WO2015064484A1 - 炭素繊維強化ポリアリーレンスルフィドの製造方法 - Google Patents
炭素繊維強化ポリアリーレンスルフィドの製造方法 Download PDFInfo
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- WO2015064484A1 WO2015064484A1 PCT/JP2014/078290 JP2014078290W WO2015064484A1 WO 2015064484 A1 WO2015064484 A1 WO 2015064484A1 JP 2014078290 W JP2014078290 W JP 2014078290W WO 2015064484 A1 WO2015064484 A1 WO 2015064484A1
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- polyarylene sulfide
- carbon fiber
- polycarbodiimide
- iii
- mass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/482—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0005—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fibre reinforcements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0286—Chemical after-treatment
- C08G75/029—Modification with organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/488—Parts, e.g. casings, sealings; Accessories, e.g. flow controlling or throttling devices
- B29B7/489—Screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
- B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/04—Polysulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
Definitions
- the present invention relates to a method for producing a carbon fiber-reinforced polyarylene sulfide having both mechanical properties and molding cycle properties with high productivity.
- a fiber reinforced composite material composed of a thermoplastic resin and a reinforcing fiber has features such that it is easy to mold using the properties of the thermoplastic resin and is excellent in recyclability.
- various forms of molding materials such as thermoplastic prepregs in which reinforcing fibers are arranged in a sheet form and pellets in which reinforcing fibers are randomly dispersed are known.
- Fiber reinforced composite materials are widely used as industrial materials for structural members such as aircraft, automobiles and ships, electronic equipment casings, sports applications, and building materials because of their excellent balance between lightness and mechanical properties.
- polyarylene sulfide is particularly excellent in heat resistance and chemical resistance, and fiber reinforced polyarylene sulfide obtained by compounding this with reinforced fiber can be expected to be used as an alternative to metal materials.
- fiber-reinforced polyarylene sulfide as an alternative to metal materials, further improvement in its mechanical properties, particularly tensile strength, has been a problem. This is because the tensile elongation of general polyarylene sulfide is lower than the tensile elongation of reinforcing fibers (for example, about 2% for carbon fibers) and the reinforcing effect of reinforcing fibers cannot be fully utilized. there were.
- One means for improving the tensile strength of the fiber-reinforced polyarylene sulfide is to increase the elongation of the polyarylene sulfide used.
- the tensile elongation of polyarylene sulfide correlates with its molecular weight, and consequently the melt viscosity.
- the melt viscosity also increases, and the composite with the reinforcing fiber is reduced. It becomes difficult.
- the process temperature is required to be higher, it is unsuitable for easily producing the fiber-reinforced polyarylene sulfide with high productivity. For this reason, it has been an important technical issue to improve both the tensile strength and productivity of fiber-reinforced polyarylene sulfide.
- Another means for improving the tensile strength of the fiber reinforced polyarylene sulfide includes modification with an additive.
- polyarylene sulfide is a common material and has a melting point of about 285 ° C., which is a high region among thermoplastic resins.
- the additive is eluted during the fiber-reinforced polyarylene sulfide molding process (also called bleed out or bleed). ) And contaminates the mold. In order to obtain a molded product having excellent appearance quality, it is necessary to periodically remove the contamination of the mold, and in this case, there is a problem that the molding cycle performance is greatly impaired.
- Patent Document 1 discloses a carbon fiber reinforced thermoplastic resin composed of carbon fiber, a thermoplastic resin, and a carbodiimide reagent.
- a carbodiimide reagent one molecule of carbodiimide group is used. Since only one compound is used, which is an additive that is easily eluted from the carbon fiber reinforced thermoplastic resin, bleed out during molding of the fiber reinforced polyarylene sulfide cannot be suppressed.
- Patent Document 2 discloses a resin composition containing polyphenylene sulfide and polycarbodiimide.
- Patent Document 2 discloses a technique in which polyphenylene sulfide and polycarbodiimide are melt-kneaded to obtain modified polyphenylene sulfide, and it is disclosed that reinforcing fibers such as carbon fibers are used. There is no disclosure regarding the means to control, bleed-out during the molding process of the fiber-reinforced polyarylene sulfide cannot be suppressed, and the molding cycle performance at the molding process of the fiber-reinforced polyarylene sulfide is insufficient.
- Patent Document 3 discloses a resin composition containing a polyarylene sulfide, an aliphatic polycarbodiimide-based resin, and a filler, but as a means for controlling bleed-out causing mold contamination during molding, The addition amount of aliphatic polycarbodiimide resin is only disclosed, the degree of mold contamination is not disclosed, and the bleed-out during the molding process of fiber reinforced polyarylene sulfide cannot be sufficiently suppressed, and the fiber The molding cycle performance of the reinforced polyarylene sulfide was insufficient.
- Patent Document 4 discloses a reinforcing material surface-treated with a carbodiimide compound and a composite material using the same, but there is no example of using polyarylene sulfide as a matrix resin, and the cause of mold contamination during molding processing. Since there is no disclosure of a means for controlling the bleed out, the bleed out cannot be sufficiently suppressed during the molding process of the fiber reinforced polyarylene sulfide, and the molding cycle property during the molding process of the fiber reinforced polyarylene sulfide is not satisfactory. It was enough.
- the present invention attempts to improve such problems of the prior art, and provides a method for producing a carbon fiber reinforced polyarylene sulfide that can suppress bleeding out during molding and has both mechanical properties and molding cycleability with high productivity.
- the issue is to provide.
- the present invention has any one of the following configurations (1) to (3).
- a method for producing a carbon fiber-reinforced polyarylene sulfide comprising the following steps (I-1) to (III-1): (I-1) 100 parts by mass of polyarylene sulfide (A) and 0.1-10 parts by mass of polycarbodiimide (B) having at least two carbodiimide groups in one molecule are mixed, and the resulting mixture is heated.
- Step (II-1) to obtain a melt-kneaded product by melt-kneading The melt-kneaded product obtained in step (I-1) is heated at a temperature not lower than the glass transition temperature and not higher than the melting point of polyarylene sulfide (A).
- the reaction of the carbodiimide group in the melt-kneaded product is promoted to obtain the polycarbodiimide-modified polyarylene sulfide (C-1) (III-1)
- the polycarbodiimide-modified polyarylene sulfide obtained in the step (II-1) (C-1) is melted and combined with 10 to 300 parts by mass of carbon fiber (D) per 100 parts by mass of polyarylene sulfide (A).
- polycarbodiimide (B) having at least two carbodiimide groups in one molecule is heated at a temperature equal to or higher than the softening point of the component (B) to promote the reaction between the carbodiimide groups.
- Step of obtaining polycarbodiimide reactant (B-2) (II-2) 100 parts by mass of polyarylene sulfide (A) and 0.1 to 10 parts by mass of polycarbodiimide reactant (B-2) are obtained.
- step (I-3) Step of obtaining a mixture obtained by mixing 100 parts by mass of polyarylene sulfide (A) and 0.1 to 10 parts by mass of polycarbodiimide (B) having at least two carbodiimide groups in one molecule (II-3) )
- the mixture obtained in step (I-3) is heated and melt-kneaded at a temperature equal to or higher than the melting point of polyarylene sulfide (A), thereby promoting the reaction of the carbodiimide group and polycarbodiimide-modified polyarylene sulfide (C -3) Step (III-3)
- the polycarbodiimide-modified polyarylene sulfide (C-3) is melted at the following temperature at the time of melt kneading in the step (II-3), and 100 parts by mass of the polyarylene sulfide (A)
- bleed-out during molding can be suppressed, and carbon fiber-reinforced polyarylene sulfide having both mechanical properties and molding cycle properties can be produced with high productivity.
- the first carbon fiber-reinforced polyarylene sulfide production method includes the steps (I-1) to (III-1). First, the steps (I-1) to (III-1) employed in the first production method will be described in more detail.
- Step (I-1) is a step in which a polyarylene sulfide (A) and a polycarbodiimide (B) are mixed and the resulting mixture is heated and melt-kneaded to obtain a melt-kneaded product.
- the method for obtaining the mixture is as follows. From the viewpoint of mixing the polyarylene sulfide (A) and the polycarbodiimide (B) as uniformly as possible, the granular polyarylene sulfide (A) and the granular polycarbodiimide ( A method of dry blending B) can be exemplified. Examples of the apparatus for performing dry blending include a Henschel mixer and a rocking mixer. Moreover, it is preferable to perform the atmosphere at the time of obtaining a mixture in non-oxidizing atmosphere, and it is also preferable to carry out under pressure reduction conditions.
- the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the mixture is 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas such as nitrogen, helium, or argon. It indicates an atmosphere, and among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling. Use of such a mixing method is preferable because it is possible to suppress a decrease in the reaction activity of the polyarylene sulfide (A) and the polycarbodiimide (B) before the next melt-kneading.
- the number average particle diameter of the polyarylene sulfide (A) and the polycarbodiimide (B) when dry blending is preferably 0.001 to 10 mm, more preferably 0.01 to 5 mm, and further preferably 0.1 to 3 mm. .
- the number average particle diameters of the polyarylene sulfide (A) and the polycarbodiimide (B) are preferably as close as possible. Such a range of the number average particle diameter is preferable because separation in the kneaded product can be reduced.
- the polycarbodiimide (B) needs to be contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide (A). It is preferable to contain a part. When the content of polycarbodiimide (B) is less than 0.1 parts by mass, the amount of polycarbodiimide (B) is not sufficient, and the effect of improving the mechanical properties of the resulting carbon fiber reinforced polyarylene sulfide does not appear.
- step (I-1) the purpose of melt kneading is to melt polyarylene sulfide (A) and polycarbodiimide (B) by heating at a temperature equal to or higher than their melting points, and knead them under melting conditions.
- the polycarbodiimide (B) needs to have at least two carbodiimide groups in one molecule.
- Examples of the apparatus for performing melt kneading in the step (I-1) include a lab plast mill mixer and an extruder.
- a lab plast mill mixer is a device that puts a predetermined amount of raw material into a mixer and performs melt kneading for a certain time, and it is easy to control the melt kneading time.
- the extruder is a device that conveys and discharges continuously charged raw materials while melting and kneading, and is excellent in the productivity of the melt-kneaded material.
- Examples of the extruder used for melt kneading in the step (I-1) include a single screw extruder and a twin screw extruder, and among them, a twin screw extruder excellent in melt kneading property can be preferably used.
- Examples of the twin screw extruder include those having a screw length / screw diameter ratio (screw length) / (screw diameter) of 20 to 100.
- the screw of the twin-screw extruder is composed of a combination of screw segments with different length and shape characteristics, such as full flight and kneading disc. However, one screw is required for improving melt kneading and reactivity. It is preferable to include the above kneading disc.
- the melt-kneading in the step (I-1) is performed under reduced pressure.
- a lab plast mill mixer it is preferable to set the area under reduced pressure so as to cover the entire melt-kneaded product.
- the area from which the melt-kneaded material is discharged (screw length) ) / (Screw diameter) is preferably placed at a position of 0 to 10 before.
- the gauge pressure is preferably ⁇ 0.05 MPa or less, more preferably ⁇ 0.08 MPa or less.
- the gauge pressure is a degree of reduced pressure measured using a vacuum gauge at an atmospheric pressure of 0 MPa.
- the temperature for melt kneading is preferably 285 to 400 ° C, more preferably 285 to 350 ° C. If the temperature at which the melt kneading is performed is higher than the above range, the polyarylene sulfide (A) and the polycarbodiimide (B) are thermally decomposed, and the mechanical properties and molding cycle properties of the obtained carbon fiber reinforced polyarylene sulfide are lowered. There is a case. If the temperature at which the melt kneading is performed is lower than this range, the polyarylene sulfide (A) may not melt and a melt-kneaded product may not be obtained.
- the time for melt kneading in the step (I-1) is preferably 0.5 to 30 minutes, more preferably 0.5 to 15 minutes, further preferably 0.5 to 10 minutes, and 0.5 to 5 minutes. Especially preferred.
- the time required for melt-kneading is longer than the time-consuming range, the polyarylene sulfide (A) is cross-linked and thickened, making it difficult to combine with the carbon fiber (D) in the step (III-1). There is.
- the time required for melt kneading is shorter than the time-consuming range, the polyarylene sulfide (A) and the polycarbodiimide (B) may not melt and a melt-kneaded product may not be obtained.
- the time required from the start of heating the mixture until the polyarylene sulfide (A) and the polycarbodiimide (B) are completely melted is t1 (seconds), the polyarylene sulfide (A) and the polyarylene sulfide (A).
- t1 seconds
- t2 seconds
- t1 here is a part of the melt kneaded material taken out appropriately after being put into the mixer, and polyarylene sulfide (A) and poly Examples of the time required until melting of the carbodiimide (B) can be confirmed.
- t2 can be calculated
- Step (II-1)> the molten kneaded product obtained in the step (I-1) is heated at a temperature not lower than the glass transition temperature and not higher than the melting point of the polyarylene sulfide (A), so that the carbodiimide in the melt kneaded material is heated.
- the reaction of the group is promoted to obtain polycarbodiimide-modified polyarylene sulfide (C-1).
- reaction (1) Reaction reaction of functional group of polyarylene sulfide (A) and carbodiimide group of polycarbodiimide (B)
- reaction (2) Carbodiimide group of polycarbodiimide (B) reacts to form a dimer or Reaction that forms a trimer and polycarbodiimide (B) forms a crosslinked structure
- the island phase composed of polycarbodiimide (B) is dispersed in the sea phase composed of the reaction product of polycarbodiimide (B) and polyarylene sulfide (A).
