowing from a melting tank and applied. Since it is easy to adjust the amount required for coating, the loss of the halogenated flame retardant (B) and the light stabilizer (C) can be reduced.

  In the method for producing a composite reinforcing fiber bundle according to the present invention, following the step of bringing the halogen-based flame retardant (B) and the light stabilizer (C) into contact with the reinforcing fiber bundle (A) in a molten state, heating is further performed. A step of impregnating the reinforcing fiber bundle (A) with 80 to 100% by weight of the supply amount of the halogen-based flame retardant (B) and the light stabilizer (C).

  Specifically, the halogenated flame retardant (B) and the light stabilizer (C) are melted in the reinforcing fiber bundle (A) in contact with the halogenated flame retardant (B) and the light stabilizer (C). The halogenated flame retardant (B) and light stabilizer (C) inside the reinforcing fiber bundle (A) by operations such as applying tension with rolls and bars, repeating widening and focusing, and applying pressure and vibration It is the process of making it impregnate.

  As a more specific example, there can be mentioned a method of widening by passing the fiber bundle so as to contact the surface of a plurality of heated rolls or bars, among which, a drawing base, a drawing roll, a roll press, a double A method of impregnation using a belt press is preferably used.

  Here, the squeezing base is a base whose diameter decreases in the traveling direction, and the halogen-based flame retardant (B) and the light stabilizer (C) that are excessively attached while focusing the reinforcing fiber bundle. It is a base that promotes impregnation at the same time as scraping off. The squeeze roll is a roller that urges impregnation at the same time as scraping off the extra halogenated flame retardant (B) and light stabilizer (C) by applying tension to the reinforcing fiber bundle with a roller. is there. The roll press is a device that continuously removes the air inside the reinforcing fiber bundle by the pressure between the two rolls and at the same time promotes the impregnation. The double belt press is a device that pushes the belt from above and below the reinforcing fiber bundle. It is a device that promotes impregnation by pressing through.

  In this step, it is necessary that 80 to 100% by weight of the supply amount of the halogen-based flame retardant (B) and the light stabilizer (C) is impregnated in the reinforcing fiber bundle (A). Since the yield is directly affected, the higher the yield from the viewpoints of economy and productivity, the better. More preferably, it is 85-100 weight%, More preferably, it is 90-100 weight%. If it is less than 80% by weight, not only from the viewpoint of economic efficiency, the halogen-based flame retardant (B) and the light stabilizer (C) may generate volatile components in this step, and the reinforcing fiber bundle ( A) A void may remain inside. The method of impregnating 80 to 100% by weight of the supply amount of the halogen-based flame retardant (B) and the light stabilizer (C) is not particularly limited. For example, the heating temperature is increased to increase the halogen-based flame retardant (B). And a method of lowering the melt viscosity of the light stabilizer (C), a method of previously opening the reinforcing fiber bundle (A), a method of combining two or more of the exemplified impregnation methods, and the like.

The impregnation amount with respect to the supply amount of the halogen-based flame retardant (B) and the light stabilizer (C) can be obtained by the following equation.
Impregnation amount (unit:% by weight) with respect to the supply amount of the halogenated flame retardant (B) and the light stabilizer (C) = w _BC / w _sp
Here, w _BC is the impregnation weight (g) of the halogen-based flame retardant (B) and the light stabilizer (C), and the weighed value W ₁ (g) of the composite reinforcing fiber bundle and the weighed composite reinforcing fiber bundle From the measured value W ₂ (g) after heating at 450 ° C. for 15 minutes in a nitrogen atmosphere, it can be obtained by the following equation.
w _BC = W ₁ −W _2
Wsp is the weight (g) of the halogenated flame retardant (B) and the light stabilizer (C) supplied when the composite reinforcing fiber bundle is produced.

  In the step of impregnating the reinforcing fiber bundle (A) with the halogen-based flame retardant (B) and the light stabilizer (C), the heating method is not particularly limited, but specifically, a method using a heated chamber, The method of performing a heating and pressurization simultaneously using a roller can be illustrated.

  Moreover, it is preferable to heat in non-oxidizing atmosphere from a viewpoint of suppressing generation | occurrence | production of an undesirable side reaction, such as a decomposition reaction of a halogenated flame retardant (B) and a light stabilizer (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 the present invention, the take-up speed when bringing the halogen-based flame retardant (B) and the light stabilizer (C) into contact with the reinforcing fiber bundle (A) and the take-up speed when impregnating directly affect the process speed. From the viewpoint of economy and productivity, the higher the better. Specifically, the take-up speed is preferably 10 to 100 m / min. More preferably, it is 20-100 m / min, More preferably, it is 30-100 m / min. Examples of the pulling method include a method of drawing with a nip roller, a method of winding with a drum winder, and a method of pulling a composite reinforcing fiber bundle while cutting it to a certain length directly with a strand cutter or the like.

