JP6561507B2 - Molding material, method for producing molded product using the same, and molded product - Google Patents

Description

  The present invention relates to a molding material, a method for producing a molded article using the molding material, and a molded article. More specifically, the present invention relates to a molding material excellent in impregnation into reinforcing fibers and excellent in mechanical properties of the obtained molded article, and a method for producing a molded article using the molding material and a molded article.

  Molding materials composed of reinforcing fibers and matrix 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 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.

  Known molding materials using a thermoplastic resin as a matrix resin include prepregs, yarns, glass mats (GMT) in which reinforcing fibers are impregnated with a thermoplastic resin, compound pellets, and long fiber pellets. These molding materials are characterized in that they can be easily molded by using the properties of the thermoplastic resin and are excellent in recyclability of the obtained molded product.

  However, in the process of producing a molding material, there is a problem in terms of economy and productivity in order to impregnate a thermoplastic resin particularly into continuous reinforcing fibers, and it is not widely used at present. It is well known that the higher the melt viscosity of the resin, the more difficult it is to impregnate the reinforcing fibers. Thermoplastic resins excellent in mechanical properties such as toughness and elongation are particularly high molecular weight bodies, and are not suitable for producing molding materials easily and with high productivity.

  As a composite material using a thermoplastic resin, for example, a fiber base material in a slurry composed of 100 parts by weight of a polyarylene sulfide resin (A), 0.1 to 30 parts by weight of an organosilane compound (B), and a dispersion medium There has been proposed a prepreg obtained by impregnating (see, for example, Patent Document 1). However, in order to produce such a prepreg, in addition to requiring equipment and time to dry the dispersion medium, it is difficult to completely remove the dispersion medium, and voids generated due to volatilization of the dispersion medium during lamination molding There was a problem that sufficient mechanical properties were not obtained. In addition, a fiber reinforced composite material comprising (A) a polyarylene sulfide having a melt viscosity of 3000 to 20000 poise and a tensile elongation at break of 10% or more and (B) a fiber substrate has been proposed ( For example, see Patent Document 2). However, even in such a composite material, molding conditions of high temperature and high pressure are necessary, and there is still a problem that mechanical properties are insufficient due to defects such as non-impregnation.

  In addition, a resin composition comprising (A) a cyclic polymerized component such as cyclic polyphenylene sulfide and (B) a thermosetting resin has been proposed (see, for example, Patent Document 3). By heat-polymerizing the resin composition, a composite cured product can be obtained by converting the component (A) into a thermoplastic resin such as polyphenylene sulfide together with the curing reaction of the component (B). However, the obtained molded product cannot be remelted and is not suitable for a molding material, and there is a problem that impregnation property and mechanical properties are insufficient.

Japanese Patent Laid-Open No. 5-39371 Japanese Patent Laid-Open No. 9-25346 International Publication No. 2012/081455

  In view of the above-mentioned problems of the prior art, the present invention provides a molding material having good impregnation properties and capable of obtaining a molded product having excellent mechanical properties, and is excellent in mechanical properties using the same. The purpose is to provide a molded product.

In order to solve the above problems, the molding material of the present invention has the following configuration. That is, (A) the reinforcing fiber includes (B) one or more selected from the group consisting of polyester, polyamide, polycarbonate, polyetheretherketone, polyetherketoneketone, polyetherimide, polysulfone, polyarylate, and polyphenylene ether. A molding material formed by impregnating a thermoplastic resin and (D) a resin composition containing (C) a cyclic polyarylene sulfide represented by the following general formula (1), comprising the components (A) to (C) 1 to 80 parts by weight of the component (A) is contained with respect to 100 parts by weight in total, and the ratio of the component (B) to the component (C) ((B) / (C)) = 10/90 to 40 / A molding material having a weight ratio of 60 , wherein the components (B) and (C) in the resin composition (D) are compatible at 320 ° C.

  In said general formula (1), Ar represents an arylene group and m represents the range of 2-50.

  The molding material of the present invention has good impregnation properties, and a molded product using the molding material of the present invention is excellent in mechanical properties. The molded article obtained by using the molding material of the present invention is extremely useful for various parts and members such as electric / electronic equipment, OA equipment, home appliances, automobiles, aircraft parts, internal members and housings.

  The molding material of the present invention is selected from the group consisting of (A) reinforcing fiber, (B) polyester, polyamide, polycarbonate, polyetheretherketone, polyetherketoneketone, polyetherimide, polysulfone, polyarylate, and polyphenylene ether. And (D) a resin composition containing (C) a cyclic polyarylene sulfide represented by the following general formula (1).

  In said general formula (1), Ar represents an arylene group and m represents the range of 2-50.

  First, these components will be described.

  (A) Reinforcing fiber used in the present invention is not particularly limited. For example, carbon fiber, glass fiber, aramid fiber, alumina fiber, silicon carbide fiber, boron fiber, metal fiber, etc., high strength, high elastic modulus fiber Is mentioned. These may be used alone or in combination of two or more. (A) By mix | blending a reinforced fiber, mechanical characteristics, such as an elasticity modulus and intensity | strength of a molded article, can be improved significantly. Among these, PAN-based, pitch-based, rayon-based and other carbon fibers are preferred from the viewpoint of further improving the mechanical properties of the obtained molded product and the effect of reducing the weight of the molded product, and the strength and elastic modulus of the obtained molded product. From the viewpoint of balance, PAN-based carbon fibers are more preferable. For the purpose of imparting conductivity, reinforcing fibers coated with a metal such as nickel, copper, or ytterbium can also be used.