- An example is a sea-island structure in which a part or all of the polycarbodiimide (B) forming the island phase is crosslinked by the reaction (2).
- the purpose of heating the melt-kneaded product obtained in the step (I-1) at a temperature not lower than the glass transition temperature and not higher than the melting point of the polyarylene sulfide (A) is the polyarylene sulfide (A). It is to reduce the bleeding out of polycarbodiimide (B) from the obtained carbon fiber reinforced polyarylene sulfide by suppressing the cross-linking reaction of itself and increasing the reaction rate of reaction (1) and reaction (2). . In particular, since polycarbodiimide (B) has at least two carbodiimide groups in one molecule, the reaction (2) can be expected to make it difficult to bleed out.
- step (II-1) as a method of heating the melt-kneaded product obtained in the step (I-1) at a temperature not lower than the glass transition temperature and not higher than the melting point of the polyarylene sulfide (A), the step (I-1)
- the melt-kneaded product obtained in step (1) is transferred to a press molding machine in the molten state and heated and pressed into a sheet form, or the melt-kneaded product obtained in step (I-1) is pelletized and then placed in an oven.
- a method of transferring and heating can be exemplified.
- Examples of the temperature not lower than the glass transition temperature and not higher than the melting point of the polyarylene sulfide (A) in the step (II-1) include 90 to 280 ° C. Further, the reaction rates of the above reactions (1) and (2) From the viewpoint of improving the temperature, 200 to 260 ° C. is preferable. In addition, the glass transition temperature and melting
- DSC differential scanning calorimeter
- the heating time of the polyarylene sulfide (A) above the glass transition temperature and below the melting point is preferably 5 to 720 minutes, more preferably 20 to 360 minutes, and further preferably 30 to 180 minutes. .
- polyarylene sulfide (A) crosslinks and thickens, making it difficult to combine with carbon fiber (D) in step (III-1) There is.
- the heating time is shorter than this range, the reaction rates of the reaction (1) and the reaction (2) become insufficient, and the molding cycle property of the obtained carbon fiber reinforced polyarylene sulfide may be lowered.
- the atmosphere for heating at a temperature higher than the glass transition temperature and lower than the melting point of the polyarylene sulfide (A) is preferably a non-oxidizing atmosphere, and is preferably performed under reduced pressure.
- the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the mixture is 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas such as nitrogen, helium, or argon. It indicates an atmosphere, and among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling. By setting it as this atmosphere, bridge
- Step (III-1) is a step in which the polycarbodiimide-modified polyarylene sulfide (C-1) obtained in step (II-1) is melted and complexed with carbon fiber (D) to obtain a composite.
- the carbon fiber (D) to be combined needs to be 10 to 300 parts by mass with respect to 100 parts by mass of the polyarylene sulfide (A), and is 10 to 200 parts by mass.
- the amount is preferably 20 to 100 parts by mass, more preferably 20 to 50 parts by mass.
- the carbon fiber (D) content is less than 10 parts by mass, the amount of carbon fiber (D) is not sufficient, and the effect of improving the mechanical properties of the resulting carbon fiber-reinforced polyarylene sulfide does not appear.
- the carbon fiber (D) content exceeds 300 parts by mass, it will be difficult to complex the polycarbodiimide-modified polyarylene sulfide (C-1) with the carbon fiber (D), and the resulting carbon fiber will be obtained. The mechanical properties of the reinforced polyarylene sulfide are reduced.
- step (III-1) as a method of combining the polycarbodiimide-modified polyarylene sulfide (C-1) with the carbon fiber (D), a melted polycarbodiimide-modified polyarylene sulfide (C-1) will be described later.
- Examples include a method of impregnating a base material made of carbon fiber (D), a method of melt-kneading polycarbodiimide-modified polyarylene sulfide (C-1) and carbon fiber (D) using an extruder, and the like. .
- step (III-1) as a method of impregnating the base material made of carbon fiber (D) with the melted polycarbodiimide-modified polyarylene sulfide (C-1), a polycarbodiimide-modified material that has been processed into a sheet shape in advance is used.
- An example is a method in which a polyarylene sulfide (C-1) and a substrate made of carbon fiber (D) are laminated, and this is heated and pressed using a press molding machine.
- the temperature at which the polycarbodiimide-modified polyarylene sulfide (C-1) is melted is preferably 285 to 400 ° C, more preferably 285 to 350 ° C. If the melting temperature is higher than the range, the polyarylene sulfide (A) and the polycarbodiimide (B) are thermally decomposed, and the mechanical properties and molding cycle properties of the obtained carbon fiber reinforced polyarylene sulfide may be deteriorated. is there. If the melting temperature is lower than this range, the polycarbodiimide-modified polyarylene sulfide (C-1) may not melt and a composite may not be obtained.
- the time required to obtain the composite after melting the polycarbodiimide-modified polyarylene sulfide (C-1) is preferably 1 to 120 minutes, more preferably 1 to 30 minutes, 1 to 10 minutes is more preferable. By setting it within such a range, carbon fiber reinforced polyarylene sulfide can be obtained with high productivity.
- the second carbon fiber reinforced polyarylene sulfide production method includes the steps (I-2) to (III-2).
- the steps (I-2) to (III-2) employed in the second production method will be described in more detail.
- Step (I-2) the polycarbodiimide (B) having at least two carbodiimide groups in one molecule is heated at a temperature equal to or higher than the softening point of the component (B), thereby reacting the carbodiimide groups. This step is promoted to obtain a polycarbodiimide reactant (B-2).
- the reaction between carbodiimide groups means that carbodiimide groups of polycarbodiimide (B) react with each other to form a dimer or trimer, and polymerize as polycarbodiimide (B) to increase the molecular weight.
- the polycarbodiimide reactant (B-2) has an effect of improving heat resistance by increasing the molecular weight, and reducing components that easily bleed out from the obtained carbon fiber reinforced polyarylene sulfide.
- step (I-2) as a method for heating the polycarbodiimide (B), from the viewpoint of productivity, a method in which the polycarbodiimide (B) can be heated in a large amount at a time is preferable, and the polycarbodiimide (B ) Can be exemplified in the oven.
- a polycarbodiimide reactant (B-2) can be obtained with high productivity by heating a large amount of the polycarbodiimide (B) at a time. Furthermore, by using the polycarbodiimide reactant (B-2), the heating time in the step after the step (I-2) can be shortened, and the productivity of the carbon fiber reinforced polyarylene sulfide is excellent.
- an oven refers to a device having a mechanism for heating contents by heated air or radiant heat emitted from a wall surface or a heating source in the furnace, such as a hot air oven, a vacuum oven, an electric furnace, etc. Can be illustrated.
- a hot air oven or a vacuum oven it is preferable to use a hot air oven or a vacuum oven from the viewpoint of easy control of the temperature in the furnace and suppression of excessive temperature rise.
- the atmosphere for heating the polycarbodiimide (B) is preferably a non-oxidizing atmosphere, and is preferably performed under reduced pressure.
- Non-oxidizing atmosphere means that the oxygen concentration in the gas phase in contact with the polycarbodiimide (B) or the polycarbodiimide reactant (B-2) is 5% by volume or less, preferably 2% by volume or less, more preferably substantially containing oxygen. That is, an inert gas atmosphere such as nitrogen, helium, argon, etc. Among them, a nitrogen atmosphere is particularly preferred from the viewpoint of economy and ease of handling.
- the standard of the degree of pressure reduction is preferably -0.05 MPa or less, more preferably -0.08 MPa or less in terms of gauge pressure.
- the gauge pressure is a degree of reduced pressure measured using a vacuum gauge at an atmospheric pressure of 0 MPa.
- Examples of the temperature above the softening point of polycarbodiimide (B) in step (I-2) include 50 to 250 ° C. Further, the temperature at which the polycarbodiimide (B) is heated in the step (I-2) is more preferably 70 to 250 ° C., and further preferably 100 to 150 ° C. By setting the temperature for heating within such a range, the resulting polycarbodiimide reactant (B-2) coexists with a structure in which carbodiimide groups react with each other and unreacted carbodiimide groups. The mechanical properties and moldability of arylene sulfide can be improved. In addition, the softening point of polycarbodiimide (B) can be calculated
- TMA thermomechanical analyzer
- the time for heating the polycarbodiimide (B) is preferably 1 to 48 hours, more preferably 2 to 30 hours, and further preferably 3 to 24 hours.
- the heating time is longer than the range that requires heating, there are few unreacted carbodiimide groups in the polycarbodiimide reactant (B-2), and the mechanical properties of the resulting carbon fiber reinforced polyarylene sulfide may not be improved.
- the heating time is shorter than the range that requires heating, the structure in which the carbodiimide groups react with each other is small, and the molding cycle property of the obtained carbon fiber reinforced polyarylene sulfide may not be improved.
- step (I-2) in order to obtain the polycarbodiimide reactant (B-2), it is necessary to use polycarbodiimide (B) having at least two carbodiimide groups in one molecule.
- polycarbodiimide (B ′) having only one carbodiimide group in one molecule polymerization cannot proceed even if carbodiimide groups are reacted with each other, and the effect of improving heat resistance is small because the molecular weight cannot be increased. Further, no carbodiimide group remains in the reaction product obtained by the reaction of carbodiimide groups of monocarbodiimide (B ′).
- Step (II-2) is obtained by mixing 100 parts by mass of polyarylene sulfide (A) and 0.1 to 10 parts by mass of the polycarbodiimide reactant (B-2) obtained in step (I-2). In this step, the mixture is heated and melt-kneaded to obtain polycarbodiimide-modified polyarylene sulfide (C-2).
- the method for obtaining the mixture is as follows. From the viewpoint of mixing the polyarylene sulfide (A) and the polycarbodiimide reactant (B-2) as uniformly as possible, the granular polyarylene sulfide (A) and the granular And a method of dry blending the polycarbodiimide reactant (B-2).
- the apparatus for performing dry blending include a Henschel mixer and a rocking mixer.
- the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the mixture is 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas such as nitrogen, helium, or argon. It indicates an atmosphere, and among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling. Use of such a mixing method is preferable because it is possible to suppress a decrease in the reaction activity of the polyarylene sulfide (A) and the polycarbodiimide reactant (B-2) before the next melt-kneading.
- the number average particle diameter of the polyarylene sulfide (A) and the polycarbodiimide reaction product (B-2) during dry blending is preferably 0.001 to 10 mm, more preferably 0.01 to 5 mm, and more preferably 0.1 to 3 mm is more preferable.
- the number average particle diameters of the polyarylene sulfide (A) and the polycarbodiimide reactant (B-2) are preferably as close as possible. Such a range of the number average particle diameter is preferable because separation in the kneaded product can be reduced.
- the polycarbodiimide reactant (B-2) needs to be contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide (A).
- the content is preferably 1 to 5 parts by mass.
- the content of the polycarbodiimide reactant (B-2) is less than 0.1 parts by mass, the amount of the polycarbodiimide reactant (B-2) is not sufficient, and the mechanical properties of the resulting carbon fiber reinforced polyarylene sulfide are not sufficient. Improvement effect does not appear.
- the content of the polycarbodiimide reactant (B-2) exceeds 10 parts by mass, the amount of the polycarbodiimide reactant (B-2) is too large. Characteristics are degraded.
- the purpose of performing melt kneading is to melt the polyarylene sulfide (A) by heating at a temperature equal to or higher than the melting point, and the polycarbodiimide reactant under the melting conditions of the polyarylene sulfide (A).
- the functional group of polyarylene sulfide (A) and the carbodiimide group of polycarbodiimide reactant (B-2) are reacted to produce polycarbodiimide-modified polyarylene sulfide (C-2). Is to get.
- the improvement of the mechanical characteristics of the carbon fiber reinforced polyarylene sulfide obtained and the molding cycle property can be compatible.
- Examples of the apparatus for performing melt kneading in the step (II-2) include a lab plast mill mixer and an extruder.
- a lab plast mill mixer is a device that puts a predetermined amount of raw material into a mixer and performs melt kneading for a certain time, and it is easy to control the melt kneading time.
- the extruder is a device that conveys and discharges continuously charged raw materials while melting and kneading, and is excellent in the productivity of the melt-kneaded material.
- Examples of the extruder used for melt kneading in the step (II-2) include a single screw extruder and a twin screw extruder, and among them, a twin screw extruder excellent in melt kneading property can be preferably used.
- Examples of the twin screw extruder include those having a screw length / screw diameter ratio (screw length) / (screw diameter) of 20 to 100.
- the screw of the twin-screw extruder is composed of a combination of screw segments with different length and shape characteristics, such as full flight and kneading disc. However, one screw is required for improving melt kneading and reactivity. It is preferable to include the above kneading disc.
- the melt-kneading in the step (II-2) is performed under reduced pressure conditions.
- a lab plast mill mixer it is preferable to set the area under reduced pressure so as to cover the entire melt-kneaded product.
- the area from which the melt-kneaded material is discharged (screw length) ) / (Screw diameter) is preferably placed at a position of 0 to 10 before.
- the gauge pressure is preferably ⁇ 0.05 MPa or less, more preferably ⁇ 0.08 MPa or less.
- the gauge pressure is a degree of reduced pressure measured using a vacuum gauge at an atmospheric pressure of 0 MPa.