  Further, the reinforcing fiber bundle (A) may be opened in advance before the step of bringing the halogen flame retardant (B) and the light stabilizer (C) into contact with the reinforcing fiber bundle (A). The opening is an operation for dividing the converged reinforcing fiber bundle (A), and an effect of further improving the impregnation property of the molten halogen flame retardant (B) and the light stabilizer (C) can be expected. By opening the fiber, the thickness of the reinforcing fiber bundle (A) is reduced, the width of the reinforcing fiber bundle (A) before opening is w1 (mm), the thickness is t1 (μm), and the reinforcing fiber bundle after opening (A ) Width is w2 (mm) and the thickness is t2 (μm), it is preferable that the opening ratio = (w2 / t2) / (w1 / t1) is 2.0 or more, and 2.5 or more. More preferably.

  The method for opening the reinforcing fiber bundle (A) is not particularly limited. For example, a method of alternately passing concave and convex rolls, a method of using a drum-type roll, a method of applying a tension fluctuation to axial vibration, and a reciprocating vertically A method of changing the tension of the reinforcing fiber bundle (A) by two moving friction bodies and a method of blowing air to the reinforcing fiber bundle (A) can be used.

  FIG. 1 is a schematic view showing an example of a cross-sectional form of a composite reinforcing fiber bundle obtained by the present invention. In the present invention, the transverse section means a section in a plane orthogonal to the axial direction. The composite reinforcing fiber bundle obtained by the production method is formed as a composite in which the reinforcing fiber bundle (A) is coated and impregnated with the halogen-based flame retardant (B) and the light stabilizer (C) (hereinafter referred to as composite). Reinforcing fiber bundles are also called composites). The form of this composite is as shown in FIG. 1, and the halogen-based flame retardant (B) and the light stabilizer (C) are filled between the single fibers of the reinforcing fiber bundle (A). That is, the single fibers of the reinforcing fiber bundle (A) are dispersed like islands in the sea of the halogen-based flame retardant (B) and the light stabilizer (C).

  In the above composite, a composite in which the reinforced fiber bundle (A) is satisfactorily impregnated with the halogen-based flame retardant (B) and the light stabilizer (C), for example, is injected together with the thermoplastic resin composition (D). When molded, the halogenated flame retardant (B) and the light stabilizer (C) melted and kneaded in the cylinder of the injection molding machine diffuse into the thermoplastic resin composition (D), and the reinforcing fiber bundle (A) As a so-called impregnation aid / dispersion aid that helps dispersion in the thermoplastic resin composition (D) and at the same time helps the thermoplastic resin composition (D) to replace and impregnate the reinforcing fiber bundle (A). Have a role.

  The molding material in this invention is comprised from the said composite_body | complex and a thermoplastic resin composition (D). Here, the molding material in the present invention means a raw material used when molding a molded product by injection molding or the like.

  In the present invention, the thermoplastic resin composition (D) refers to a composition obtained by blending other various additives and fillers with a thermoplastic resin. The thermoplastic resin used here is not particularly limited, but polycarbonate resin, styrene resin, polyamide resin, polyester resin, polyphenylene sulfide resin (PPS resin), modified polyphenylene ether resin (modified PPE resin), polyacetal resin (POM). Resin), liquid crystal polyester, polyarylate, acrylic resin such as polymethyl methacrylate resin (PMMA), vinyl chloride, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone, polyethersulfone, polyketone , Polyetherketone, Polyetheretherketone (PEEK) Polyethylene such as polyethylene, polypropylene, modified polyolefin, phenolic resin, phenoxy resin, and ethylene Propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / diene copolymer, ethylene / carbon monoxide / diene copolymer, ethylene / (meth) ethyl acrylate copolymer, ethylene / (meta ) Glycidyl acrylate, ethylene / vinyl acetate / glycidyl (meth) acrylate copolymer, polyether ester elastomer, polyether ether elastomer, polyether ester amide elastomer, polyester amide elastomer, polyester ester elastomer and various other elastomers These may be used alone or in combination of two or more. In particular, polypropylene resins, polyamide resins, polycarbonate resins, and polyphenylene sulfide resins that are highly versatile are preferable.

  Moreover, the various additives and fillers which are mix | blended with a thermoplastic resin composition (D) can select arbitrary things in the range which does not impair the objective of this invention. Examples of additives and fillers include, for example, inorganic fillers, conductivity imparting agents, crystal nucleating agents, flame retardant aids, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, Examples include heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, or coupling agents. Use one or more of these in combination. You may do it. In particular, it is preferable that a flame retardant aid is blended from the viewpoint of further improving the flame retardancy, and since it exhibits a high synergistic effect with the halogen-based flame retardant, an antimony oxide compound is more preferable, and an antimony trioxide is further added. preferable.