  (A) Although the compounding quantity of a reinforced fiber can be selected according to the form of a molding material, it is 1-80 weight part with respect to a total of 100 weight part of said component (A)-(C). When the blending amount of the (A) reinforcing fiber is less than 1 part by weight, the mechanical properties of the (A) reinforcing fiber are not sufficiently exhibited, and the mechanical properties of the molded product are deteriorated. From the viewpoint of further improving mechanical properties, 5 parts by weight or more is preferable, and 8 parts by weight or more is more preferable. On the other hand, when the blending amount of (A) reinforcing fiber exceeds 80 parts by weight, the amount of matrix resin is relatively decreased, and thus an unimpregnated part is likely to occur, and the mechanical properties of the molded product may be deteriorated. Preferably it is 70 weight part or less, More preferably, it is 65 weight part or less.

  Component (B) used in the present invention is at least one heat selected from the group consisting of polyester, polyamide, polycarbonate, polyetheretherketone, polyetherketoneketone, polyetherimide, polysulfone, polyarylate, and polyphenylene ether. It is a plastic resin. By blending these thermoplastic resins, the mechanical properties of the molded product can be improved due to the toughness of the resin.

  Although it does not specifically limit as polyester, The polymer or copolymer obtained by the condensation reaction which has dicarboxylic acid and diol as a main component is mentioned. Specific examples include polybutylene terephthalate, polyethylene terephthalate, polylactic acid, and liquid crystal polyester. Two or more of these may be blended. Polybutylene terephthalate is marketed as “DURANEX” (registered trademark) manufactured by Wintech Polymer Co., Ltd., “Trecon” (registered trademark) manufactured by Toray Industries, Inc., and “Novaduran” manufactured by Mitsubishi Engineering Plastics Co., Ltd. You can also get what you have. Polyethylene terephthalate is marketed as “Kaneka Hyperlite” (registered trademark) manufactured by Kaneka Co., Ltd., “Rinite” (registered trademark) manufactured by DuPont Co., Ltd., and “Viopet” (registered trademark) manufactured by Toyobo Co., Ltd. You can also get what you have. As polylactic acid, commercially available products such as “Lacia” (registered trademark) manufactured by Mitsui Chemicals, Inc. and “Ecodia” (registered trademark) manufactured by Toray Industries, Inc. can be obtained and used. As liquid crystal polyester, "Siberus" (registered trademark) manufactured by Toray Industries, Inc., "Sumikasuper" (registered trademark) LCP manufactured by Sumitomo Chemical Co., Ltd., "Vectra" (registered trademark) manufactured by Celanese Japan Co., Ltd., etc. You can also obtain and use what is on the market.

  Although it does not specifically limit as polyamide, The polymer or copolymer obtained by the condensation reaction which has an amino acid, lactam, or diamine, and dicarboxylic acid as a main component is mentioned. Specific examples include nylon 6, nylon 66, nylon 46, nylon 610, nylon 11, nylon 12, nylon 6T, nylon 9T, and copolymers thereof. Two or more of these may be blended. In addition, “Amilan” (registered trademark) manufactured by Toray Industries, Inc., “Gramide” (registered trademark) manufactured by Toyobo Co., Ltd., “Zytel” (registered trademark) manufactured by DuPont Co., Ltd., “Genesta” manufactured by Kuraray Co., Ltd. What is marketed as (registered trademark) can also be obtained and used.

  Although it does not specifically limit as a polycarbonate, The polymer or copolymer which has a carbonate ester structure in a principal chain obtained by making bihydric phenol and a carbonate precursor react is mentioned. For example, it can be produced by a phosgene method, a transesterification method or 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.

  Polyetheretherketone is a polymer in which benzene rings are arranged via ether bonds, ether bonds, and ketone bonds. For example, “Vesta Keep” (registered trademark) manufactured by Daicel Evonik Co., Ltd., “VICTREX” (registered trademark) manufactured by Victrex Japan Co., Ltd., etc. can be obtained and used.

  Polyetherketone ketone is a polymer in which a benzene ring is arranged via an ether bond, a ketone bond, and a ketone bond. Although not particularly limited, those marketed as “Cypek” manufactured by Cytec Fiberte Co., Ltd., “KEPSTAN” (registered trademark) manufactured by Arkema Co., Ltd., etc. can be obtained and used.

  Polyetherimide is a polymer having an imide bond and an ether bond. Although not particularly limited, it is also possible to obtain and use what is marketed as “Ultem” (registered trademark) manufactured by SABIC Innovative Plastics Japan, “Aurum” (registered trademark) manufactured by Mitsui Chemicals, Inc. it can.

  Polysulfone is a polymer having a repeating unit containing a sulfonyl group. For example, commercially available products such as “Udel” (registered trademark) manufactured by Solvay and “Sumika Excel” (registered trademark) manufactured by Sumitomo Chemical Co., Ltd. can be obtained and used.

  The polyarylate is not particularly limited, and examples thereof include an aromatic polyester polymer obtained by polycondensation of a bisphenol compound and a phthalic acid compound. For example, what is marketed as “U Polymer” (registered trademark) manufactured by Unitika Ltd. can be obtained and used.

  The polyphenylene ether is a polymer having a repeating unit represented by the following general formula (14) as a main constituent unit, and contains 80 mol% or more of the repeating unit represented by the following general formula (14) in all repeating units. It is preferable.

  In the general formula (14), R6 to R9 represent hydrogen, halogen, or an optionally substituted hydrocarbon group, and may be the same or different. The hydrocarbon group preferably has 1 to 3 carbon atoms. n represents the range of 2-50, and it is preferable that n is 10-30.