- the temperature for melt kneading is preferably 285 to 400 ° C, more preferably 285 to 350 ° C. If the temperature at which melt-kneading is performed is higher than the above range, the polyarylene sulfide (A) and the polycarbodiimide reactant (B-2) are thermally decomposed, and the mechanical properties and molding cycle of the resulting carbon fiber reinforced polyarylene sulfide. May decrease. If the temperature at which the melt kneading is performed is lower than this range, the polyarylene sulfide (A) may not melt and a melt-kneaded product may not be obtained.
- the time for melt kneading in the step (II-2) is preferably 0.5 to 30 minutes, more preferably 0.5 to 15 minutes, further preferably 0.5 to 10 minutes, and 0.5 to 5 minutes. Especially preferred.
- the time required for melt kneading is longer than the range that takes time, the polyarylene sulfide (A) is cross-linked and thickened, making it difficult to combine with the carbon fiber (D) in the step (III-3). There is.
- the time required for melt kneading is shorter than the time-consuming range, the polyarylene sulfide (A) may not melt and a melt-kneaded product may not be obtained.
- the polycarbodiimide-modified polyarylene sulfide (C-2) is melt-kneaded, then transferred to a press molding machine in a molten state and heated and pressed into a sheet shape, It is preferable to process into a sheet by a method of discharging the melt-kneaded material into a sheet from a T die or slit die attached to the tip.
- Step (III-2)> the polycarbodiimide-modified polyarylene sulfide (C-2) obtained in the step (II-2) is melted, and 10 to 300 parts by mass with respect to 100 parts by mass of the polyarylene sulfide (A). This is a step of obtaining a composite by combining with carbon fiber (D).
- the carbon fiber (D) to be combined needs to be 10 to 300 parts by mass with respect to 100 parts by mass of the polyarylene sulfide (A), and is 10 to 200 parts by mass.
- the amount is preferably 20 to 100 parts by mass, more preferably 20 to 50 parts by mass.
- the carbon fiber (D) content is less than 10 parts by mass, the amount of carbon fiber (D) is not sufficient, and the effect of improving the mechanical properties of the resulting carbon fiber-reinforced polyarylene sulfide does not appear.
- the carbon fiber (D) content exceeds 300 parts by mass, it will be difficult to complex the polycarbodiimide-modified polyarylene sulfide (C-2) with the carbon fiber (D), and the resulting carbon fiber will be obtained. The mechanical properties of the reinforced polyarylene sulfide are reduced.
- step (III-2) as a method of combining the polycarbodiimide-modified polyarylene sulfide (C-2) with the carbon fiber (D), a melted polycarbodiimide-modified polyarylene sulfide (C-2) will be described later.
- Examples include a method of impregnating a base material made of carbon fiber (D) and a method of melt-kneading polycarbodiimide-modified polyarylene sulfide (C-2) and carbon fiber (D) using an extruder. .
- step (III-2) as a method of impregnating the base material made of carbon fiber (D) with the melted polycarbodiimide-modified polyarylene sulfide (C-2), it is further modified with polycarbodiimide modified into a sheet shape in advance.
- An example is a method in which a polyarylene sulfide (C-2) and a base material made of carbon fiber (D) are laminated, and this is heated and pressed using a press molding machine.
- the temperature at which the polycarbodiimide-modified polyarylene sulfide (C-2) is melted is preferably 285 to 400 ° C, more preferably 285 to 350 ° C. If the melting temperature is higher than the range, the polyarylene sulfide (A) and the polycarbodiimide reaction product (B-2) are thermally decomposed, and the resulting carbon fiber reinforced polyarylene sulfide has mechanical properties and molding cycle characteristics. May decrease. If the melting temperature is lower than this range, the polycarbodiimide-modified polyarylene sulfide (C-2) may not melt and a composite may not be obtained.
- the time required for obtaining the composite after melting the polycarbodiimide-modified polyarylene sulfide (C-2) is preferably 1 to 120 minutes, more preferably 1 to 30 minutes, 1 to 10 minutes is more preferable. By setting it within such a range, carbon fiber reinforced polyarylene sulfide can be obtained with high productivity.
- the third method for producing a carbon fiber-reinforced polyarylene sulfide according to an embodiment of the present invention includes the steps (I-3) to (III-3).
- the steps (I-3) to (III-3) employed in the third production method will be described in more detail.
- Step (I-3) is a step of obtaining a mixture in which 100 parts by mass of polyarylene sulfide (A) and 0.1 to 10 parts by mass of polycarbodiimide (B) having at least two carbodiimide groups in one molecule are mixed. is there.
- step (I-3) as a method for obtaining a mixture, from the viewpoint of mixing the polyarylene sulfide (A) and the polycarbodiimide (B) as uniformly as possible, the granular polyarylene sulfide (A) and the granular polycarbodiimide are mixed.
- a method of dry blending (B) can be exemplified. Examples of the apparatus for performing dry blending include a Henschel mixer and a rocking mixer. Moreover, it is preferable to perform the atmosphere at the time of obtaining a mixture in non-oxidizing atmosphere, and it is also preferable to carry out under pressure reduction conditions.
- the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the mixture is 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, an inert gas such as nitrogen, helium, or argon. It indicates an atmosphere, and among these, a nitrogen atmosphere is particularly preferable from the viewpoints of economy and ease of handling. Use of such a mixing method is preferable because it is possible to suppress a decrease in the reaction activity of the polyarylene sulfide (A) and the polycarbodiimide (B) before the next melt-kneading.
- the number average particle diameter of the polyarylene sulfide (A) and the polycarbodiimide (B) when dry blending is preferably 0.001 to 10 mm, more preferably 0.01 to 5 mm, and further preferably 0.1 to 3 mm. .
- the number average particle diameters of the polyarylene sulfide (A) and the polycarbodiimide (B) are preferably as close as possible. Such a range of the number average particle diameter is preferable because separation in the kneaded product can be reduced.
- the polycarbodiimide (B) needs to be contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide (A). It is preferable to contain a part. When the content of the polycarbodiimide (B) is less than 0.1 parts by mass, the amount of the polycarbodiimide (B) is not sufficient, and the effect of improving the resulting carbon fiber reinforced polyarylene sulfide mechanical properties does not appear.
- step (II-3) the mixture obtained in the step (I-3) is heated and melt-kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide (A), thereby promoting the reaction of the carbodiimide group.
- This is a step of obtaining a carbodiimide-modified polyarylene sulfide (C-3).
- the reaction between the functional group of the arylene sulfide (A) and the carbodiimide group of the polycarbodiimide (B) and the carbodiimide group of the polycarbodiimide (B) react with each other to form a dimer or trimer, and the polycarbodiimide ( B) refers to a reaction that forms a crosslinked structure.
- an island phase composed of polycarbodiimide (B) is dispersed in a sea phase composed of a reaction product of polycarbodiimide (B) and polyarylene sulfide (A).
- Examples thereof include a sea-island structure in which a part or all of the polycarbodiimide (B) forming the island phase is cross-linked by a reaction between carbodiimide groups of the polycarbodiimide (B).
- polycarbodiimide (B) since polycarbodiimide (B) has at least two carbodiimide groups in one molecule, it is expected that the carbodiimide groups react with each other to form a dimer or trimer, so that it is difficult to bleed out. it can.
- monocarbodiimide (B ′) having only one carbodiimide group in one molecule polyarylene sulfide (A) and unreacted monocarbodiimide (B ′) are excessive, and the resulting carbon fiber reinforced polyarylene sulfide is molded. Cycle performance is reduced.
- Examples of the apparatus for performing melt kneading in the step (II-3) include a lab plast mill mixer and an extruder.
- a lab plast mill mixer is a device that puts a predetermined amount of raw material into a mixer and performs melt kneading for a certain time, and it is easy to control the melt kneading time.
- the extruder is a device that conveys and discharges continuously charged raw materials while melting and kneading, and is excellent in the productivity of the melt-kneaded material.
- Examples of the extruder used for melt kneading in the step (II-3) include a single screw extruder and a twin screw extruder, and among them, a twin screw extruder excellent in melt kneading property can be preferably used.
- Examples of the twin screw extruder include those having a screw length / screw diameter ratio (screw length) / (screw diameter) of 20 to 100.
- the screw of the twin-screw extruder is composed of a combination of screw segments with different length and shape characteristics, such as full flight and kneading disc. However, one screw is required for improving melt kneading and reactivity. It is preferable to include the above kneading disc.
- the melt-kneading in the step (II-3) is performed under reduced pressure conditions.
- a lab plast mill mixer it is preferable to set the area under reduced pressure so as to cover the entire melt-kneaded product.
- the area from which the melt-kneaded material is discharged (screw length) ) / (Screw diameter) is preferably placed at a position of 0 to 10 before.
- the gauge pressure is preferably ⁇ 0.05 MPa or less, more preferably ⁇ 0.08 MPa or less.
- the gauge pressure is a degree of reduced pressure measured using a vacuum gauge at an atmospheric pressure of 0 MPa.
- step (II-3) the temperature above the melting point of component (A), that is, the temperature at which polycarbodiimide-modified polyarylene sulfide (C-3) is obtained by melt kneading is preferably 330 to 400 ° C. 360 degreeC is more preferable.
- melt-kneading at 330 ° C. or higher the reaction between the polyarylene sulfide (A) and the polycarbodiimide (B) can be performed in a short time, and the productivity of the polycarbodiimide-modified polyarylene sulfide (C-3) is excellent.
- the temperature at which the melt kneading is performed is higher than the above range, the polyarylene sulfide (A) and the polycarbodiimide (B) are thermally decomposed, and the mechanical properties and molding cycle properties of the obtained carbon fiber reinforced polyarylene sulfide are lowered. There is a case.
- the time for melt kneading in the step (II-3) is preferably 0.5 to 30 minutes, more preferably 0.5 to 15 minutes, further preferably 0.5 to 10 minutes, and 0.5 to 5 minutes. Especially preferred.
- the time required for melt kneading is longer than the range that takes time, the polyarylene sulfide (A) is cross-linked and thickened, making it difficult to combine with the carbon fiber (D) in the step (III-3). There is.
- the time required for melt kneading is shorter than the time-consuming range, the polyarylene sulfide (A) and the polycarbodiimide (B) may not melt and a melt-kneaded product may not be obtained.
- the polycarbodiimide-modified polyarylene sulfide (C-3) is melt-kneaded, transferred to a press molding machine in a molten state and heated and pressed into a sheet shape, It is preferable to process into a sheet by a method of discharging the melt-kneaded material into a sheet from a T die or slit die attached to the tip.
- Step (III-3) the polycarbodiimide-modified polyarylene sulfide (C-3) is melted at the following temperature during the melt-kneading in the step (II-3), and the polyarylene sulfide (A) is 100 parts by mass.
- This is a step of obtaining a composite by combining with 10 to 300 parts by mass of carbon fiber (D).
- the temperature at which the polycarbodiimide-modified polyarylene sulfide (C-3) is melted is set to the following temperature at the time of melt kneading in the step (II-3), whereby the carbon fiber (D)
- the carbon fiber (D) When complexing, generation of volatile components derived from thermal decomposition of polycarbodiimide-modified polyarylene sulfide (C-3) can be suppressed. Furthermore, since the volatile matter generated at the time of compounding can be reduced, adhesion between the polycarbodiimide-modified polyarylene sulfide (C-3) and the reinforcing fiber (D) can be enhanced. For these reasons, improvement in mechanical properties and molding cycle performance of the obtained carbon fiber reinforced polyarylene sulfide can be achieved.
- the temperature below the melt kneading in the step (II-3), that is, the temperature at the time of melting the polycarbodiimide-modified polyarylene sulfide (C-3) is 280 to 330 ° C. 280 to 300 ° C. is more preferable. If the melting temperature is higher than this range, in the case of polycarbodiimide-modified polyarylene sulfide (C-3), the mechanical properties and molding cycle properties of carbon fiber reinforced polyarylene sulfide obtained by thermal decomposition may be lowered. If the melting temperature is lower than this range, the polycarbodiimide-modified polyarylene sulfide (C-3) may not melt and a composite may not be obtained.
- the time required for obtaining the composite after melting the polycarbodiimide-modified polyarylene sulfide (C-3) is preferably 1 to 120 minutes, more preferably 1 to 30 minutes, 1 to 10 minutes is more preferable. By setting it within such a range, carbon fiber reinforced polyarylene sulfide can be obtained with high productivity.
- the carbon fiber (D) to be combined needs to be 10 to 300 parts by mass with respect to 100 parts by mass of the polyarylene sulfide (A), and is 10 to 200 parts by mass.
- the amount is preferably 20 to 100 parts by mass, more preferably 20 to 50 parts by mass.
- the carbon fiber (D) content is less than 10 parts by mass, the amount of carbon fiber (D) is not sufficient, and the effect of improving the mechanical properties of the resulting carbon fiber-reinforced polyarylene sulfide does not appear.
- step (III-3) as a method of combining the polycarbodiimide-modified polyarylene sulfide (C-3) with the carbon fiber (D), a melted polycarbodiimide-modified polyarylene sulfide (C-3) will be described later.
- Examples thereof include a method of impregnating a substrate made of carbon fiber (D), a method of melt-kneading polycarbodiimide-modified polyarylene sulfide (C-3) and carbon fiber (D) using an extruder. .
- step (III-3) as a method of impregnating the base material composed of carbon fiber (D) with the melted polycarbodiimide-modified polyarylene sulfide (C-3), it is further modified with polycarbodiimide modified into a sheet shape in advance.
- An example is a method of laminating a polyarylene sulfide (C-3) and a substrate made of carbon fiber (D) and then heat-pressing the laminate using a press molding machine.