  Further, the form of the molding material composed of the composite and the thermoplastic resin composition (D) in the present invention is not particularly limited. For example, the composite is cut into a chopped strand and the thermoplastic resin composition ( D) and the composite and the thermoplastic resin composition (D) are separated and treated, or the thermoplastic resin composition (D) is bonded and integrated with the composite. The thermoplastic resin composition (D) was bonded and integrated with the composite from the viewpoint of flowability during molding, uniformity of mechanical properties of the molded product, and concerns about blocking in the molding process. Those are more preferred. Specifically, using an extruder and a coating die for the wire coating method, the composite is continuously flattened around the composite with the thermoplastic resin composition (D), or rolled, etc. A film-like thermoplastic resin composition (D) melted by using an extruder and a T-die from one side or both sides of the composite is placed 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 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 molding material of the present invention, as shown in FIG. 2, the reinforcing fiber bundle (A) is arranged substantially parallel to the axial direction of the molding material, and the length of the reinforcing fiber bundle (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 long axis of the reinforcing fiber bundle (A) and the long 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. Further, “substantially the same length” means, for example, in a pellet-shaped molding material, the reinforcing fiber bundle (A) is cut in the middle of the pellet, or the reinforcing fiber bundle (A) significantly shorter than the entire length of the pellet. ) Is not substantially included. In particular, the amount of the reinforcing fiber bundle (A) shorter than the entire length of the pellet is not specified, but the content of the reinforcing fiber bundle (A) having a length of 50% or less of the total length of the pellet is 30% by weight or less. If it is, it is evaluated that the reinforcing fiber bundle (A) significantly shorter than the entire length of the pellet is substantially not contained. Furthermore, the content of the reinforcing fiber bundle (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 reinforcing fiber bundle (A) orientation direction in a pellet. Since the reinforcing fiber bundle (A) 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.

  3 to 6 each schematically show an example of the longitudinal cross-sectional form of the molding material of the present invention, and FIGS. 7 to 11 schematically show examples of the cross-sectional form of the molding material of the present invention. It is a representation.

  The cross-sectional form of the molding material is arranged such that the thermoplastic resin composition (D) adheres to the composite comprising the reinforcing fiber bundle (A), the halogen-based flame retardant (B), and the light stabilizer (C). However, it is not limited to the one shown in the figure, but preferably, as shown in FIGS. 3 to 5, the composite is a core material and is sandwiched and arranged in layers with the thermoplastic resin composition (D) Is preferred.

  Moreover, as FIG. 7-9 shows, the structure arrange | positioned at the core sheath structure which makes a composite_body | complex a core structure and the circumference | surroundings are covered with a thermoplastic resin composition (D) is preferable. Moreover, when arrange | positioning so that a composite thermoplastic resin composition (D) may coat | cover several composite_body | complex as shown in FIG. 11, the number of composite_body | complexes is about 2-6.

  The boundary between the composite and the thermoplastic resin composition (D) is bonded, and the thermoplastic resin composition (D) partially enters a part of the composite near the boundary to form a halogen flame retardant ( B) and the light stabilizer (C) may be in a compatible state, or the reinforcing fiber may be impregnated.

  The molding material of the present invention is kneaded by a technique such as injection molding or press molding to form a final molded product. From the viewpoint of the handling property of the molding material, it is more preferable that the composite and the thermoplastic resin composition (D) are not separated while being bonded until the molding is performed, and the shape as described above is maintained. The composite and the thermoplastic resin composition (D) are completely different in shape (size, aspect ratio), specific gravity, and mass, so they are classified and molded at the time of transportation and handling of materials until molding, and at the time of material transfer in the molding process. There are cases where the mechanical properties of the product vary, the fluidity is lowered and the mold is clogged, or blocking occurs in the molding process.

  From such a viewpoint, the configuration arranged in the core-sheath structure as illustrated in FIGS. If it is such arrangement | positioning, a thermoplastic resin composition (D) will restrain a composite_body | complex and a stronger composite can be performed. 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 is cut into a certain length. May be. Preferably, it is cut into 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.

  Further, the molding material of the present invention can be used depending on the molding method even if it is continuous or long. For example, as a thermoplastic yarn prepreg, it 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 while keeping them continuous in one direction. Such a prepreg can be applied to fields where lightness, high strength, elastic modulus, and impact resistance are required, such as automobile members.

  The proportion of the thermoplastic resin composition (D) in the molding material is 10 to 1000 parts by weight, preferably 50 to 700 parts by weight, and more preferably 100 to 400 parts by weight with respect to 100 parts by weight of the composite. Yes, by using within this range, a molded article having excellent mechanical properties can be obtained.

  The molding method of the molding material obtained in the present invention is not particularly limited, but can be applied to molding methods having excellent productivity such as injection molding, autoclave molding, press molding, filament winding molding, stamping molding, etc. It can also be used. 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 obtained by the above molding methods 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, intake manifolds, pedals Aircraft parts such as automobile parts, parts and skins, landing gear pods, winglets, spoilers, edges, ladders, failings, ribs, etc., parts and skins, tools such as monkeys, wrenches, telephones, facsimiles , VTRs, photocopiers, televisions, microwave ovens, audio equipment, toiletries, laser discs (registered trademark), refrigerators, air conditioners, and other home / office electrical product parts. Further, there may be mentioned a housing used for a personal computer, a mobile phone or the like, or a member for electric / electronic equipment represented by a keyboard support which is a member for supporting a keyboard inside the personal computer. In the present invention, when a carbon fiber bundle having conductivity is used as the reinforcing fiber bundle (A), such a member for electric / 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.