  The polyphenylene ether is not particularly limited, and examples thereof include aromatic polyether polymers obtained by oxidative polymerization of 2,6-xylenol, such as poly (2,6-dimethyl-1,4-phenylene). Ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4) -Phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like. Moreover, polyphenylene ether copolymers such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol) are also included. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl- 1,4-phenylene ether) is more preferable. For example, “Zylon” (registered trademark) manufactured by Asahi Kasei Chemicals Corporation, “Iupiace” (registered trademark) manufactured by Mitsubishi Engineering Plastics Co., Ltd., etc. can be obtained and used.

  From the viewpoints of heat resistance and durability, polyether ether ketone, polyether ketone ketone, polyether imide, polysulfone, polyarylate, and polyphenylene ether are preferable. Polyether ketone ketone (PEKK), polyether imide, polysulfone, polyarylate, Polyphenylene ether is more preferable, and polyether ketone ketone (PEKK) and polyphenylene ether are more preferable.

  In the present invention, PEKK preferably contains a repeating unit represented by the following general formula (2). In the following general formula (2), Ph represents a 1,4-phenylene group or a 1,3-phenylene group which may be substituted with an alkyl group having 1 to 8 carbon atoms. Ph in a plurality of repeating units may be the same or different. Of all the repeating units, the repeating unit represented by the following general formula (2) is preferably 50% by weight or more, and more preferably 70% by weight or more.

  Moreover, it is preferable that the glass transition temperature of PEKK is 150-170 degreeC. If the glass transition temperature is 150 ° C. or higher, the heat resistance of the obtained molded product can be improved. On the other hand, if the glass transition temperature is 170 ° C. or lower, the toughness of the molded product can be further improved.

  The melting point of PEKK is preferably 280 to 400 ° C. If melting | fusing point is 280 degreeC or more, the heat resistance of a molded article can be improved. 290 ° C. or higher is more preferable. On the other hand, if the melting point is 400 ° C. or lower, the moldability is excellent. 370 ° C. or lower is more preferable.

  Moreover, in this invention, although the melt viscosity of a component (B) is not specifically limited, It is preferable that the melt viscosity in 320 degreeC is 50-5000 Pa.s. Here, attention is focused on 320 ° C. for the following reason. In general, the higher the temperature, the lower the melt viscosity of the thermoplastic resin. On the other hand, as described later, since component (C) is converted to (E) polyarylene sulfide by heating, polymerization of component (C) proceeds at a high temperature, resulting in melting of (D) resin composition. Viscosity may increase. Therefore, attention was paid to 320 ° C., which is a temperature at which the polymerization of the component (C) hardly occurs in the temperature range in which the component (B) and the component (C) are melted. If the melt viscosity at 320 ° C. is 50 Pa · s or more, the mechanical properties of the obtained molded product can be further improved. 100 Pa · s or more is more preferable, and 500 Pa · s or more is more preferable. On the other hand, if the melt viscosity at 320 ° C. is 5000 Pa · s or less, it can be stably impregnated into the inside of the reinforcing fiber bundle (A) by a general impregnation method, and the impregnation property can be further improved. . 3000 Pa · s or less is more preferable, and 2000 Pa · s or less is more preferable. Here, although attention is paid to the melt viscosity of the component (B) at 320 ° C., as described later, the temperature at which the (D) thermoplastic resin composition is produced or impregnated can be appropriately selected.

  In addition, the melt viscosity of a component (B) can be measured on the conditions of 0.5 Hz and 320 degreeC using a 40-mm parallel plate using a viscoelasticity measuring device.

  Further, the glass transition temperature of the component (B) is not particularly limited. However, the higher the glass transition temperature, the higher the effect of improving the heat resistance of the obtained molded product. The above is more preferable. As an upper limit, 350 degreeC or less is preferable and 320 degreeC or less is more preferable from a compatible viewpoint with the below-mentioned cyclic polyarylene sulfide and workability.

  The cyclic polyarylene sulfide represented by the general formula (1) used in the present invention has a repeating unit of-(Ar-S)-as a main constituent unit, and preferably the repeating unit is 80 mol% in all repeating units. Contains above. Here, Ar represents an arylene group, S represents a sulfide, and m represents a range of 2 to 50.

  Here, the component (C) is a so-called oligomer, has a low melt viscosity, and is excellent in (A) impregnation into the reinforcing fiber. Moreover, since it can convert into (E) polyarylene sulfide by heating so that it may mention later, the mechanical characteristic of the obtained molded article can be improved greatly.

  Examples of Ar in the general formula (1) include groups represented by the following general formulas (3) to (11). Among these, a group represented by the following general formula (3) is preferable.

  In the general formulas (3) to (11), R1 and R2 represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a halogen group. , R1 and R2 may be the same or different. A plurality of R1 and R2 may be the same or different. R3 and R4 represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 24 carbon atoms, or a halogen group, and may be the same or different. R5 is a saturated hydrocarbon group having 1 to 12 carbon atoms. Moreover, a and b represent the range of 0-2, and may be same or different. A represents a carbonyl group, a sulfonyl group or an ether bond. )

  In the general formula (1), different — (Ar—S) — repeating units may be included randomly, in blocks, or both. Further, as Ar, two or more groups represented by the general formulas (3) to (11) may be included.

  Typical cyclic polyarylene sulfides represented by the general formula (1) include cyclic polyarylene sulfides, cyclic polyarylene sulfide sulfones, cyclic polyarylene sulfide ketones, and cyclic random copolymers containing these repeating units. And cyclic block copolymers. Two or more of these may be blended. Among these, the cyclic polyphenylene sulfide containing 80 mol% or more of the units derived from p-phenylene sulfide represented by the following structural formula (12) in the total repeating units is more preferable, and the cyclic polyphenylene sulfide containing 90 mol% or more is more preferable. preferable.