- a substrate made of non-woven carbon fiber (D) that is relatively easily impregnated with polycarbodiimide-modified polyarylene sulfide (C-1), (C-2), or (C-3) is preferably used.
- the non-woven carbon fiber (D) is preferably a case where carbon fiber single yarns are randomly dispersed.
- the carbon fiber (D) single yarn has a number average fiber length of 0.01 to 20 mm is preferable, and 0.01 to 10 mm is more preferable. By setting it within this range, a carbon fiber reinforced polyarylene sulfide excellent in mechanical properties and fluidity during molding can be obtained. Further, the longer the fiber length of the carbon fiber (D), the better the mechanical properties of the resulting polycarbodiimide-modified polyarylene sulfide.
- step (IV) Any of the production methods of the present invention preferably further includes the following step (IV).
- step (IV) the complex obtained in step (III-1), (III-2) or (III-3) is heated at a temperature not lower than the glass transition temperature and not higher than the melting point of polyarylene sulfide (A). This is a step of promoting the reaction of the carbodiimide group in the composite.
- the polyarylene sulfide (A) having the functional group and the polycarbodiimide (A) performed in the step (II-1), (I-2), (II-2) or (II-3) The reaction rate of the reaction in which the reaction of the carbodiimide group of B) and the carbodiimide group of polycarbodiimide (B) react to form a dimer or trimer, and the polycarbodiimide (B) forms a crosslinked structure. It can be further increased, and bleeding of the polyarylene sulfide (B) from the resulting carbon fiber-reinforced polyarylene sulfide can be reduced.
- Examples of the temperature not lower than the glass transition temperature and not higher than the melting point of the polyarylene sulfide (A) in the step (IV) include 90 to 280 ° C.
- the functional group of the polyarylene sulfide (A) and the polycarbodiimide The reaction rate of the reaction in which the reaction of the carbodiimide group of B) and the carbodiimide group of polycarbodiimide (B) react to form a dimer or trimer, and the polycarbodiimide (B) forms a crosslinked structure. From the viewpoint of improving, 200 to 260 ° C. is preferable.
- fusing point of polyarylene sulfide (A) can be calculated
- the heating time of the polyarylene sulfide (A) above the glass transition temperature and below the melting point is preferably 5 to 720 minutes, more preferably 20 to 360 minutes, and further preferably 30 to 180 minutes.
- the polyarylene sulfide (A) may be cross-linked and thickened, which may make further heat forming difficult.
- Step (V) is a step of injection molding or press molding the composite obtained in Step (III-1), (III-2) or (III-3) or the composite obtained through Step (IV).
- the injection molding can be exemplified by a method using an in-line screw type injection molding machine.
- the composite is measured in a cylinder of the injection molding machine to obtain a molten state, and then the composite in the molten state is obtained.
- a method of taking out as an injection-molded product of a predetermined shape by injecting into a molding die, cooling and solidifying can be exemplified.
- examples of the press molding include a method in which the composite is deformed into a predetermined shape by heating and compressing in a molding die, and then cooled and solidified to be taken out as a press molded product.
- the molding processing temperature at the time of injection molding or press molding in the step (V) is lower than the temperature at which the composite is obtained in the step (III-1), (III-2) or (III-3). Preferably it is done.
- it is possible to suppress the generation of volatile components derived from the thermal decomposition of the composite during the molding process in the step (V), and to reduce the volatile components generated during the molding process.
- the adhesion between the component (C-1), (C-2) or (C-3) and the reinforcing fiber (D) can be improved, and the mechanical properties of the carbon fiber reinforced polyarylene sulfide are improved. And molding cycle properties are preferable.
- the molding temperature in step (V) refers to the cylinder temperature of the injection molding machine or the molding die temperature of the press molding machine, and can be exemplified by 280 to 330 ° C, more preferably 280 to 300 ° C. If the molding temperature in the step (V) is higher than the range, the mechanical properties and molding cycle properties of the obtained carbon fiber reinforced polyarylene sulfide may be deteriorated due to the thermal decomposition of the composite. If the molding temperature is lower than the range, the composite may not be processed.
- the time required for molding the composite is preferably 0.15 to 120 minutes, more preferably 0.15 to 30 minutes, and further preferably 0.15 to 10 minutes. By setting it within such a range, carbon fiber reinforced polyarylene sulfide can be obtained with high productivity.
- the method for producing a carbon fiber reinforced polyarylene sulfide of the present invention comprises the steps (I-1) to (III-1), (I-2) to (III-2), or (I-3) to (III-3). ) And, if necessary, through steps (IV) and / or (V) in addition to these steps, the polyarylene sulfide (B) can be obtained while maintaining the molding processability of the resulting composite. Bleed-out can be reduced.
- polyarylene sulfide (A), polycarbodiimide (B), and carbon fiber (D) will be described.
- the polyarylene sulfide (A) (hereinafter, the polyarylene sulfide may be abbreviated as PAS) has a repeating unit of the formula, — (Ar—S) —, as a main constituent unit, preferably 80 mol of the repeating unit. % Or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more.
- Ar includes units represented by the following formulas (a) to (k), among which the unit represented by the formula (a) is particularly preferable.
- R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, and a halogen group. May be the same or different.
- this repeating unit is a main constituent unit, it can contain a small amount of branching units or crosslinking units represented by the following formulas (l) to (n).
- the copolymerization amount 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.
- PAS (A) may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.
- PAS (A) include polyphenylene sulfide (formula (a), formula (b), formula (f) to formula (k)), polyphenylene sulfide sulfone (formula (d)), polyphenylene sulfide ketone. (Formula (c)), polyphenylene sulfide ether (formula (e)), random copolymers thereof, block copolymers, and mixtures thereof.
- Particularly preferred PAS (A) is a p-phenylene sulfide unit as the main structural unit of the polymer.
- PPS polyphenylene sulfide
- PAS (A) has a mass average molecular weight of preferably 10,000 to 80,000, more preferably 10,000 to 60,000, and still more preferably 10,000 to 40,000. PAS (A) having a smaller mass average molecular weight is preferred because it has a lower melt viscosity, facilitates complexation with carbon fiber (D), and is excellent in productivity of carbon fiber-reinforced polyarylene sulfide.
- the mass average molecular weight of PAS (A) can be measured using generally known GPC (gel permeation chromatography) such as size exclusion chromatography (SEC). 1-chloronaphthalene is used as the eluent, the column temperature is 210 ° C., and the weight average molecular weight in terms of polystyrene is calculated.
- GPC gel permeation chromatography
- SEC size exclusion chromatography
- PAS (A) preferably has a functional group at the end of the main chain and / or side chain.
- the main chain as used herein refers to the longest chain structure portion in the polymer structure, and the portion branched from the main chain is referred to as a side chain.
- the polymer structure refers to a part where a single structural unit is repeatedly connected, or a part where a plurality of structural units are regularly or randomly connected, and the terminal is the last structural unit where the connection stops. Point to.
- the functional group possessed by PAS (A) is preferably at least one position on either the main chain and / or the end of the side chain of the polymer structure, and the proportion of PAS having such a functional group in PAS (A) is 50 mass% or more is preferable, 60 mass% or more is more preferable, and 80 mass% or more is further more preferable.
- a carbon fiber reinforced polyarylene sulfide having excellent mechanical properties can be obtained.
- the functional group possessed by PAS (A) includes those in which the functional group of the monomer used in the polymerization remains, a functional group formed by incorporating a catalyst, an auxiliary agent or a solvent during polymerization into the terminal, or a polymer structure
- Functional groups formed by cleavage by thermal decomposition or hydrolysis, and those functional groups modified by oxidation, reduction, and denaturing agents can be used.
- the modifier include epichlorohydrin, polyfunctional epoxy resin, acid anhydride and the like. Among them, since the damage to the polymer structure is small and the molecular weight is easy to control, the functional group of the monomer used during polymerization remains, and the catalyst, auxiliary agent and solvent during polymerization are incorporated at the terminal.
- the functional group formed in this way is preferably used.
- Specific examples of functional groups possessed by PAS (A) include thiol groups, epoxy groups, carboxyl groups, metal salts of carboxyl groups, amino groups, hydroxyl groups, isocyanate groups, oxazoline groups, and sulfonic acid groups.
- a thiol group, an epoxy group, a carboxyl group, a metal salt of a carboxyl group, an amino group, and a hydroxyl group are preferable in terms of reactivity with a carbodiimide group, and a thiol group, a carboxyl group, an amino group, and a hydroxyl group are particularly preferable.
- the amount of oligomer extracted with chloroform is preferably 2% by mass or less, and more preferably 1% by mass or less.
- the amount of oligomer extracted with chloroform is an indicator of the amount of low-polymerization organic component (oligomer), and the residual after treatment with Soxhlet extraction for 5 hours using 200 mL of chloroform for 10 g of PAS (A) to be measured. It can be calculated from the quantity.
- PAS (A) is produced in a high yield by recovering PAS (A) from a polymerization reaction product obtained by reacting a polyhalogen aromatic compound and a sulfidizing agent in a polar organic solvent and post-treating it. Can do.
- a polyhalogenated aromatic compound means a compound having two or more halogen atoms in one molecule.
- Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexa
- Examples include chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene and the like.
- p-dichlorobenzene is preferably used. It is also possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a p-dihalogenated aromatic compound as the main component.
- the polyhalogenated aromatic compound is used in an amount of 0.9 to 2.0 moles, preferably 0.95 to 1 moles per mole of sulfidizing agent, in order to obtain a PAS (A) having a weight average molecular weight suitable for processing.
- a range of 0.5 mol, more preferably 1.005 to 1.2 mol can be exemplified.
- sulfidizing agent examples include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.
- alkali metal sulfide examples include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used.
- These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.
- alkali metal hydrosulfide examples include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used.
- These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.
- the amount of the sulfidizing agent charged is the residual amount obtained by subtracting the loss from the actual amount charged when a partial loss of the sulfiding agent occurs before the start of the polymerization reaction due to dehydration operation or the like. It shall mean quantity.
- alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfidizing agent.
- alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more of these.
- alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.
- an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95 to 1.
- a range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.
- the sulfidizing agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the temperature of the mixture containing the organic polar solvent and the sulfidizing agent is increased, and excess water is removed from the system. It is preferable to remove it. In addition, when water is removed excessively by this operation, it is preferable to add and replenish the deficient water.
- an alkali metal sulfide prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank can be used.
- Desirable conditions for preparing the alkali metal sulfide are normal temperature to 150 ° C., more preferably normal temperature to 100 ° C. in an inert gas atmosphere, and an alkali metal hydrosulfide and alkali metal hydroxide are added to the organic polar solvent.
- the temperature is raised to 150 ° C. or higher, more preferably 180 to 260 ° C. under normal pressure or reduced pressure, to distill off water.
- a polymerization aid may be added at this stage.
- moisture content you may react by adding toluene etc.
- the amount of water in the polymerization system is preferably 0.5 to 10.0 moles per mole of the charged sulfidizing agent.
- the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system.
- the water to be charged may be in any form such as water, an aqueous solution, and crystal water.
- a more preferable range of the water content is 0.75 to 2.5 mol per mol of the sulfidizing agent, and a range of 1.0 to 1.25 mol is more preferable. In order to adjust the moisture to such a range, it is also possible to add moisture before or during the polymerization.
- PAS (A) is prepared by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent such as N-methyl-2-pyrrolidone within a temperature range of 200 ° C. or higher and 290 ° C. or lower. Manufacturing.
- a sulfidizing agent and a polyhalogenated aromatic compound are added to an organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 220 ° C., preferably 100 to 220 ° C.
- a polymerization aid such as sodium acetate may be added.
- the polymerization assistant means a substance having an action of adjusting the viscosity of the obtained PAS (A). The order in which these raw materials are charged may be out of order or may be simultaneous.
- the temperature of such a mixture is usually raised to a range of 200 ° C to 290 ° C. Although there are no particular limitations on the rate of temperature increase, a rate of 0.01 to 5 ° C./min is usually selected, and a range of 0.1 to 3 ° C./min is more preferable.
- the temperature is raised to a temperature of 250 to 290 ° C., and the reaction is carried out at that temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.
- the method of raising the temperature to 250 to 290 ° C. after reacting at a temperature of, for example, 200 ° C. to 245 ° C. for a certain period of time before reaching the final temperature is effective for obtaining a higher degree of polymerization.
- the reaction time at 200 ° C. to 245 ° C. is usually selected within the range of 0.25 hours to 20 hours, preferably within the range of 0.25 to 10 hours.
- a solid is recovered from the polymerization reaction product containing a polymer, a solvent and the like.
- a recovery method for example, a flash method, that is, a polymerization reaction product is flashed from a high temperature and high pressure (usually 245 ° C. or more, 0.8 MPa or more) state to an atmosphere of normal pressure or reduced pressure, and the polymer is granulated simultaneously with solvent recovery.
- the quenching method that is, the polymerization reaction product is gradually cooled from a high temperature and high pressure state to precipitate the PAS component in the reaction system, and is filtered off at a temperature of 70 ° C. or higher, preferably 100 ° C. or higher.
- a method of recovering the solid containing the PAS component in the form of granules may be mentioned.
- the recovery method of PAS (A) is not limited to either the quench method or the flash method, but there are few oligomer components as typified by chloroform extraction components, and the resulting carbon fiber reinforced polyarylene sulfide molding cycle Since it is excellent in property, it is preferable that it is PAS (A) obtained by a quench method.