(1) Measurement of melt viscosity of impregnated compound Using a viscoelasticity measuring instrument (manufactured by Anton Paar Japan) and using a 40 mm parallel plate, the impregnated compound in a temperature range of 100 to 250 ° C. under the condition of 0.5 Hz. The melt viscosity of was measured.

(2) Measurement of impregnation amount with respect to supply amount of compound to be impregnated The composite was continuously collected for 1 minute, and placed in a heat-resistant glass container. Next, this container was vacuum-dried for 3 hours, cooled to room temperature while taking care not to absorb moisture, and the weighed value was defined as W ₁ (g). Next, the whole container was heated at 450 ° C. for 15 minutes in a nitrogen atmosphere, then cooled to room temperature while taking care not to absorb moisture, and the weighed value was defined as W ₂ (g). Through the above treatment, the impregnation weight of the compound to be impregnated was determined by the following formula, and the average value was defined as the impregnation weight wBC (measured n number = 5).
w _BC = W ₁ −W ₂

In the case where the sizing agent is granted to the reinforcing fiber, w _BC was calculated from the following equation.
w _BC = W ₁ −W ₂ −w _Sz
Here, w _Sz is the adhesion weight (g) of the sizing agent, and was obtained by the following equation using the value of W _Sz obtained in Reference Example 2 described later.
w _Sz = W _Sz W ₂ / (100−W _Sz )

Next, the supplied impregnated compound was sampled for 1 minute in the same manner as in the composite, and the weight was measured to determine the supply weight _wsp of the impregnated compound. .
Impregnation amount with respect to supply amount of impregnated compound = w _BC / w _sp (unit: wt%)

(3) Calculation of weight ratio (b) / (B) of sizing agent (b) and halogen flame retardant (B) The blending ratio of halogen flame retardant (B) and light stabilizer (C) is r _B : r _C and then, it was calculated by the following formula impregnation amount W _B of the halogen-based flame retardant (B).
W _B = W _BC × {r _B / (r _B + r _C )} (unit: weight%)
Here, W _BC is the impregnation amount of the halogen flame retardant (B) and the light stabilizer (C), and was obtained by the following formula using the values of W ₁ and W ₂ in the above (2).
W _BC = {(W ₁ −W ₂ ) / W ₂ } × 100
In addition, when a sizing agent was given to the reinforcing fiber bundle (A) in the composite, W _BC was obtained by the following equation using the value of w _{Sz in} (2) above.
W _BC = {(W ₁ −W ₂ −w _Sz ) / W ₂ } × 100
And calculated W _B using the values of W _Sz obtained by Reference Example 2 described later, it was calculated by the following formula (b) / (B).
(B) / (B) = W _Sz / W _B

(4) Bending test Based on ISO 178, the fulcrum distance was set to 64 mm using a three-point bending test jig (indenter radius 5 mm), and the bending strength was measured under the test conditions of a test speed of 2 mm / min. As a testing machine, an “Instron (registered trademark)” universal testing machine type 5566 (manufactured by Instron) was used.

(5) Flame retardancy FMVSS No. Using a square plate with dimensions of 100 mm x 150 mm x 3 mmt in accordance with 302 fire spread test, a gas burner flame with a height of 38 mm was contacted until the end of the square plate was ignited, and from the end to the marked line The self-extinguishing properties during were measured.
Judgment was made based on the following criteria, and ◎, ○, and Δ were regarded as acceptable.
A: Self-extinguishment within 30 seconds after flame contact.
○: Self-extinguishment within 30 seconds to 3 minutes after flame ignition.
Δ: Self-extinguishing within 3-7 minutes after flame contact.
X: It does not self-extinguish or it spreads to the marked line within 7 minutes after ignition.

(6) Weather resistance Using a UV long life fade meter (manufactured by Suga Test Machine Co., Ltd.), light was irradiated to a square plate having dimensions of 100 mm × 100 mm × 3 mmt under the condition of 83 ° C. and no water spray cycle. The surface of the test piece when the light irradiation time passed 500 hours was observed with a digital microscope (Model: VHX-900, manufactured by Keyence Corporation), and the weather resistance was measured in the state of the surface.
Judgment was made based on the following criteria, and ◎, ○, and Δ were regarded as acceptable.
A: No crack or surface roughness.
○: Although the number of cracks that can be counted is generated, the surface feel is smooth.
(Triangle | delta): The fine crack has arisen over the test piece surface whole surface, and the carbon fiber which is rough in the surface tactile sense is not exposed.
X: Innumerable cracks are generated on the entire surface of the test piece, and the carbon fibers on the surface are exposed.