  The repeating number m in the general formula (1) is 2-50. As will be described later, the conversion to (E) polyarylene sulfide by heating the component (C) is preferably performed at a temperature equal to or higher than the temperature at which the component (C) melts, but when m increases, the melting solution temperature of the component (C) Therefore, m is set to 50 or less from the viewpoint that the conversion of the component (C) to the component (E) can be performed at a lower temperature. m is preferably 25 or less, and more preferably 20 or less. On the other hand, m is preferably 3 or more. Here, the repetition number m in the general formula (1) can be obtained by performing structural analysis by NMR and mass analysis.

  In addition, the component (C) may be either a single compound having a single repeating number m or a mixture of cyclic compounds having different repeating numbers m as the compound represented by the general formula (1). However, a mixture of cyclic compounds having different numbers of repetitions tends to have a lower melt solution temperature than a single compound having a single number of repetitions, and the temperature during conversion to component (E) is lower. This is preferable because it is possible.

  The component (C) can be obtained, for example, by heating and reacting a reaction mixture containing at least a sulfidizing agent (sulfur component), a dihalogenated aromatic compound (arylene component) and an organic polar solvent. Examples of the sulfidizing agent include alkali metal sulfides such as sodium sulfide. Examples of the dihalogenated aromatic compound include dichlorobenzene. Examples of the organic polar solvent include N-methylpyrrolidone.

  From the viewpoint of efficiently producing the component (C), it is desirable to heat the reaction mixture beyond the reflux temperature under normal pressure. The reaction temperature is preferably 180 to 320 ° C, more preferably 225 to 300 ° C. Further, it may be a one-step reaction in which the reaction is carried out at a constant temperature, a multi-stage reaction in which the reaction is carried out by raising the temperature stepwise, or a form in which the reaction is carried out by continuously changing the temperature.

  The reaction time is preferably 0.1 hour or longer, more preferably 0.5 hour or longer. On the other hand, the reaction time has no particular upper limit, and the reaction proceeds sufficiently even within 40 hours, preferably within 6 hours.

  Moreover, there is no restriction | limiting in particular in the pressure at the time of reaction, 0.05 MPa or more is preferable at a gauge pressure, and 0.3 MPa or more is more preferable. Since the pressure rise due to the self-pressure of the reaction mixture occurs at the preferable reaction temperature, the pressure at such a reaction temperature is preferably 0.25 MPa or more, more preferably 0.3 MPa or more in terms of gauge pressure. On the other hand, the pressure during the reaction is preferably 10 MPa or less, and more preferably 5 MPa or less. In order to make the pressure during the reaction within the preferred range, it is also preferable to pressurize the reaction system with an inert gas at any stage such as before starting the reaction or during the reaction, preferably before starting the reaction. It is. Here, the gauge pressure is a relative pressure based on the atmospheric pressure, and is equivalent to a pressure difference obtained by subtracting the atmospheric pressure from the absolute pressure.

  In the present invention, the organic carboxylic acid metal salt may be present throughout the entire process of reacting the reaction mixture, or the organic carboxylic acid metal salt may be present only in a part of the process.

  The molding material of the present invention is obtained by impregnating (A) reinforcing fibers with (D) a resin composition containing the above components (B) and (C). (D) In the resin composition, the weight ratio of component (B) to component (C) ((B) / (C)) is 10/90 to 40/60. When the weight ratio of the component (B) is less than 10, mechanical properties such as toughness of the molded product may be deteriorated. The weight ratio of component B is preferably 15 or more. On the other hand, when the weight ratio of the component (B) exceeds 40, the impregnation property to the (A) reinforcing fiber is lowered and mechanical properties such as toughness of the molded product are lowered. The weight ratio of component B is preferably 35 or less.

  As for the molding material of this invention, it is preferable that the component (B) and the component (C) are compatible in (D) resin composition at 320 degreeC. The state of being compatible means that the (D) resin composition at 320 ° C. cannot be confirmed as undissolved lump or agglomerate when observed at 100 times magnification using an optical microscope. Refers to that. When component (B) and component (C) are compatible and uniform, when component (A) is impregnated into component (A), it can be more stably impregnated.

  Here, attention is focused on 320 ° C. for the following reason. The higher the temperature of the thermoplastic resin, the lower the melt viscosity. On the other hand, the component (C) is converted to (E) polyarylene sulfide by heating as described later. When component (C) is mixed, polymerization of component (C) proceeds, and as a result, the melt viscosity of the mixed resin composition may increase. Therefore, 320 ° C., which is a temperature at which the polymerization of the component (C) hardly proceeds in the temperature range where the component (B) and the component (C) melt, is important. Here, although attention was paid to the compatibility of the component (B) and the component (C) at 320 ° C., as will be described later, the temperature at which the (D) thermoplastic resin composition is produced or impregnated is appropriately selected. be able to.

  The means for compatibilizing component (B) and component (C) is not particularly limited. For example, it is preferable to knead at 320 ° C. while component (B) and component (C) are melted. Since both are melted, it is easy to uniformly disperse and to be compatible. Although it does not specifically limit as a kneading apparatus, An extruder, a kneader, etc. can be mentioned. Further, as the component (B), selecting a component having a melt viscosity at 320 ° C. of 50 to 5000 Pa · s as described above makes it easy to uniformly disperse the component (B) and the component (C). It is preferable because it is easy to dissolve.

  The molding material of the present invention may be blended with fillers and additives other than the components (A) to (C) as long as the object of the present invention is not impaired. Examples of these include inorganic fillers other than the reinforcing fibers (B), flame retardants, conductivity imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insecticides, and deodorants. , Anti-coloring agents, heat stabilizers, release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, coupling agents, and the like. ) And (C) may be contained in the resin composition (D).