- the amount of PAS oligomer extracted with chloroform of PAS obtained by the quench method can be exemplified by 2% by mass or less, more preferably 1% by mass or less.
- PAS (A) is produced through the above polymerization and recovery steps, and then used after being subjected to hot water treatment or washing with an organic solvent (post treatment step). Since the PAS (A) obtained through the recovery step contains ionic impurities such as alkali metal halides and alkali metal organic substances, which are polymerization by-products, washing is usually performed.
- the cleaning liquid include a method of cleaning using water or an organic solvent, and cleaning with water can be exemplified as a preferable method in terms of obtaining PAS (A) easily and inexpensively.
- As the kind of water to be used ion exchange water and distilled water are preferably used.
- the washing temperature when washing PAS (A) is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 150 ° C. or higher and 200 ° C. or lower, and further preferably 180 ° C. or higher and 200 ° C. or lower.
- the treatment with a liquid at 100 ° C. or higher is usually performed by charging a predetermined amount of liquid with a predetermined amount of PAS (A), and heating and stirring at normal pressure or in a pressure vessel.
- the washing may be performed a plurality of times, and the washing temperature in each washing may be different, but in order to obtain PAS (A) having a small amount of ionic impurities, at least once, preferably 2 at a temperature of 150 ° C. or higher. It is preferable to perform washing more than once, and it is a more preferable method to pass a filtration step of separating the polymer and the washing liquid between each washing.
- a washing additive may be used when washing is performed, and examples of the washing additive include acids, alkali metal salts, and alkaline earth metal salts.
- the PAS to be cleaned is immersed in an aqueous solution made acidic by adding an organic acid or an inorganic acid to the water used for the cleaning, so that the pH of the aqueous solution after heating and cleaning becomes 2-8. It is preferable to do.
- the organic acid and inorganic acid include acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid and the like, but are not limited thereto, but acetic acid and hydrochloric acid are preferable.
- PAS (A) using an acid as a cleaning additive is referred to as an acid-terminated product.
- an alkali metal salt or alkaline earth metal salt as a cleaning additive
- a method of immersing PAS to be cleaned in an aqueous solution in which an alkali metal salt or alkaline earth metal salt is added to water used for cleaning can be exemplified.
- the amount of the alkali metal salt or alkaline earth metal salt is preferably 0.01 to 5% by mass, more preferably 0.1 to 0.7% by mass, based on PAS (A).
- the alkali metal salt and alkaline earth metal salt include, but are not limited to, calcium salts, potassium salts, sodium salts, magnesium salts, and the like of the above organic acids or inorganic acids.
- the washing additive may be used at any stage of the washing process, but in order to efficiently wash with a small amount of additive, the solid collected in the collecting process is washed with water several times. Then, a method of impregnating PAS to be cleaned in an aqueous solution to which a cleaning additive is added and treating at 150 ° C. or higher is preferable.
- the ratio of the PAS and the cleaning liquid in the cleaning is preferably larger in the cleaning liquid.
- a bath ratio of 10 to 500 g of PAS (A) is preferably selected with respect to 1 liter of the cleaning liquid, and more preferably 50 to 200 g.
- the PAS (A) thus obtained is dried under normal pressure and / or under reduced pressure.
- a drying temperature is preferably in the range of 120 to 280 ° C, more preferably in the range of 140 to 250 ° C.
- the drying atmosphere may be an inert atmosphere such as nitrogen, helium or reduced pressure, an oxidizing atmosphere such as oxygen or air, or a mixed atmosphere of air and nitrogen, but an inert atmosphere is preferred from the viewpoint of melt viscosity.
- the drying time is preferably 0.5 to 50 hours, more preferably 1 to 30 hours, still more preferably 1 to 20 hours.
- polycarbodiimide (B) examples include aliphatic polycarbodiimide and aromatic polycarbodiimide.
- the polycarbodiimide (B) is not limited to either aliphatic polycarbodiimide or aromatic polycarbodiimide, but because the reactivity of the carbodiimide group is high and the fiber-reinforced polyarylene sulfide obtained has excellent molding cycle properties.
- An aliphatic polycarbodiimide is preferred.
- the aliphatic polycarbodiimide is represented by the general formula —N ⁇ C ⁇ N—R 3 — (wherein R 3 is a divalent organic group of an alicyclic compound such as cyclohexylene, or methylene, ethylene, propylene, methylethylene.
- R 3 is a divalent organic group of an alicyclic compound such as cyclohexylene, or methylene, ethylene, propylene, methylethylene.
- the method for synthesizing the aliphatic polycarbodiimide is not particularly limited.
- the organic polyisocyanate is reacted in the presence of a catalyst that promotes the carbodiimidization reaction of the isocyanate group (hereinafter also referred to as “carbodiimidization catalyst”).
- a catalyst that promotes the carbodiimidization reaction of the isocyanate group hereinafter also referred to as “carbodiimidization catalyst”.
- the organic polyisocyanate used for the synthesis of the aliphatic polycarbodiimide is preferably an organic diisocyanate.
- organic diisocyanates include cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate, and cyclohexylene-1.
- organic polyisocyanate used together with organic diisocyanate in some cases, for example, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methyl isocyanate), 3,5-dimethylcyclohexane-1,3,5-tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2 Trifunctional or higher organic polyisocyanates such as' -triisocyanate and dicyclohexylmethane-2,4,4'-triisocyanate, and the stoichiometric excess of these trifunctional or higher organic polyisocyanates and 2 Terminal isocyanates obtained by reaction with polyfunctional active hydrogen-containing compounds above functionality Or the like can be mentioned the polymer.
- the other organic polyisocyanates can be used singly or in combination of two or more, and the amount used is preferably 0 to 40 per 100 parts by mass of the organic diisocyanate. Parts by mass, more preferably 0 to 20 parts by mass.
- the molecular weight of the resulting aliphatic polycarbodiimide can be appropriately controlled by adding an organic monoisocyanate as necessary.
- organic monoisocyanates examples include alkyl monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, lauryl isocyanate, stearyl isocyanate, cyclohexyl isocyanate, Examples thereof include cycloalkyl monoisocyanates such as 4-methylcyclohexyl isocyanate and 2,5-dimethylcyclohexyl isocyanate.
- organic monoisocyanates can be used singly or in combination of two or more.
- the amount used varies depending on the desired molecular weight of the aliphatic polycarbodiimide.
- the amount is preferably 0 to 40 parts by weight, more preferably 0 to 20 parts by weight per 100 parts by weight of the isocyanate component.
- Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 1-phenyl-3-methyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-sulfide, -Phenyl-3-methyl-2-phospholene-1-sulfide, 1-ethyl-2-phospholene-1-oxide, 1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene 1-sulfide, 1-ethyl-3-methyl-2-phospholene-1-sulfide, 1-methyl-2-phospholene-1-oxide, 1-methyl-3-methyl-2-phospholene-1-oxide, 1 -Methyl-2-phospholene-1-sulfide, 1-methyl-3-methyl-2-phospholene-1-sulfide and their 3-phospholene derivatives Phospholene compounds such as pentacarbonyl iron, nonacarbonyl diiron, tetracarbonyl nickel, hexacarbonyl tungsten, hexacarbony
- the carbodiimidization catalyst can be used singly or in combination of two or more.
- the amount of the catalyst used is preferably 0.001 to 30 parts by mass, more preferably 0.01 to 10 parts by mass per 100 parts by mass of the organic polyisocyanate component.
- the temperature of the synthesis reaction of the aliphatic polycarbodiimide is appropriately selected according to the type of organic polyisocyanate, organic monoisocyanate, and carbodiimidization catalyst, but is usually 20 to 200 ° C.
- the organic polyisocyanate and the organic monoisocyanate component may be added in total before the reaction, or a part or all of them may be added continuously or stepwise during the reaction. Also good.
- a compound capable of reacting with an isocyanate group is added at an appropriate reaction stage from the initial stage to the late stage of the synthesis reaction of the aliphatic polycarbodiimide, and the terminal isocyanate group of the aliphatic polycarbodiimide is sealed.
- the molecular weight of the aliphatic polycarbodiimide can be adjusted, and the molecular weight of the resulting aliphatic polycarbodiimide can be regulated to a predetermined value by adding at the latter stage of the synthesis reaction of the aliphatic polycarbodiimide.
- Examples of the compound capable of reacting with such an isocyanate group include alcohols such as methanol, ethanol, isopropanol and cyclohexanol, and amines such as dimethylamine, diethylamine and benzylamine.
- Aromatic polycarbodiimide is a general formula —N ⁇ C ⁇ N—R 4 — (wherein R 4 is a divalent organic group of a cyclic unsaturated compound such as benzene, toluene, xylene, biphenyl, naphthalene, anthracene, etc.
- R 4 is a divalent organic group of a cyclic unsaturated compound such as benzene, toluene, xylene, biphenyl, naphthalene, anthracene, etc.
- aromatic polycarbodiimide examples include “STABAXOL (registered trademark)” P manufactured by Rhein Chemie and “STABAXOL (registered trademark)” P400 manufactured by Rhein Chemie.
- the polycarbodiimide (B) has a mass average molecular weight of preferably 500 to 40,000, more preferably 1,000 to 5,000. If the mass average molecular weight of the polycarbodiimide (B) is smaller than 500, the molding cycle property of the resulting carbon fiber reinforced polyarylene sulfide may be lowered. If the mass average molecular weight of the polycarbodiimide (B) is larger than 40,000, the melt kneading property with PAS (A) may be lowered, and the molding cycle property of the resulting carbon fiber reinforced polyarylene sulfide may be lowered. In addition, the mass average molecular weight of polycarbodiimide (B) can be calculated
- Carbon fiber (D) As the carbon fiber (D), polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, rayon-based carbon fiber, or the like can be used, and two or more of these fibers can be mixed.
- PAN polyacrylonitrile
- the tensile strength of the carbon fiber (D) is preferably 2,000 MPa or more, more preferably 3,000 MPa or more, and further preferably 4,000 MPa or more. Further, the carbon fiber (D) preferably has a tensile modulus of 200 GPa or more and 700 GPa or less. Further, the carbon fiber (D) has a tensile elongation of preferably 0.5% or more, more preferably 1.0% or more, still more preferably 1.8% or more, and particularly preferably. 2.0% or more.
- the carbon fiber (D) having a high elongation because the mechanical properties such as tensile strength and elongation of the carbon fiber reinforced polyarylene sulfide obtained by the present invention can be achieved at a high level.
- PAN-based carbon fibers are preferably used as the carbon fibers (D).
- the carbon fiber (D) has a surface oxygen concentration ratio (O / C) which is a ratio of the number of atoms of oxygen (O) and carbon (C) on the fiber surface measured by X-ray photoelectron spectroscopy (XPS) is 0. It is preferably from 0.05 to 0.50, more preferably from 0.08 to 0.40, still more preferably from 0.10 to 0.30.
- the surface oxygen concentration ratio (O / C) of the carbon fiber (D) is determined by X-ray photoelectron spectroscopy according to the following procedure. First, the carbon fibers (D) from which the sizing agent and the like have been removed with a solvent are cut and spread and arranged on a copper sample support, and then the photoelectron escape angle is 90 °, and MgK ⁇ 1,2 is used as the X-ray source. Keep the sample chamber at 1 ⁇ 10 ⁇ 8 Torr. As a correction of the peak accompanying charging during measurement, the kinetic energy value (KE) of the main peak of C1S is adjusted to 969 eV. The C1S peak area is the K.S. E.
- the O1S peak area E Is obtained by drawing a straight base line in the range of 958 to 972 eV.
- the O1S peak area E Is obtained by drawing a straight base line in the range of 714 to 726 eV.
- the surface oxygen concentration ratio (O / C) is calculated as an atomic ratio from the ratio of the O1S peak area to the C1S peak area using a sensitivity correction value unique to the apparatus.
- the means for controlling the surface oxygen concentration ratio (O / C) is not particularly limited.
- techniques such as electrolytic oxidation treatment, chemical oxidation treatment, and vapor phase oxidation treatment can be employed.
- An oxidation treatment is preferred.
- the average fiber diameter of the carbon fiber (D) is preferably in the range of 1 to 20 ⁇ m, and more preferably in the range of 3 to 15 ⁇ m. By making it within such a range, in step (III-1), (III-2), or (III-3), the carbon of the component (C-1), (C-2) or (C-3) This is preferable because it can be easily combined with the fiber (D).
- Carbon fiber (D) is surface-treated with a compound (hereinafter abbreviated as compound (E)) having at least three functional groups selected from the group consisting of carboxyl group, hydroxyl group and epoxy group in one molecule. It is preferable that Two or more kinds of the functional groups may be mixed in one molecule, or two or more compounds having three or more one kind of functional groups in one molecule may be used in combination. When only the compound having less than 3 functional groups in one molecule is used, the surface functional group of the carbon fiber (D) and the component (C-1), (C-2) or (C-3) There may be a shortage of reaction points and the mechanical properties of the resulting carbon fiber reinforced polyarylene sulfide may deteriorate.
- compound (E) having at least three functional groups selected from the group consisting of carboxyl group, hydroxyl group and epoxy group in one molecule. It is preferable that Two or more kinds of the functional groups may be mixed in one molecule, or two or more compounds having three or more one kind of functional groups in one molecule
- the present invention is intended when a silane coupling agent having one alkoxysilane and one epoxy group per molecule is used.
- the carbon fiber reinforced polyarylene sulfide having excellent mechanical properties may not be obtained.