(Reference Example 1-1) Production of carbon fiber-1 Spinning, baking treatment and electrolytic 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 unit length. A continuous carbon fiber having a mass per unit thickness of 1.6 g / m, a specific gravity of 1.8 g / cm 3 and a surface oxygen concentration [O / C] of 0.06 was obtained. The continuous carbon fiber had a strand tensile strength of 4880 MPa and a strand tensile modulus of 225 GPa.

(Reference Example 1-2) Production of carbon fiber-2 Spinning, baking treatment and electrolytic 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 unit length. A continuous carbon fiber having a mass per unit weight 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 continuous carbon fiber had a strand tensile strength of 4880 MPa and a strand tensile modulus of 225 GPa.

(Reference Example 2) Application of Sizing Agent A sizing agent mother liquor in which a sizing agent is dissolved or dispersed in water is prepared, and a sizing agent is applied to reinforcing fibers by a method of immersing in a sizing agent mother liquor via a roller. Drying was performed at ° C.

The adhesion amount W _Sz of the sizing agent was measured by the following method. About 5 g of reinforcing fiber to which a sizing agent was added was collected and placed in a heat-resistant glass container. Next, this container was vacuum-dried for 3 hours, cooled to room temperature while taking care not to absorb moisture, and the weighed value was defined as w ₁ (g). Next, the whole container was heated in a nitrogen atmosphere at 450 ° C. for 15 minutes, then cooled to room temperature while taking care not to absorb moisture, and the weighed value was defined as w ₂ (g). Through the above processing, the adhesion amount of the sizing agent was determined by the following equation, and the average value was defined as the adhesion amount W _Sz (measurement n number = 5).
W _Sz = {(w ₁ −w ₂ ) / w ₂ } × 100 (unit: wt%).

Reference Example 3 Production of Composite A liquid film in which the impregnated compound was heated and melted was formed on a roll heated to a temperature at which the impregnated compound was brought into contact with the reinforcing fiber bundle (hereinafter also referred to as coating temperature). . A reverse roll was used to form a film having a constant thickness on the roll. The continuous reinforcing fiber bundle (A) was passed through the roll while being in contact therewith to adhere the impregnated compound. Next, it passed between 5 sets of 50 mm diameter roll presses in the chamber heated to the impregnation temperature. By this operation, the compound to be impregnated was impregnated to the inside of the fiber bundle to form a composite having a predetermined blending amount.

(Reference Example 4) Production of thermoplastic resin composition (D) -1 A JSW TEX-30α type twin screw extruder (screw diameter 30 mm, die diameter 5 mm, barrel temperature 220 ° C., screw rotation speed 150 rpm) was used. Polypropylene resin (Prime Polymer Co., Ltd. Prime Polypro J105G resin) (D-1), maleic acid-modified polypropylene resin (Mitsui Chemicals Co., Ltd. Admer QE840) (D-2), Antimony trioxide (Showa Chemical Co., Ltd.) (Made) (D-3) is dry blended at a weight ratio of D-1 / D-2 / D-3 = 100/20/3 from the main hopper, while degassing from the downstream vacuum vent, The molten resin was discharged from the die port, and the obtained strand was cooled and then cut with a cutter to obtain a melt-kneaded pellet of the thermoplastic resin composition (D) -1.

(Reference Example 5) Production of molding material The composite obtained in Reference Example 3 was installed at the tip of a Nippon Steel Works TEX-30α type twin screw extruder (screw diameter 30 mm, L / D = 32). Then, the mixture was passed through a coating die for the wire coating method, and the thermoplastic resin composition (D) -1 obtained in Reference Example 4 was discharged from the extruder into the die in a molten state to cover the periphery of the composite. Were arranged continuously. At this time, the amount of the composite and the amount of the thermoplastic resin composition (D) -1 were adjusted so as to obtain a desired reinforcing fiber content. The obtained continuous molding material was cooled and then cut with a cutter to obtain a 7 mm long fiber pellet molding material.

Example 1
Carbon fiber-1 obtained according to Reference Example 1-1 was used as the reinforcing fiber bundle (A), and as the impregnated compound, the halogen-based flame retardant (B) was brominated flame retardant (manufactured by Maruhishi Oil Chemical Co., Ltd.). For the nonene PR-2) ((B) -1) and the light stabilizer (C), an amino ether type hindered amine light stabilizer (Tinuvin 123 manufactured by BASF Japan Ltd.) ((C) -1) was used. According to Reference Example 3, at a coating temperature of 120 ° C., an impregnation temperature of 180 ° C., and a take-off speed of 30 m / min, brominated flame retardant (B) -1 is 25 parts by weight with respect to 100 parts by weight of the reinforcing fiber bundle (A). The amount of supply was adjusted so that 1 part by weight of the amino ether type hindered amine light stabilizer (C) -1 was impregnated to obtain a composite. Here, the melt viscosity of the impregnated compound measured according to the above (1) was 0.07 Pa · s at 120 ° C. Subsequently, according to the above (2), the impregnation amount with respect to the supply amount of the brominated flame retardant (B) -1 and the amino ether type hindered amine light stabilizer (C) -1 was measured.