  Next, the manufacturing method of the molding material of this invention is demonstrated. (1) A method comprising mixing a component (B) and a component (C) to obtain (D) a resin composition, and (2) (D) impregnating the component (A) with the resin composition in this order. preferable.

  The step (1) is not particularly limited as long as it is a method of uniformly dispersing the component (B) and the component ((C). Examples of the method of uniformly dispersing include the component (B) and the component ( (C) and, if necessary, a method of melting and dispersing other components by heating, a method of mechanically dispersing, a method of dispersing using a solvent, etc. Preferably, component (B), component ((C) and This is a method in which other components are heated and melted and dispersed if necessary, and examples of the apparatus for heating and melting and dispersing include, for example, an extruder, a kneader, etc. The heating temperature is the components (B) and (C). Although it is not particularly limited as long as it can be made compatible, it is preferably 350 ° C. or lower from the viewpoint of suppressing unintended polymerization of component (C), while the view of melting component (B) and component ((C)). From, preferably equal to or greater than 250 ℃.

  Next, a molding material can be obtained through the step (2) of impregnating the component (A) with the resin composition (D) obtained in the step (1). The method of impregnating the resin composition (D) obtained in step (1) is not particularly limited. For example, a method of immersing component (A) in a molten (D) resin composition and impregnating it with a solvent Examples include a method of impregnation by dissolving the component (A) in the dissolved resin composition (D) and volatilizing the solvent. (D) When component (B) and component (C) are compatible at 320 ° C., the resin composition can be impregnated more uniformly.

  Next, the manufacturing method of the molded article using the molding material of this invention is demonstrated. By heating the molding material of the present invention, the component (C) can be converted to (E) polyarylene sulfide to obtain a molded product.

  (E) The polyarylene sulfide is a polymer or copolymer having a repeating unit of-(Ar-S)-as a main constituent unit, preferably containing 80 mol% or more of the repeating unit in all repeating units. . Here, Ar represents an arylene group. Examples of Ar include groups represented by the general formulas (3) to (11). Among them, the group represented by the general formula (3) is particularly preferable.

  As long as the repeating unit of-(Ar-S)-is used as the main structural unit, it can contain a small amount of branching units or crosslinking units represented by the following general formula (13). The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-S)-units.

  Component (E) in the present invention may contain different — (Ar—S) — repeating units at random, may be contained in blocks, or may contain both. Further, as Ar, two or more groups represented by the general formulas (3) to (11) may be included.

  Examples of the component (E) include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and a random copolymer or block copolymer thereof. Two or more of these may be used. Among all the repeating units, polyphenylene sulfide containing 80 mol% or more of the unit derived from p-phenylene sulfide represented by the structural formula (12) is preferable, and polyphenylene sulfide containing 90 mol% or more is more preferable.

  The weight average molecular weight of the component (E) is preferably 10,000 or more, and the mechanical properties of the molded product can be further improved. 15,000 or more is more preferable, and 17,000 or more is more preferable. Here, the weight average molecular weight of polyphenylene sulfide can be determined using gel permeation chromatography.

  Further, the conversion rate of the component (C) to the component (E) is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. By setting the conversion ratio of the low molecular weight component (C) to the component (E) to 70% or more, the mechanical properties of the obtained molded product can be further improved.

  The heating temperature of the molding material can be appropriately selected according to the composition and molecular weight of the (D) resin composition and the environment during heating. From the viewpoint of converting the component (C) to the component (E) in a shorter time, it is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, and further preferably 280 ° C. or higher. On the other hand, from the viewpoint of suppressing side reactions such as decomposition reactions, the heating temperature is preferably 450 ° C. or lower, and more preferably 400 ° C. or lower.

  The heating time can be appropriately selected according to conditions such as (D) various characteristics of the resin composition and heating temperature. From the viewpoint of sufficiently adding the component (C) to the component (E), the heating time is preferably 0.01 hours or more, and more preferably 0.05 hours or more. On the other hand, from the viewpoint of suppressing side reactions such as decomposition reactions, 100 hours or less is preferable, 20 hours or less is more preferable, 10 hours or less is more preferable, 6 hours or less is further preferable, and 3 hours or less is more preferable.

  The molding method of the molded product of the present invention is not particularly limited, and examples thereof include molding methods with excellent productivity such as injection molding, autoclave molding, press molding, filament winding molding, stamping molding, and the like. Can be used.

  Next, the molded product of the present invention will be described. In the molded product, the phase separation structure of the resin composition (F) containing the component (B) and the component (E) is not particularly limited, and it has a uniform structure in which the components (B) and (E) are compatible. It may be a two-phase continuous structure or a dispersed structure. Among them, the so-called sea-island structure in which the component (B) is the sea phase and the component (E) is the island phase is preferable, the toughness of the component (B) is more effectively expressed, and the mechanical properties of the molded product are further improved. Can be made. Here, the sea-island structure is a phase-separated structure in which particles (island phases) whose main component is the other resin component are interspersed in a matrix (sea phase) whose main component is one of the resin components. Refers to that.