- the compound (E) include a polyfunctional epoxy resin, an acrylic acid polymer, a polyhydric alcohol, and the like.
- the surface functional group of the carbon fiber (D) and the components (C-1), (C- A polyfunctional epoxy resin having high reactivity with 2) or (C-3) is preferred.
- polyfunctional epoxy resins include tri- or higher functional aliphatic epoxy resins and phenol novolac type epoxy resins.
- the trifunctional or higher aliphatic epoxy resin means an aliphatic epoxy resin having three or more epoxy groups in one molecule.
- tri- or higher functional aliphatic epoxy resin examples include, for example, glycerol triglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane triglycidyl ether.
- polyglycidyl ethers of aliphatic polyhydric alcohols such as pentaerythritol polyglycidyl ether.
- glycerol triglycidyl ether diglycerol poly (polyglycerol) are included because they contain many highly reactive epoxy groups in one molecule, have high water solubility, and can be easily applied to carbon fibers (D).
- Glycidyl ether and polyglycerol polyglycidyl ether are preferably used in the present invention.
- An acrylic acid polymer is a polymer of acrylic acid, methacrylic acid and maleic acid, and is a generic name for polymers containing 3 or more carboxyl groups in one molecule. Specific examples include polyacrylic acid, a copolymer of acrylic acid and methacrylic acid, a copolymer of acrylic acid and maleic acid, or a mixture of two or more of these. Furthermore, the acrylic acid polymer may be one obtained by partially neutralizing a carboxyl group with an alkali (that is, a carboxylate salt) as long as the number of functional groups is 3 or more in one molecule. good. Examples of the alkali include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide, and ammonium hydroxide. As the acrylic acid-based polymer, polyacrylic acid containing more carboxyl groups in one molecule is preferably used.
- polyhydric alcohol examples include polyvinyl alcohol, glycerol, diglycerol, polyglycerol, sorbitol, arabitol, trimethylolpropane, pentaerythritol and the like.
- polyvinyl alcohol containing more hydroxyl groups in one molecule is preferably used.
- the compound (E) preferably has a value obtained by dividing the mass average molecular weight by the number of the functional groups in one molecule (the total number of carboxyl groups, hydroxyl groups and epoxy groups) of 40 to 150. With such a range, the compound (E) can react with the surface functional group of the carbon fiber (D) or the reactive site with the carbodiimide group of the component (C-1), (C-2) or (C-3). The density can be made more uniform, and the mechanical properties of the resulting carbon fiber reinforced polyarylene sulfide can be further enhanced.
- Compound (E) is preferably present at the interface between component (C-1), (C-2) or (C-3) and carbon fiber (D). For this reason, the compound (E) is applied to the surface of the single yarn of the carbon fiber (D). By applying the compound (E) to the carbon fiber (D) in advance, the surface of the carbon fiber (D) can be effectively modified even with a small amount of adhesion.
- the content of the compound (E) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the carbon fiber (D).
- the content of the compound (E) is less than 0.01 parts by mass, the compound (E) may not be able to sufficiently coat the surface of the carbon fiber (D), and the mechanical properties of the resulting carbon fiber reinforced polyarylene sulfide are improved. The effect is less likely to appear.
- the content rate of a compound (E) exceeds 5 mass parts, since the thickness of the film which a compound (E) forms on the surface of carbon fiber (D) will increase too much, the carbon fiber reinforced polyarylene sulfide obtained is obtained. May reduce the mechanical properties.
- a preferred range of the thickness of the film formed by the compound (E) on the surface of the carbon fiber (D) is 10 to 150 nm.
- the compound (E) for example, a method of immersing a base material made of the carbon fiber (D) in the compound (E) via a roller, the compound (E) The method of spraying on the base material which consists of carbon fiber (D) in mist form, etc. are mentioned.
- the temperature at which the compound (E) is diluted or applied with a solvent or the yarn tension is controlled so that the amount of the compound (E) attached to the single yarn of the carbon fiber (D) becomes more uniform. It is preferable to do.
- Examples of the solvent for diluting the compound (E) include water, methanol, ethanol, dimethylformamide, dimethylacetamide, acetone and the like, but water is preferable from the viewpoint of easy handling and disaster prevention. Such a solvent is removed by evaporation by heating after the compound (E) is applied to the base material composed of the carbon fiber (D).
- an emulsifier or a surfactant As the emulsifier or surfactant, an anionic emulsifier, a cationic emulsifier, a nonionic emulsifier, or the like can be used. Among these, it is preferable to use a nonionic emulsifier having a small interaction because it is difficult to inhibit the effect of the compound (E).
- an impact resistance improver such as an elastomer or a rubber component
- other fillers and additives may be contained in the carbon fiber reinforced polyarylene sulfide within a range not impairing the effects of the present invention.
- additives include flame retardants, conductivity imparting agents, crystal nucleating agents, UV absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, anti-coloring agents, thermal stabilizers, mold release agents Agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, or antifoaming agents.
- the carbon fiber reinforced polyarylene sulfide obtained by the present invention is suitable as an electronic device casing, and is suitably used for computers, televisions, cameras, audio players and the like.
- the carbon fiber reinforced polyarylene sulfide obtained in the present invention is suitable for electrical and electronic component applications, and includes connectors, LED lamps, sockets, optical pickups, terminal boards, printed boards, speakers, small motors, magnetic heads, power modules, and power generators. It is preferably used for machines, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, and the like.
- the carbon fiber reinforced polyarylene sulfide obtained in the present invention is suitable for automobile parts and vehicle-related parts, and includes safety belt parts, instrument panels, console boxes, pillars, roof rails, fenders, bumpers, door panels, roof panels, Hood panel, trunk lid, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, garnish, intake manifold, fuel pump, engine coolant joint, window washer nozzle, wiper, battery peripheral parts, wire harness connector, lamp housing, It is suitably used for lamp reflectors, lamp sockets and the like.
- the carbon fiber reinforced polyarylene sulfide obtained in the present invention is suitable as a building material, such as a wall of a civil engineering building, a roof, a ceiling material related component, a window material related component, a heat insulating material related component, a floor material related component, and a seismic isolation system. It is suitably used for vibration member related parts, lifeline related parts and the like.
- the carbon fiber reinforced polyarylene sulfide obtained by the present invention is suitable as a sports equipment, such as a golf club shaft, a golf-related equipment such as a golf ball, a sports racquet-related equipment such as a tennis racket or a badminton racket, American football or baseball, Suitable for sports equipment such as masks such as softball, helmets, chest pads, elbow pads, knee pads, fishing gear related items such as fishing rods, reels, lures, and winter sports related items such as skis and snowboards.
- a sports equipment such as a golf club shaft, a golf-related equipment such as a golf ball, a sports racquet-related equipment such as a tennis racket or a badminton racket, American football or baseball
- sports equipment such as masks such as softball, helmets, chest pads, elbow pads, knee pads, fishing gear related items such as fishing rods, reels, lures, and winter sports related items such as skis and snowboards.
- the obtained carbon fiber reinforced polyarylene sulfide was processed into the shape of a test piece (200 mm x 200 mm, thickness 1 mm).
- the test piece was sandwiched between two stainless steel plates (300 mm ⁇ 300 mm, thickness 10 mm, mirror finish) preheated to 300 ° C., and placed in a press molding machine to perform press molding.
- the press molding temperature was 300 ° C.
- the press molding pressure was 0.5 MPa
- the press molding time was 3 minutes.
- the test piece was taken out from the press molding machine while being sandwiched between two stainless steel plates, cooled to room temperature, and then separated from the test piece and the stainless steel plate.
- the above operation was taken as one shot, and only a stainless steel plate was reused to perform multiple shot molding, and the bleeding property during the molding cycle was evaluated.
- the evaluation was performed at the 10th and 30th shots, and the presence or absence of cloudiness on the surface of the stainless steel plate was used as a criterion for evaluation. The evaluation was made in the following three stages, and excellent or good was accepted. excellent: The surface of the stainless steel plate was not cloudy even at the 30th shot. good: The surface of the stainless steel plate was not fogged at the 10th shot, and the surface of the stainless steel plate was clouded at the 30th shot. bad: Cloudiness was observed on the surface of the stainless steel plate at the 10th shot.
- step (V) the mold contamination during the molding process cycle was evaluated by observing the surface of the mold during injection molding.
- the composite obtained in the step (III-1), (III-2) or (III-3) or the composite obtained through the step (IV) is made into a molten state in a cylinder of an injection molding machine, and then the molten state The operation until the composite is injected into a molding die, cooled and solidified to be taken out as an injection molded product of a predetermined shape, one shot is performed, the molding die is reused, and multiple shot molding is performed.
- the mold contamination during the molding cycle was evaluated.
- the evaluation was performed at the 10th and 30th shots, with the presence or absence of fogging on the surface of the molding die as a criterion for evaluation, and the evaluation was made in the following three stages, and excellent or good was accepted.
- excellent The surface of the molding die was not cloudy even at the 30th shot.
- good There was no cloudiness on the surface of the molding die at the 10th shot, and cloudiness was seen on the surface of the molding die at the 30th shot.
- Bad Cloudiness was observed on the surface of the molding die at the 10th shot.
- PAS (A) used in Examples and Comparative Examples is as follows.
- PPS-1 Polyphenylene sulfide having a melting point of 285 ° C., a glass transition temperature of 90 ° C., a weight average molecular weight of 30,000, an acid-terminated product, and a chloroform extract of 0.5% by mass
- the polycarbodiimide (B) used for the reference examples, examples and comparative examples is as follows.
- (CDI-1) Aliphatic polycarbodiimide “Carbodilite (registered trademark) HMV-8CA (manufactured by Nisshinbo Chemical Co., Ltd.)” (carbodiimide group equivalent 278, mass average molecular weight 3,000, softening point 70 ° C.)
- the monocarbodiimide (B ′) used in the comparative example is as follows. (CDI-2) N, N′-dicyclohexylcarbodiimide (manufactured by Wako Pure Chemical Industries, Ltd.) (carbodiimide group equivalent 206, mass average molecular weight 206)
- the carbon fibers (D) used in the reference examples, examples and comparative examples are as follows.
- a continuous carbon fiber strand having a total number of 12,000 single yarns was obtained by spinning, firing, and surface oxidation treatment using a copolymer having (CF-1) polyacrylonitrile as a main component.
- the characteristics of this carbon fiber were as follows.
- CF-1 was cut to a length of 6 mm with a cartridge cutter to obtain chopped carbon fibers.
- a carbon fiber dispersion liquid having a carbon fiber concentration of 0.05% by mass was obtained.
- This carbon fiber dispersion is transferred to a cylindrical container having a mesh structure with a diameter of 500 mm at the bottom, subjected to suction filtration, and then the residue is heated and dried in a drying furnace at 200 ° C. for 30 minutes, whereby a non-woven carbon fiber base is formed.
- a material (CFM-1) was obtained.
- the basis weight of the obtained CFM-1 was 50 g / m 2 .
- Example 1 Using the components and conditions shown in Table 1, carbon fiber-reinforced polyarylene sulfide was produced and evaluated by the first production method according to an embodiment of the present invention according to the following procedure.
- Step (I-1) A mixture obtained by dry blending PAS (A) and polycarbodiimide (B) was obtained, and this was put into a lab plast mill apparatus (Toyo Seiki Seisakusho 4C150 type, R-60 type mixer). A melt-kneaded product was obtained by melt-kneading.
- Step (II-1) The obtained melt-kneaded product was transferred to a press molding machine in a molten state to obtain a film made of polycarbodiimide-modified polyarylene sulfide (C-1).
- Step (III-1) The obtained film was alternately laminated with a non-woven carbon fiber substrate (CFM-2), and charged into a press molding machine to produce carbon fiber reinforced polyarylene sulfide.
- CFM-2 non-woven carbon
- Example 1 Example 1 except that the melt-kneading time in step (I-1) was changed to 3,600 seconds, the pressing temperature in step (II-1) was changed to 50 ° C., and the pressing time was changed to 300 seconds.
- the melt-kneading time in step (I-1) was changed to 3,600 seconds
- the pressing temperature in step (II-1) was changed to 50 ° C.
- the pressing time was changed to 300 seconds.
- Example 2 A test piece was prepared in the same manner as in Example 1 except that the press time in the step (II-1) was changed to 1,800 seconds and subjected to each evaluation. The evaluation results are shown in Table 1.
- Example 3 Except having changed the press time in process (II-1) into 900 second, the test piece was produced by the method similar to Example 1, and it used for each evaluation. The evaluation results are shown in Table 1.
- Example 4 Except having changed the press temperature in process (II-1) into 200 degreeC, the test piece was produced by the method similar to Example 1, and it used for each evaluation. The evaluation results are shown in Table 1.
- Example 5 Except having changed the press temperature in process (II-1) to 150 degreeC, the test piece was produced by the method similar to Example 1, and it used for each evaluation. The evaluation results are shown in Table 1.
- Example 2 Except having changed the press temperature in process (II-1) to 50 degreeC, the test piece was produced by the method similar to Example 1, and it used for each evaluation. The evaluation results are shown in Table 1.
- Example 6 A test piece was prepared in the same manner as in Example 1 except that the melt-kneading time in the step (I-1) was changed to 45 seconds and used for each evaluation. The evaluation results are shown in Table 1.
- Example 7 A test piece was prepared in the same manner as in Example 1 except that the amount of polycarbodiimide (B) was changed to 1 part by mass with respect to 100 parts by mass of PAS (A), and used for each evaluation. did. The evaluation results are shown in Table 1.