  Subsequently, according to Reference Example 4, the produced polypropylene resin composition (D) -1 was obtained, and according to Reference Example 5, a long fiber pellet-shaped molding material was obtained. Under the present circumstances, the discharge amount of polypropylene resin composition (D) -1 was adjusted so that polypropylene resin composition (D) -1 might be 240 weight part with respect to 100 weight part of composites.

  Next, using the SE75DUZ-C250 type injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., injection time: 10 seconds, holding pressure: molding lower limit pressure + 10 MPa, holding pressure time: 10 A test piece for characteristic evaluation (molded product) was molded at a second, cylinder temperature: 230 ° C., and mold temperature: 60 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test pieces for characteristic evaluation (molded products) were evaluated according to the injection molded product evaluation methods shown in the above (4) to (6). The evaluation results are summarized in Table 1.

(Example 2)
Carbon fiber-1 obtained according to Reference Example 1-1 was used as the reinforcing fiber bundle (A), and as the impregnated compound, the halogen-based flame retardant (B) was brominated flame retardant (manufactured by Maruhishi Oil Chemical Co., Ltd.). For the nonene PR-2) ((B) -1) and the light stabilizer (C), an amino ether type hindered amine light stabilizer (Tinuvin 123 manufactured by BASF Japan Ltd.) ((C) -1) was used. According to Reference Example 3, at a coating temperature of 120 ° C. and an impregnation temperature of 180 ° C., 25 parts by weight of the brominated flame retardant (B) -1 and 100 parts by weight of the reinforcing fiber bundle (A), an amino ether type hindered amine light The supply amount was adjusted so that 1 part by weight of the stabilizer (C) -1 was impregnated to obtain a composite. Here, the melt viscosity of the impregnated compound measured according to the above (1) was 0.07 Pa · s at 120 ° C. Subsequently, according to the above (2), the impregnation amount with respect to the supply amount of the brominated flame retardant (B) -1 and the amino ether type hindered amine light stabilizer (C) -1 was measured.

  Subsequently, the obtained composite was cut with a cutter to obtain a 6 mm carbon fiber chopped strand. Next, according to Reference Example 4, the produced polypropylene resin composition (D) -1 and the carbon fiber chopped strand were mixed with 240 parts by weight of the polypropylene resin composition (D) -1 with respect to 100 parts by weight of the carbon fiber chopped strand. A dry blended molding material was obtained.

  Next, the obtained dry blended molding material was subjected to injection time: 10 seconds, holding pressure: molding lower limit pressure + 10 MPa, holding pressure time: 10 seconds, cylinder using Sumitomo Heavy Industries, Ltd. SE75DUZ-C250 type injection molding machine. A test piece for characteristic evaluation (molded product) was molded at a temperature of 230 ° C. and a mold temperature of 60 ° C. The obtained test piece was subjected to a characteristic evaluation test after being left in a constant temperature and humidity chamber adjusted to a temperature of 23 ° C. and 50% RH for 24 hours. Next, the obtained test pieces for characteristic evaluation (molded products) were evaluated according to the injection molded product evaluation methods shown in the above (4) to (6). The evaluation results are summarized in Table 1.

(Example 3)
In the composite, the amount of impregnation of the brominated flame retardant impregnated into the reinforcing fiber bundle (A) (non-nene PR-2 manufactured by Maruhishi Oil Chemical Co., Ltd.) ((B) -1) is the reinforcing fiber bundle (A). 80 parts by weight with respect to 100 parts by weight, and in the long fiber pellet-shaped molding material, 170 parts by weight of the polypropylene resin composition (D) -1 is coated on 100 parts by weight of the composite. Molding evaluation was performed in the same manner as in Example 1 except that. The evaluation results are summarized in Table 1.

Example 4
In the composite, the amount of impregnation of the brominated flame retardant impregnated into the reinforcing fiber bundle (A) (non-nene PR-2 manufactured by Maruhishi Oil Chemical Co., Ltd.) ((B) -1) is the reinforcing fiber bundle (A). 10 parts by weight with respect to 100 parts by weight, and 300 parts by weight of the polypropylene resin composition (D) -1 is coated on 100 parts by weight of the composite in the long fiber pellet-shaped molding material. Molding evaluation was performed in the same manner as in Example 1 except that. The evaluation results are summarized in Table 1.

(Example 5)
In the composite, the impregnation amount of the amino ether type hindered amine light stabilizer (C) -1 impregnated in the reinforcing fiber bundle (A) is 10 parts by weight with respect to 100 parts by weight of the reinforcing fiber bundle (A). In the long fiber pellet-shaped molding material, molding evaluation was performed in the same manner as in Example 1 except that 100 parts by weight of the composite was coated with 250 parts by weight of the polypropylene resin composition (D) -1. went. The evaluation results are summarized in Table 1.