  Here, the method of forming the phase separation structure can be appropriately selected according to the type and blending ratio of the components constituting the resin composition (F), the shape of the molded product, etc. Examples thereof include a method for adjusting the solidification rate after conversion into the component (E). Since the system that was in the stable region rapidly becomes an unstable region due to the conversion of component (C) to component (E), the (D) resin composition that was in a compatible state undergoes spinodal decomposition, respectively. These components form a continuous phase and form a three-dimensionally entangled structure, that is, a co-continuous structure. From this state, when the solidification rate is increased, for example, by rapidly cooling with ice water or the like, the structure is fixed in a state where the component (C) is converted to the component (E), so that a uniform structure or a two-phase continuous structure is likely to occur. Tend. On the other hand, the sea-island structure can be formed by developing the phase separation structure by a method such as further heating to increase the melting time or gradually cooling the resin composition to reduce the solidification rate. For this reason, for example, after converting a component (C) into a component (E) by heating, a sea-island structure can be formed by cooling slowly. The cooling rate is preferably 20 ° C./min or less. Moreover, it becomes easy to form a sea-island structure also by using the component (B) whose melt viscosity in 320 degreeC exists in the above-mentioned preferable range.

  By forming a phase separation structure by conversion of the component in the (D) resin composition in a compatible state, the component to be converted can be an island phase. That is, in the present invention, by converting the component (C) to the component (E), a sea-island structure in which the component (E) is the island phase and the component (B) is the sea phase can be formed. By using the component (B) having high toughness as the sea phase, the toughness of the molded product can be further improved.

  In the sea-island structure, the interparticle distance between island phases is preferably 0.01 to 10 μm. When the distance between particles is 0.01 μm or more, the characteristics of each resin are expressed, and the toughness of the molded product can be improved. 0.1 μm or more is more preferable, and 0.5 μm or more is more preferable. On the other hand, if the interparticle distance is 10 μm or less, the mechanical properties of the molded product can be further improved. 5 μm or less is more preferable.

  Here, the method for adjusting the interparticle distance to the above range can be appropriately selected according to the type and blending ratio of the components constituting the resin composition (F), the shape of the molded product, and the like. Examples thereof include a method for adjusting the solidification rate after conversion of B) into component (E). As described above, since the phase structure of the component (E) that is an island grows with the conversion to the component (E), the interparticle distance can be adjusted to a desired range by adjusting the solidification rate. it can. Examples of means for slowing the solidification rate include a method of selecting a component (B) having a low glass transition temperature and a melting point, and a method of slowing the cooling rate after converting the component (B) to the component (E). Can be mentioned. Moreover, the growth of the phase structure of the component (E) which is an island phase can also be adjusted by adjusting the conversion rate of the component (C) to the component (E). That is, by increasing the polymerization rate, the conversion of the component (C) to the component (E) is completed before the phase structure grows, and the phase structure can be reduced by cooling it. Also, the phase structure can be reduced by mixing the components (B) and (C) before the conversion of the component (C) to the component (E).

  Here, the interparticle distance between the island phases of the molded product in the present invention can be measured by, for example, the following method by observing the cross section of the molded product with a transmission electron microscope. First, 10 straight lines are randomly drawn on a square electron microscope observation photograph, and an appropriate observation magnification is adjusted so that 10 or more and less than 100 island phases touch each straight line. At such an appropriate observation magnification, the distance of the line segment from end to end of a straight line drawn randomly in the observation image is divided by the number of touching islands. The same operation is performed for 10 straight lines. This operation is performed on 10 electron microscope observation photographs randomly selected from the cross section of the molded product, and the interparticle distance can be obtained by calculating the number average value thereof. The distance of the line segment here is an actual distance, and the actual distance can be obtained based on the scale bar in the observation photograph.

  Molded articles of the present invention include automotive panels such as instrument panels, door beams, under covers, lamp housings, pedal housings, radiator supports, spare tire covers, front ends, etc., cylinder head covers, bearing retainers, intake manifolds, pedals, etc. , Parts and skins, landing gear pods, winglets, spoilers, edges, ladders, failings, ribs and other aircraft related parts, parts and skins, tools such as monkeys, wrenches, telephones, facsimiles, VTRs, copiers , Housings used for household and office electrical product parts such as TVs, microwave ovens, audio equipment, toiletries, optical discs, refrigerators, air conditioners, personal computers, mobile phones, and personal computers It can be suitably applied to applications such as electrical and electronic equipment member typified by a keyboard support which is a member for supporting the keyboard inside.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.

The following were used as raw materials for each of the examples and comparative examples.
(B) One or more thermoplastic resins selected from the group consisting of polyester, polyamide, polycarbonate, polyetheretherketone, polyetherketoneketone, polyetherimide, polysulfone, polyarylate, and polyphenylene ether (B-1) Arkema “KEPSTAN” (registered trademark) 6003: Polyether ketone ketone (glass transition temperature: 161 ° C., melting point: 303 ° C.)
(B-2) “Panlite” (registered trademark) L1225L manufactured by Teijin Limited: Polycarbonate (glass transition temperature: 148 ° C., melting point: 250 ° C.)
(B-3) “Amilan” (registered trademark) CM1010 manufactured by Toray Industries, Inc .: polyamide (glass transition temperature: 50 ° C., melting point: 225 ° C.)
(B-4) “ULTEM” (registered trademark) 1010 manufactured by Savic Co., Ltd .: polyetherimide (glass transition temperature: 217 ° C., melting point: no clear melting point)
(B-5) 150P: polyetheretherketone (glass transition temperature: 143 ° C., melting point: 343 ° C.) manufactured by Victrex Co., Ltd.
(B-6) “Udel” (registered trademark) P-3500 manufactured by Solvay: Polysulfone (glass transition temperature: 190 ° C., melting point: no clear melting point)
(B-7) “U Polymer” (registered trademark) U-100 manufactured by Unitika Ltd .: Polyarylate (glass transition temperature: 195 ° C., melting point: no clear melting point)
(B-8) YPX-100F manufactured by Mitsubishi Gas Chemical Co., Ltd .: polyphenylene ether (glass transition temperature: 210 ° C., melting point: no clear melting point)
Evaluation in each example and comparative example was performed by the following method.