- Example 3 A test piece was prepared in the same manner as in Example 1 except that the polycarbodiimide (B) was not included, and subjected to each evaluation. The evaluation results are shown in Table 1.
- Example 4 A test piece was prepared in the same manner as in Example 1 except that the amount of polycarbodiimide (B) was changed to 20 parts by mass with respect to 100 parts by mass of PAS (A), and used for each evaluation. did. The evaluation results are shown in Table 1.
- Example 5 A test piece was prepared in the same manner as in Example 1 except that CDI-2, which is a monocarbodiimide (B ′), was used instead of the polycarbodiimide (B), and used for each evaluation. The evaluation results are shown in Table 1.
- Example 8 The amount of carbon fiber (D) is 25 parts by mass with respect to 100 parts by mass of PAS (A), with the amount of component (E) attached being 1 part by mass with respect to 100 parts by mass of carbon fiber (D).
- a test piece was prepared in the same manner as in Example 1 except that the content of the nonwoven fabric-shaped carbon fiber base material (CFM-2) was changed, and subjected to each evaluation. The evaluation results are shown in Table 1.
- Example 9 The amount of the carbon fiber (D) is 100 parts by mass with respect to 100 parts by mass of the PAS (A) while the amount of the component (E) is 1 part by mass with respect to 100 parts by mass of the carbon fiber (D).
- a test piece was prepared in the same manner as in Example 1 except that the content of the nonwoven fabric-shaped carbon fiber base material (CFM-2) was changed, and subjected to each evaluation. The evaluation results are shown in Table 1.
- Example 10 In order to change the component (E) to E-2, a test piece was prepared in the same manner as in Example 1 except that a non-woven carbon fiber base material (CFM-3) was used. did. The evaluation results are shown in Table 1.
- Example 11 A test piece was prepared in the same manner as in Example 1 except that a non-woven carbon fiber substrate (CFM-4) was used to change the component (E) to E-3, and the test piece was used for each evaluation. did.
- the evaluation results are shown in Table 1.
- Example 12 A test piece was prepared in the same manner as in Example 1 except that a nonwoven fabric-shaped carbon fiber base material (CFM-1) was used so as not to include the component (E), and used for each evaluation. The evaluation results are shown in Table 1.
- CFM-1 nonwoven fabric-shaped carbon fiber base material
- step (I-1) the mixer part of the lab plast mill device is covered with a vacuum vessel equipped with a vacuum gauge and a vacuum pump, and the degree of vacuum in the vacuum vessel during melt-kneading is adjusted to -0.1 MPa.
- a test piece was prepared in the same manner as in Example 3 except for the above, and subjected to each evaluation. The evaluation results are shown in Table 1.
- Example 14 The carbon fiber reinforced polyarylene sulfide obtained in step (III-1) is charged again into the press molding machine as step (IV) and heated under the conditions of a press temperature of 250 ° C., a press pressure of 0.5 MPa, and a press time of 3600 seconds. Except having performed, the test piece was produced by the same method as Example 3, and it used for each evaluation. The evaluation results are shown in Table 1.
- Example 1 Since Example 1 satisfies all the requirements of steps (I-1) to (III-1), it has both mechanical properties and molding cycle properties, and is excellent in productivity of carbon fiber reinforced polyarylene sulfide.
- Example 6 From a comparison between Example 1 and Example 6, it can be seen that the bleed component of the carbon fiber-reinforced polyarylene sulfide obtained in the step (I-1) where t1 ⁇ t2 is obtained is reduced, and the molding cycle property is improved.
- Example 1 From a comparison between Example 1 and Comparative Example 5, a carbon fiber reinforced polyarylene sulfide having both mechanical properties and molding cycle properties is obtained by using a polycarbodiimide (B) having at least two carbodiimide groups in one molecule.
- B polycarbodiimide
- Examples 1, 8, and 9 show that carbon fiber-reinforced polyarylene sulfide having both mechanical properties and molding cycle properties can be obtained even when the amount of carbon fiber (D) is changed.
- Example 13 From the comparison between Example 13 and Example 3, by performing the melt-kneading in the step (I-1) under reduced pressure conditions, the bleed component of the obtained carbon fiber reinforced polyarylene sulfide is reduced and the molding cycle property is improved. I understand that.
- step (IV) the carbon fiber-reinforced polyarylene sulfide obtained in step (III-1) was heated at a temperature not lower than the glass transition temperature and not higher than the melting point of PAS (A). It can be seen that by heating, the bleed component of the obtained carbon fiber reinforced polyarylene sulfide is reduced and the molding cycle property is improved.
- step (I-2) CDI-3 is obtained as a polycarbodiimide reactant (B-2) by heating polycarbodiimide (B) in a hot air oven at the heating temperature and heating time shown in Table 2. It was. The heat resistance temperature of the obtained CDI-3 was measured with a thermogravimetric analyzer, and the evaluation results are shown in Table 2.
- a polycarbodiimide reactant (B-2) is obtained by heating the polycarbodiimide (B) in the same manner as in Reference Example 5 except that the heating temperature is 300 ° C. and the heating time is changed to 0.5 hour.
- CDI-5 was obtained.
- the heat resistance temperature of the obtained CDI-5 was measured with a thermogravimetric analyzer, and the evaluation results are shown in Table 2.
- Polycarbodiimide (B) was prepared in the same manner as in Reference Example 5 except that a vacuum oven and a vacuum pump were used instead of the hot air oven and the degree of vacuum in the vacuum oven was adjusted to be -0.1 MPa.
- CDI-6 was obtained as a polycarbodiimide reactant (B-2).
- the heat resistance temperature of the obtained CDI-6 was measured with a thermogravimetric analyzer, and the evaluation results are shown in Table 2.
- Example 16 A test piece was prepared in the same manner as in Example 15 except that CDI-4 was used as the polycarbodiimide reactant (B-2) and subjected to each evaluation. The evaluation results are shown in Table 3.
- Example 17 A test piece was prepared in the same manner as in Example 15 except that CDI-5 was used as the polycarbodiimide reactant (B-2) and subjected to each evaluation. The evaluation results are shown in Table 3.
- Example 18 A test piece was prepared in the same manner as in Example 15 except that CDI-6 was used as the polycarbodiimide reactant (B-2) and subjected to each evaluation. The evaluation results are shown in Table 3.
- Example 19 A test piece was prepared in the same manner as in Example 15 except that CDI-7 was used as the polycarbodiimide reactant (B-2) and subjected to each evaluation. The evaluation results are shown in Table 3.
- Example 20 The carbon fiber reinforced polyarylene sulfide obtained in step (III-2) is charged again into the press molding machine as step (IV), and heated under the conditions of a press temperature of 250 ° C., a press pressure of 0.5 MPa, and a press time of 3600 seconds.
- a test piece was prepared in the same manner as in Example 19 except that the above was performed and used for each evaluation. The evaluation results are shown in Table 3.
- Example 6 A test piece was prepared in the same manner as in Example 15 except that the polycarbodiimide reactant (B-2) was not included, and subjected to each evaluation. The evaluation results are shown in Table 3.
- Example 7 A test piece was prepared in the same manner as in Example 15 except that CDI-2, which is a monocarbodiimide (B ′), was used instead of the polycarbodiimide reactant (B-2) and subjected to each evaluation. .
- the evaluation results are shown in Table 3.
- Example 21 The amount of carbon fiber (D) is 25 parts by mass with respect to 100 parts by mass of PAS (A), with the amount of component (E) attached being 1 part by mass with respect to 100 parts by mass of carbon fiber (D).
- a test piece was prepared in the same manner as in Example 15 except that the content of the nonwoven fabric-shaped carbon fiber substrate (CFM-2) was changed, and subjected to each evaluation. The evaluation results are shown in Table 3.
- Example 22 The amount of the carbon fiber (D) is 100 parts by mass with respect to 100 parts by mass of the PAS (A) while the amount of the component (E) is 1 part by mass with respect to 100 parts by mass of the carbon fiber (D).
- a test piece was prepared in the same manner as in Example 15 except that the content of the nonwoven fabric-shaped carbon fiber substrate (CFM-2) was changed, and subjected to each evaluation. The evaluation results are shown in Table 3.
- Example 23 A test piece was prepared in the same manner as in Example 15 except that a nonwoven fabric-shaped carbon fiber base material (CFM-1) was used so as not to include the component (E), and was used for each evaluation. The evaluation results are shown in Table 3.
- Comparison of Reference Examples 5 to 8 and Reference Example 10 shows that heat resistance is insufficient when monocarbodiimide (B ′) is used instead of polycarbodiimide (B).
- Example 15 Since Example 15 satisfies all the requirements of steps (I-2) to (III-2), it has both mechanical properties and molding cycle properties, and is excellent in productivity of carbon fiber reinforced polyarylene sulfide.
- a comparison of Examples 15 to 18 shows that the lower the temperature at which the polycarbodiimide (B) in step (II-2) is heated at a temperature equal to or higher than the softening point of the component, the lower the carbon fiber obtained, the more obtainable carbon fiber. It can be seen that the mechanical properties of the reinforced polyarylene sulfide can be improved.
- the carbon fiber reinforced polyarylene sulfide obtained in the step (III-2) was heated at a temperature not lower than the glass transition temperature and not higher than the melting point of PAS (A). It can be seen that by heating, the bleed component of the obtained carbon fiber reinforced polyarylene sulfide is reduced and the molding cycle property is improved.
- Examples 15, 21, and 22 show that carbon fiber-reinforced polyarylene sulfide having both mechanical properties and molding cycle properties can be obtained even when the amount of carbon fiber (D) is changed.
- Example 15 From the comparison between Example 15 and Example 23, it can be seen that by using the component (E), a carbon fiber-reinforced polyarylene sulfide having more excellent mechanical properties can be obtained.
- Step (I-3) A mixture obtained by dry blending PAS (A) and polycarbodiimide (B) was obtained.
- Step (II-3): The obtained mixture was main-fed to a twin-screw extruder (JSW company TEX-30 ⁇ , (screw length) / (screw diameter) 31.5) and melt-kneaded.
- the melt kneading was performed at a cylinder temperature of 350 ° C., and the time (melt kneading time) required from the main feed to the discharge of each component was 300 seconds.
- the melt-kneaded product was discharged from a T-die attached to the tip of the twin screw extruder and cooled with a cooling roll to obtain a film made of polycarbodiimide-modified polyarylene sulfide (C-3).
- Step (III-3) The obtained film is cut into a predetermined size, laminated with non-woven carbon fiber base material (CFM-2) alternately, and put into a press molding machine to be carbon fiber reinforced polyarylene. Sulfide was produced.
- Example 25 A test piece was prepared in the same manner as in Example 24 except that the cylinder temperature of the twin screw extruder in Step (II-3) was changed to 330 ° C., and used for each evaluation. The evaluation results are shown in Table 4.
- Example 26 The carbon fiber reinforced polyarylene sulfide obtained in step (III-3) is charged again into the press molding machine as step (IV), and heated under the conditions of a press temperature of 250 ° C., a press pressure of 0.5 MPa, and a press time of 3600 seconds. Except having performed, the test piece was produced by the method similar to Example 25, and it used for each evaluation. The evaluation results are shown in Table 4.
- Example 8 The test was conducted in the same manner as in Example 24, except that the cylinder temperature of the twin-screw extruder in step (II-3) was changed to 300 ° C., and the press temperature in step (III-3) was changed to 350 ° C. Pieces were prepared and subjected to each evaluation. The evaluation results are shown in Table 4.
- Example 9 A test piece was prepared in the same manner as in Example 24 except that the pressing temperature in the step (III-3) was changed to 420 ° C. As a result, the polycarbodiimide-modified polyarylene sulfide in the step (III-3) ( Compounding of C-3) and carbon fiber (D) was difficult, and carbon fiber-reinforced polyarylene sulfide could not be obtained.
- the evaluation results are shown in Table 4.
- Example 10 A test piece was prepared in the same manner as in Example 24 except that the polycarbodiimide (B) was not included, and subjected to each evaluation. The evaluation results are shown in Table 4.
- Example 11 A test piece was prepared in the same manner as in Example 24 except that the amount of polycarbodiimide (B) was changed to 20 parts by mass with respect to 100 parts by mass of PAS (A), and used for each evaluation. did. The evaluation results are shown in Table 4.
- Example 27 The amount of carbon fiber (D) is 25 parts by mass with respect to 100 parts by mass of PAS (A), with the amount of component (E) attached being 1 part by mass with respect to 100 parts by mass of carbon fiber (D).
- a test piece was prepared in the same manner as in Example 24 except that the content of the nonwoven fabric-shaped carbon fiber substrate (CFM-2) was changed, and subjected to each evaluation. The evaluation results are shown in Table 4.
- Example 28 The amount of the carbon fiber (D) is 100 parts by mass with respect to 100 parts by mass of the PAS (A) while the amount of the component (E) is 1 part by mass with respect to 100 parts by mass of the carbon fiber (D).
- a test piece was prepared in the same manner as in Example 24 except that the content of the nonwoven fabric-shaped carbon fiber substrate (CFM-2) was changed, and subjected to each evaluation. The evaluation results are shown in Table 4.
- Example 29 A test piece was prepared in the same manner as in Example 24 except that a non-woven carbon fiber base material (CFM-1) was used so as not to include the component (E), and the test piece was used for each evaluation.
- the evaluation results are shown in Table 4.
- Examples 24 and 25 satisfy all the requirements of steps (I-3) to (III-3), they have both mechanical properties and molding cycle properties, and are excellent in productivity of carbon fiber-reinforced polyarylene sulfide.