(Example 6)
As a compound to be impregnated into the reinforcing fiber bundle (A) at the time of preparing the composite, a halogen flame retardant (B) and a chlorine flame retardant (Empano 70 manufactured by Ajinomoto Fine Techno Co., Ltd.) ((B) -2) are used. The coating temperature was 150 ° C., the impregnation temperature was 200 ° C., and 50 parts by weight of 100 parts by weight of the reinforcing fiber bundle (A) was impregnated. Here, the melt viscosity of the impregnated compound measured according to the above (1) was 0.05 Pa · s at 150 ° C. Further, in the long fiber pellet-shaped molding material, molding evaluation was carried out in the same manner as in Example 1 except that 100 parts by weight of the composite was coated with 200 parts by weight of the polypropylene resin composition (D) -1. Went. The evaluation results are summarized in Table 1.

(Example 7)
As an impregnated compound to be impregnated into the reinforcing fiber bundle (A) at the time of producing the composite, the light stabilizer (C) is added to a non-aminoether type hindered amine light stabilizer (Chimassor2020 FDL, manufactured by BASF Japan Ltd.) ((C)- Molding evaluation was performed in the same manner as in Example 1 except that 2) was used. The evaluation results are summarized in Table 1.

(Example 8)
As the compound to be impregnated into the reinforcing fiber bundle (A) at the time of producing the composite, a benzoate light stabilizer (Tinuvin 120 manufactured by BASF Japan Ltd.) ((C) -3) was used as the light stabilizer (C). Except for the above, molding evaluation was carried out in the same manner as in Example 1. The evaluation results are summarized in Table 1.

Example 9
According to the above (3) and Reference Example 2, the carbon fiber used as the reinforcing fiber bundle (A) is replaced with a polyglycerol polyglycidyl ether ((b) -1) as a sizing agent (b) and a halogen flame retardant (B). The weight ratio of (b) / (B) = 0.08 / 1 was applied, and molding evaluation was performed in the same manner as in Example 1 except that the take-up speed at the time of producing the composite was 50 m / min. . The evaluation results are summarized in Table 2.

(Example 10)
According to the above (3) and Reference Example 2, the carbon fiber used as the reinforcing fiber bundle (A) is replaced with a polyglycerol polyglycidyl ether ((b) -1) as a sizing agent (b) and a halogen flame retardant (B). The weight ratio of (b) / (B) was set to 0.4 / 1, and molding evaluation was performed in the same manner as in Example 1 except that the take-up speed at the time of producing the composite was 80 m / min. . The evaluation results are summarized in Table 2.

(Example 11)
Example 1 except that the compound to be impregnated into the reinforcing fiber bundle (A) was prepared according to Reference Example 3 at a coating temperature of 100 ° C., an impregnation temperature of 180 ° C., and a take-up speed of 35 m / min. The molding was evaluated in the same manner as described above. The melt viscosity of the impregnated compound measured according to the above (1) was 0.14 Pa · s at 100 ° C. The evaluation results are summarized in Table 2.

(Example 12)
As an impregnated compound to be impregnated into the reinforcing fiber bundle (A) at the time of producing the composite, a halogen-based flame retardant (B) and a brominated flame retardant (Nonnen PR-2 manufactured by Maruhishi Oil Chemical Co., Ltd.) ((B) -1) and bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. jER1003) mixed at a weight ratio of 3: 1 ((B) -3), light stabilizer (C) and amino ether type hindered amine light stabilizer Agent (BASF Japan Co., Ltd. Tinuvin 123) ((C) -1), coating temperature 120 ° C., impregnation temperature 180 ° C., take-up speed 35 m / min, with respect to 100 parts by weight of reinforcing fiber bundle (A) Molding evaluation was performed in the same manner as in Example 1 except that 35 parts by weight was impregnated. The melt viscosity of the impregnated compound measured according to the above (1) was 0.12 Pa · s at 120 ° C. The evaluation results are summarized in Table 2.

(Example 13)
Example 12 except that the compound to be impregnated into the reinforcing fiber bundle (A) was prepared according to Reference Example 3 at a coating temperature of 100 ° C., an impregnation temperature of 180 ° C., and a take-up speed of 40 m / min. The molding was evaluated in the same manner as described above. The melt viscosity of the impregnated compound measured according to the above (1) was 1.2 Pa · s at 100 ° C. The evaluation results are summarized in Table 2.

(Example 14)
Molding evaluation was performed in the same manner as in Example 1 except that carbon fiber-2 obtained according to Reference Example 1-2 was used as the reinforcing fiber bundle (A). The evaluation results are summarized in Table 2.

(Example 15)
Molding evaluation was performed in the same manner as in Example 9 except that carbon fiber-2 obtained according to Reference Example 1-2 was used as the reinforcing fiber bundle (A). The evaluation results are summarized in Table 2.