(1) Observation of compatible state at 320 ° C. (D) Resin composition in which components (B) and (C) used in each Example and Comparative Example are blended in a predetermined amount in each Example and Comparative Example Mixed in and heated in a 320 ° C. oven for 5 minutes with occasional stirring. A part of the obtained resin composition (D) was collected on a cover glass and covered with another cover glass from above to prepare a preparation. The preparation was observed at an observation magnification of 100 times using an optical microscope while being heated to 320 ° C. on a hot stage (Rinkham, model 10002). The case where no lump or aggregate was observed was “compatible”, and the case where it was observed was “incompatible”.

(2) Viscosity measurement of component (B) About the component (B) used for each Example and the comparative example, using a 40-mm parallel plate using a viscoelasticity measuring device, conditions of 0.5 Hz and 320 degreeC The viscosity was measured at

(3) Porosity Measurement of Molding Material The porosity (%) of the molding material was calculated according to ASTM D2734 (1997) test method. Determination of the porosity of the molding material was performed according to the following criteria, and A to C were determined to be acceptable.
A: 0 to less than 10% B: 10% to less than 20% C: 20% to less than 40% D: 40% or more.

(4) Strength measurement of molded product A test piece having a length of 50 mm, a width of 10 mm, and a thickness of 0.5 mm using a diamond cutter in a state where the molded product obtained in each example and comparative example was fixed by a vise. Was cut out. Using the obtained test piece, a tensile test was performed in a 90 ° direction with respect to the longitudinal direction of the reinforcing fiber at a crosshead speed of 5 mm / min at a chuck distance of 10 mm, and the tensile strength was measured. The measurement was carried out for each of five test pieces, and the average value was calculated.

(5) (F) Observation of phase-separated structure of resin composition From a molded product obtained in each example and comparative example, a cross-sectional observation of about 2 mm × about 1 mm with a diamond knife using a Leica ultramicrotome (EM UC7). A sample was prepared. With a transmission electron microscope (H-7100 manufactured by Hitachi, Ltd.), the phase structure of the cross section of the observation sample was observed at an acceleration voltage of 100 kV at 1000 to 10000 times. About the sample which has formed sea island structure, the distance between particles of an island phase was calculated | required with the following method. In addition, the sea-island structure is a structure in which one component is formed into particles, the main component of which is the main component, and a matrix, the other component of which is the main component, and the matrix is interspersed with particles. Refers to that.

  First, 10 straight lines were randomly drawn on a square electron microscope observation photograph, and an appropriate observation magnification was adjusted so that 10 or more and less than 100 island phases were in contact with any of the straight lines. At such an appropriate observation magnification, the distance of the line segment from end to end of a straight line drawn randomly in the observation image was divided by the number of touching islands. The same operation was performed for 10 straight lines. This operation was performed on 10 randomly selected electron microscopic observation photographs on the sample, and the number average value thereof was calculated to determine the interparticle distance between island phases. Here, the distance of the line segment is an actual distance, and the actual distance was obtained based on the scale bar in the observation photograph.

(6) Evaluation of island phase component About the molded product in which the sea-island structure was formed in the transmission electron microscope observation described in (5) above, 95 samples prepared by the same method as the cross-sectional observation sample described in (5) were used. After being immersed in 1% sulfuric acid for 1 minute and taken out, the surface was washed with running water for 10 minutes. Next, after drying in a 60 ° C. hot air dryer for 1 hour, the surface of the sample was observed with a field emission scanning electron microscope (JEOL JSM-6301NF) at an acceleration voltage of 5 kV and an emission current of 12 μA. Observed. The remaining component is (E) polyphenylene sulfide which is not attacked by sulfuric acid, and it was determined by this surface observation whether or not the island phase component was (E) polyphenylene sulfide.

(7) Evaluation of heat resistance With a molded product obtained by each example and comparative example fixed in a vise, a test piece having a length of 50 mm, a width of 10 mm, and a thickness of 0.1 mm was cut out using a diamond cutter. It was. At this time, the length direction of the test piece was set to be 90 ° with respect to the longitudinal direction of the reinforcing fiber. The test piece obtained was held in a cantilevered state so that the test piece was held in a horizontal state at 20 mm and left standing in an oven at 110 ° C. for 4 minutes. The amount of change (horizontal distance) drooped by was measured, and the heat resistance was evaluated. The measurement was carried out for each of five test pieces, and the average value was calculated. The smaller the amount of change, the better the heat resistance.

Reference Example 1 Component (C) -1 (Preparation of cyclic polyphenylene sulfide (PPS))
A stainless steel autoclave equipped with a stirrer was charged with 14.03 g (0.120 mol) of a 48 wt% aqueous solution of sodium hydrosulfide and 12.50 g of a 48 wt% aqueous sodium hydroxide solution prepared using 96 wt% sodium hydroxide. (0.144 mol), 615.0 g (6.20 mol) of N-methyl-2-pyrrolidone (NMP) and 18.08 g (0.123 mol) of p-dichlorobenzene (p-DCB) were charged. The reaction vessel was sufficiently purged with nitrogen, and then sealed under nitrogen gas.

  While stirring at 400 rpm, the temperature was raised from room temperature to 200 ° C. over about 1 hour. At this stage, the pressure in the reaction vessel was 0.35 MPa as a gauge pressure. Next, the temperature was raised from 200 ° C. to 270 ° C. over about 30 minutes. The pressure in the reaction vessel at this stage was 1.05 MPa as a gauge pressure. After maintaining at 270 ° C. for 1 hour, the contents were recovered after quenching to near room temperature.