(Comparative Example 1)
Molding evaluation was performed in the same manner as in Example 1 except that the light stabilizer (C) was not used as the compound to be impregnated into the reinforcing fiber bundle (A) when the composite was produced. The evaluation results are summarized in Table 3.

(Comparative Example 2)
In the composite, the amount of impregnation of the brominated flame retardant impregnated into the reinforcing fiber bundle (A) (non-nene PR-2 manufactured by Maruhishi Oil Chemical Co., Ltd.) ((B) -1) is the reinforcing fiber bundle (A). 120 parts by weight with respect to 100 parts by weight, and 100 parts by weight of the polypropylene resin composition (D) -1 is coated on 100 parts by weight of the composite in the long fiber pellet-shaped molding material. Molding evaluation was performed in the same manner as in Example 1 except that. The evaluation results are summarized in Table 3.

(Comparative Example 3)
In the composite, the impregnation amount of the amino ether type hindered amine light stabilizer (C) -1 impregnated in the reinforcing fiber bundle (A) is 15 parts by weight with respect to 100 parts by weight of the reinforcing fiber bundle (A). In the long fiber pellet-shaped molding material, molding evaluation was performed in the same manner as in Example 1 except that 100 parts by weight of the composite was coated with 210 parts by weight of the polypropylene resin composition (D) -1. went. The evaluation results are summarized in Table 3.

  As mentioned above, in Examples 1-15, the molded article obtained from the composite reinforcing fiber bundle in the present invention and the molding material showed excellent flame retardancy and weather resistance. In addition, a composite reinforcing fiber bundle having good impregnation properties and few voids was obtained by the method for manufacturing a composite reinforcing fiber bundle in the present invention.

  On the other hand, the composite reinforcing fiber bundles obtained in Comparative Examples 1 to 3 and molded articles molded using the molding materials did not sufficiently exhibit flame retardancy and weather resistance, or markedly deteriorated mechanical properties.

  The composite reinforcing fiber bundle of the present invention, the production method thereof, and the molding material have good resin impregnation into the reinforcing fiber bundle, and can give a molded product having excellent flame retardancy and weather resistance. It is extremely useful for various parts and members such as electrical / electronic equipment, office automation equipment, home appliances, or automobile parts, internal members, and housings.

1 Single fiber of reinforcing fiber 2 Halogen flame retardant (B) and light stabilizer (C)
3 Composite Reinforced Fiber Bundle 4 Thermoplastic Resin Composition (D)

Claims (12)

A composite reinforcing fiber bundle obtained by impregnating 10 to 100 parts by weight of a halogenated flame retardant (B) and 0.2 to 10 parts by weight of a light stabilizer (C) with respect to 100 parts by weight of a reinforcing fiber bundle (A). The composite reinforcing fiber bundle according to claim 1, wherein the component (C) is an amino ether type hindered amine light stabilizer. The composite reinforcing fiber bundle according to claim 1 or 2, wherein the component (A) includes a reinforcing fiber (a) and a sizing agent (b). The composite reinforcing fiber bundle according to claim 3, wherein a weight ratio (b) / (B) of the component (b) to the component (B) is 0.01 / 1 to 0.5 / 1. The composite reinforcing fiber bundle according to claim 3 or 4, wherein the component (b) is a trifunctional or higher polyfunctional aliphatic epoxy. The composite reinforcing fiber bundle according to any one of claims 1 to 5, wherein the component (A) is a carbon fiber bundle. The halogen-based flame retardant (B) and the light stabilizer (C) are brought into contact with the reinforcing fiber bundle (A) in a molten state at 100 to 320 ° C. and further heated to be halogenated flame retardant (B) and the light stabilizer (C The method for producing a composite reinforcing fiber bundle according to any one of claims 1 to 6, wherein the reinforcing fiber bundle (A) is impregnated with 80 to 100% by weight of the supply amount of (A). In the step of bringing the component (B) and the component (C) into contact with the component (A) in a molten state at 100 to 320 ° C., the melt viscosity of the component (B) and the component (C) is 0.01 to The method for producing a composite reinforcing fiber bundle according to claim 7, which is 10 Pa · s. 9. The halogen flame retardant (B) and the light stabilizer (C) are supplied using at least one selected from dipping, reverse roll, forward rotation roll, kiss roll, spray and curtain. A method for producing a composite reinforcing fiber bundle. The method for producing a composite reinforcing fiber bundle according to any one of claims 7 to 9, wherein the reinforcing fiber bundle (A) is impregnated using at least one selected from a drawing base, a drawing roll, a roll press and a double belt press. . The composite reinforcement according to any one of claims 7 to 10, wherein a take-up speed at the time of contacting and impregnating the reinforcing fiber bundle (A) with the halogen-based flame retardant (B) and the light stabilizer (C) is 10 to 100 m / min. A method of manufacturing a fiber bundle. A molding material comprising the composite reinforcing fiber bundle according to any one of claims 1 to 6 and a thermoplastic resin composition (D).

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