  As a result of analyzing the obtained contents by gas chromatography and high performance liquid chromatography, the consumption rate of monomeric p-DCB was 93%, and the cyclic PPS was assumed when all sulfur components in the reaction mixture were converted to cyclic PPS. The production rate was found to be 18.5%.

  500 g of the obtained contents were diluted with about 1500 g of ion-exchanged water, and then filtered through a glass filter having an average opening of 10 to 16 μm. The filter-on component was dispersed in about 300 g of ion-exchanged water, stirred at 70 ° C. for 30 minutes, and subjected to the same filtration again three times in total to obtain a white solid. This was vacuum dried at 80 ° C. overnight to obtain a dry solid.

  The obtained solid matter was charged into a cylindrical filter paper, and Soxhlet extraction was performed for about 5 hours using chloroform as a solvent, thereby separating low molecular weight components contained in the solid content.

  The solid component remaining in the cylindrical filter paper after the extraction operation was dried under reduced pressure at 70 ° C. overnight to obtain about 6.98 g of an off-white solid. As a result of analysis, this was a compound having a phenylene sulfide structure, and the weight average molecular weight was 6,300, from the absorption spectrum in infrared spectroscopic analysis.

  After removing the solvent from the extract obtained by the chloroform extraction operation, about 5 g of chloroform was added to prepare a slurry, which was added dropwise to about 300 g of methanol while stirring. The precipitate thus obtained was collected by filtration and vacuum dried at 70 ° C. for 5 hours to obtain 1.19 g of a white powder. This white powder was confirmed to be a compound composed of phenylene sulfide units from an absorption spectrum in infrared spectroscopic analysis. Moreover, this white powder has p-phenylene sulfide unit as the main constituent unit based on the mass spectrum analysis of the component divided by high performance liquid chromatography (apparatus; M-1200H manufactured by Hitachi) and molecular weight information by MALDI-TOF-MS. It was found to contain about 99% by weight of a cyclic compound having 4 to 13 repeating units. As a result of GPC measurement, (C) -1 was completely dissolved in 1-chloronaphthalene at room temperature, and the weight average molecular weight was 900.

Example 1
In a kneader, polyether ketone ketone (B) -1 (KEPSTAN 6003 manufactured by Arkema Co., Ltd.) 15 mass% as component (B), and (C) -1 85 mass obtained in Reference Example 1 as component (C) % Was heated to 320 ° C. and kneaded for 5 minutes to obtain a resin composition (D). When the compatible state at 320 ° C. was observed, it was found to be compatible. Next, (D) resin composition was poured into a 100 mm × 100 mm mold in which CF-1 (carbon fiber manufactured by Toray Industries, Inc .: T700S-24K) was installed in one direction, and a heating press machine heated to 360 ° C. Then, the molding material was obtained by heating at 1.5 MPa for 5 minutes. The obtained molding material was further heated for 2 hours at 1.5 MPa in a heating press heated to 360 ° C., gradually cooled at a rate of 10 ° C./min, and cooled to room temperature, thereby being 100 mm × A molded product of 100 mm × 0.5 mm and a molded product of 100 mm × 100 mm × 0.1 mm were obtained. The evaluation results are summarized in Table 1.

Examples 2-8 , 10-12 , Comparative Examples 1-3 , Reference Example 1
A resin composition and a molded product were obtained in the same manner as in Example 1 except that the type and amount of each component, the molding temperature and the molding time were changed as shown in Tables 1 to 3. The evaluation results are summarized in Tables 1 to 3.

As mentioned above, the molding material obtained in Examples 1-8 and 10-12 was excellent in the impregnation property, and the molded article excellent in the mechanical characteristic was obtained.

  On the other hand, the molding materials obtained in Comparative Examples 1 and 3 were insufficient in impregnation properties, and good molding materials were not obtained. The molded product using the molding material obtained in Comparative Example 2 had insufficient mechanical properties.

  The molding material of the present invention is a molding material having excellent impregnation properties, and it is possible to obtain a molded product having excellent mechanical properties, which can be developed for various uses. It is particularly suitable for automotive applications, aircraft applications, electrical / electronic components, and household / office electrical product components.

Claims (5)

(A) One or more thermoplastics selected from the group consisting of (B) polyester, polyamide, polycarbonate, polyetheretherketone, polyetherketoneketone, polyetherimide, polysulfone, polyarylate, and polyphenylene ether. A molding material formed by impregnating a resin and (C) a resin composition containing (D) a cyclic polyarylene sulfide represented by the following general formula (1), wherein a total of 100 components (A) to (C) 1 to 80 parts by weight of the component (A) is contained with respect to parts by weight, and the ratio of the component (B) to the component (C) ((B) / (C)) = 10/90 to 40/60 ( A molding material in which the components (B) and (C) in the resin composition (D) are compatible at 320 ° C.

(In the general formula (1), Ar represents an arylene group, and m represents a range of 2 to 50.) Molding material according to claim 1 melt viscosity at 320 ° C. of the component (B) is 50~5000Pa · s. The molding material according to claim 1 or 2 , wherein the component (B) contains one or more thermoplastic resins selected from the group consisting of polyether ketone ketone, polyether imide, polysulfone, polyarylate, and polyphenylene ether. By heating at 250 to 400 ° C. The molding material according to claim 1-3, method for producing a molded article to convert the components contained in the molding material (C) to (E) polyarylene sulfide. The (F) resin composition containing the component (B) and the component (E) forms a sea-island structure in which the component (B) is a sea phase and the component (E) is an island phase. The interparticle distance of 0.5-5
The manufacturing method of the molded article according to claim 4 , which is μm.