- step (IV) the carbon fiber reinforced polyarylene sulfide obtained in step (III-3) was heated at a temperature not lower than the glass transition temperature of PAS (A) and not higher than the melting point. It can be seen that by heating, the bleed component of the obtained carbon fiber reinforced polyarylene sulfide is reduced and the molding cycle property is improved.
- Comparative Example 8 does not satisfy the requirements of the step (III-3), and thus the obtained carbon fiber reinforced polyarylene sulfide is inferior in molding cycle property.
- Example 24 From the comparison between Example 24 and Comparative Examples 10 and 11, the amount of polycarbodiimide (B) was 0.1 to 10 parts by mass with respect to 100 parts by mass of PAS (A). It can be seen that a carbon fiber reinforced polyarylene sulfide having both of the above can be obtained.
- Example 24 From a comparison between Example 24 and Comparative Example 12, a carbon fiber reinforced polyarylene sulfide having both mechanical properties and molding cycle properties is obtained by using a polycarbodiimide (B) having at least two carbodiimide groups in one molecule.
- B polycarbodiimide
- Examples 24, 27, and 28 show that carbon fiber-reinforced polyarylene sulfide having both mechanical properties and molding cycle properties can be obtained even if the amount of carbon fiber (D) is changed.
- Example 24 From the comparison between Example 24 and Example 29, it can be seen that by using the component (E), a carbon fiber-reinforced polyarylene sulfide having more excellent mechanical properties can be obtained.
- the composite obtained in the step (III-1) of Example 1 is cut into pellets having an average particle size of 5 mm, and the pellet is obtained using an injection molding machine (JSW J150EII-P).
- JSW J150EII-P injection molding machine
- a test piece was prepared by using for injection molding. Injection molding was performed at a cylinder temperature of 300 ° C. and a mold temperature of 150 ° C., and the maximum pressure during injection molding was taken as the injection molding pressure.
- the evaluation results are shown in Table 5.
- Example 31 Except having used the composite_body
- Example 32 A test piece was prepared in the same manner as in Example 31 except that the cylinder temperature of the injection molding in the step (V) was changed to 290 ° C., and used for each evaluation. The evaluation results are shown in Table 5.
- Example 33 A test piece was prepared in the same manner as in Example 31 except that the cylinder temperature of the injection molding in the step (V) was changed to 350 ° C., and used for each evaluation. The evaluation results are shown in Table 5.
- Example 34 Except having used the composite_body
- Example 30 Since Example 30 satisfies the steps (I-1) to (III-1) and the step (V), it has both mechanical properties and molding cycle properties, and is excellent in productivity of carbon fiber reinforced polyarylene sulfide.
- Example 34 in order to satisfy the steps (I-1) to (III-1), the step (IV), and the step (V), both the mechanical properties and the molding cycle property are achieved, and the productivity of the carbon fiber reinforced polyarylene sulfide is improved. Also excellent.
- step (V) the composite obtained in step (III-2) of Example 15 was cut into pellets having an average particle diameter of 5 mm.
- a test piece was prepared by using an injection molding machine (JSW J150EII-P) and using the pellets for injection molding. Injection molding was performed at a cylinder temperature of 300 ° C. and a mold temperature of 150 ° C., and the maximum pressure during injection molding was taken as the injection molding pressure. The evaluation results are shown in Table 6.
- Example 36 Except having used the composite_body
- Example 37 A test piece was prepared in the same manner as in Example 36 except that the cylinder temperature of the injection molding in the step (V) was changed to 290 ° C., and used for each evaluation. The evaluation results are shown in Table 6.
- Example 38 A test piece was prepared in the same manner as in Example 36 except that the cylinder temperature of the injection molding in the step (V) was changed to 350 ° C., and used for each evaluation. The evaluation results are shown in Table 6.
- Example 39 Except having used the composite_body
- Example 35 Since Example 35 satisfies the steps (I-2) to (III-2) and the step (V), it has both mechanical properties and molding cycle properties, and is excellent in productivity of carbon fiber reinforced polyarylene sulfide.
- Example 39 in order to satisfy the steps (I-2) to (III-2), the step (IV), and the step (V), both the mechanical properties and the molding cycle property are obtained, and the productivity of the carbon fiber reinforced polyarylene sulfide is improved. Also excellent.
- step (V) the composite obtained in step (III-3) of Example 24 was cut into pellets having an average particle diameter of 5 mm.
- a test piece was prepared by using an injection molding machine (JSW J150EII-P) and using the pellets for injection molding. Injection molding was performed at a cylinder temperature of 300 ° C. and a mold temperature of 150 ° C., and the maximum pressure during injection molding was taken as the injection molding pressure. The evaluation results are shown in Table 7.
- Example 41 Except having used the composite_body
- Example 42 A test piece was prepared in the same manner as in Example 41 except that the cylinder temperature of the injection molding in the step (V) was changed to 290 ° C., and used for each evaluation. The evaluation results are shown in Table 7.
- Example 43 A test piece was prepared in the same manner as in Example 41 except that the cylinder temperature of the injection molding in the step (V) was changed to 350 ° C., and used for each evaluation. The evaluation results are shown in Table 7.
- Example 44 Except having used the composite_body
- Example 40 Since Example 40 satisfies the steps (I-3) to (III-3) and the step (V), it has both mechanical properties and molding cycle properties, and is excellent in productivity of carbon fiber reinforced polyarylene sulfide.
- Example 44 in order to satisfy the steps (I-3) to (III-3) and the steps (IV) and (V), both the mechanical properties and the molding cycleability were achieved, and the productivity of the carbon fiber reinforced polyarylene sulfide was improved. Also excellent.
- the carbon fiber reinforced polyarylene sulfide obtained in the present invention can be suitably used for electronic equipment casings, electrical / electronic parts applications, automotive parts, vehicle-related parts, building materials, sports equipment, and the like.
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Abstract
Description
(1)下記(I‐1)~(III‐1)の工程を含む、炭素繊維強化ポリアリーレンスルフィドの製造方法。
(I‐1)ポリアリーレンスルフィド(A)100質量部とカルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)0.1~10質量部を混合し、得られた混合物を加熱して溶融混練することで溶融混練物を得る工程
(II‐1)工程(I‐1)で得られる溶融混練物を、ポリアリーレンスルフィド(A)のガラス転移温度以上かつ融点以下の温度で加熱することで、溶融混練物内のカルボジイミド基の反応を促進してポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)を得る工程
(III‐1)工程(II‐1)で得られるポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程
(2)下記(I‐2)~(III‐2)の工程を含む、炭素繊維強化ポリアリーレンスルフィドの製造方法。
(I‐2)カルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)を、該成分(B)の軟化点以上の温度で加熱することで、カルボジイミド基同士の反応を促進してポリカルボジイミド反応物(B‐2)を得る工程
(II‐2)ポリアリーレンスルフィド(A)100質量部と前記ポリカルボジイミド反応物(B‐2)0.1~10質量部を混合し、得られた混合物を加熱して溶融混練することでポリカルボジイミド変性ポリアリーレンスルフィド(C‐2)を得る工程
(III‐2)工程(II‐2)で得られるポリカルボジイミド変性ポリアリーレンスルフィド(C‐2)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程
(3)下記(I‐3)~(III‐3)の工程を含む、炭素繊維強化ポリアリーレンスルフィドの製造方法。
(I‐3)ポリアリーレンスルフィド(A)100質量部とカルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)0.1~10質量部を混合した混合物を得る工程
(II‐3)工程(I‐3)で得られる混合物を、ポリアリーレンスルフィド(A)の融点以上の温度で加熱して溶融混練することで、カルボジイミド基の反応を促進してポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)を得る工程
(III‐3)工程(II‐3)における溶融混練時以下の温度で前記ポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程
工程(I‐1)は、ポリアリーレンスルフィド(A)とポリカルボジイミド(B)を混合し、得られた混合物を加熱して溶融混練することで溶融混練物を得る工程である。
工程(II‐1)は、工程(I‐1)で得られる溶融混練物を、ポリアリーレンスルフィド(A)のガラス転移温度以上かつ融点以下の温度で加熱することで、溶融混練物内のカルボジイミド基の反応を促進してポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)を得る工程である。
反応(1):ポリアリーレンスルフィド(A)が有する官能基とポリカルボジイミド(B)が有するカルボジイミド基の反応
反応(2):ポリカルボジイミド(B)が有するカルボジイミド基同士が反応して2量体または3量体を形成し、ポリカルボジイミド(B)が架橋構造を形成する反応
工程(III‐1)は、工程(II‐1)で得られるポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)を溶融させ、炭素繊維(D)と複合化させて複合体を得る工程である。
工程(I‐2)は、カルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)を、該成分(B)の軟化点以上の温度で加熱することで、カルボジイミド基同士の反応を促進してポリカルボジイミド反応物(B‐2)を得る工程である。
工程(II‐2)は、ポリアリーレンスルフィド(A)100質量部と工程(I‐2)で得られたポリカルボジイミド反応物(B‐2)0.1~10質量部を混合し、得られた混合物を加熱して溶融混練することでポリカルボジイミド変性ポリアリーレンスルフィド(C‐2)を得る工程である。
工程(III‐2)は、工程(II‐2)で得られるポリカルボジイミド変性ポリアリーレンスルフィド(C‐2)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程である。
工程(I‐3)は、ポリアリーレンスルフィド(A)100質量部とカルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)0.1~10質量部を混合した混合物を得る工程である。
工程(II‐3)は、工程(I‐3)で得られる混合物を、ポリアリーレンスルフィド(A)の融点以上の温度で加熱して溶融混練することで、カルボジイミド基の反応を促進してポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)を得る工程である。
工程(III‐3)は、工程(II‐3)における溶融混練時以下の温度で前記ポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程である。
前記した炭素繊維(D)からなる基材としては、連続した炭素繊維(D)を一方向に配列させてシート状とした一方向配列基材や、織物(クロス)、不織布、編み物、組み紐、ヤーン、トウ、などが挙げられる。中でも、ポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)、(C‐2)、または(C‐3)が比較的含浸し易い不織布状の炭素繊維(D)からなる基材が好ましく用いられる。不織布状の炭素繊維(D)としては、炭素繊維の単糸がランダムに分散している場合が好ましく、かかる炭素繊維(D)の単糸の繊維長は、数平均繊維長で0.01~20mmが好ましく、0.01~10mmがより好ましい。かかる範囲内とすることで、力学特性と成形加工時の流動性に優れた炭素繊維強化ポリアリーレンスルフィドが得られる。また、炭素繊維(D)の繊維長が長くなるほど、得られるポリカルボジイミド変性ポリアリーレンスルフィドの力学特性が向上する。
本発明のいずれの製造方法にも、さらに次に示す工程(IV)を含むことが好ましい。工程(IV)は、工程(III‐1)、(III‐2)または(III‐3)で得られる複合体を、ポリアリーレンスルフィド(A)のガラス転移温度以上かつ融点以下の温度で加熱することで、複合体内のカルボジイミド基の反応を促進する工程である。
本発明のいずれの製造方法にも、さらに次に示す工程(V)を含むことが好ましい。工程(V)は、工程(III‐1)、(III‐2)または(III‐3)において得られる複合体または工程(IV)を経た複合体を、射出成形またはプレス成形する工程である。
ポリアリーレンスルフィド(A)(以下、ポリアリーレンスルフィドをPASと略することもある)は、式、-(Ar-S)-の繰り返し単位を主要構成単位とする、好ましくは当該繰り返し単位を80モル%以上、より好ましくは90モル%以上、さらに好ましくは95モル%以上含有するホモポリマーまたはコポリマーである。Arとしては次の式(a)~式(k)などで表される単位などがあるが、なかでも式(a)で表される単位が特に好ましい。
ポリカルボジイミド(B)としては、脂肪族ポリカルボジイミドおよび芳香族ポリカルボジイミドが例示できる。ポリカルボジイミド(B)は、脂肪族ポリカルボジイミド、芳香族ポリカルボジイミドいずれかに限定されるものではないが、カルボジイミド基の反応性が高く、得られる繊維強化ポリアリーレンスルフィドの成形サイクル性に優れるために、脂肪族ポリカルボジイミドであることが好ましい。
炭素繊維(D)としては、ポリアクリロニトリル(PAN)系炭素繊維、ピッチ系炭素繊維、レーヨン系炭素繊維などが使用でき、これらの繊維を2種以上混在させることもできる。
本発明では、本発明の効果を損なわない範囲で、エラストマーあるいはゴム成分などの耐衝撃性向上剤、他の充填材や添加剤を、炭素繊維強化ポリアリーレンスルフィドに含有しても良い。添加剤の例としては、難燃剤、導電性付与剤、結晶核剤、紫外線吸収剤、酸化防止剤、制振剤、抗菌剤、防虫剤、防臭剤、着色防止剤、熱安定剤、離型剤、帯電防止剤、可塑剤、滑剤、着色剤、顔料、染料、発泡剤、あるいは制泡剤が挙げられる。
本発明で得られる炭素繊維強化ポリアリーレンスルフィドは、電子機器筐体として好適であり、コンピューター、テレビ、カメラ、オーディオプレイヤーなどに好適に使用される。
得られた炭素繊維強化ポリアリーレンスルフィドを、試験片(200mm×200mm、厚み1mm)の形状に加工した。この試験片を300℃に予熱した2枚のステンレス板(300mm×300mm、厚み10mm、鏡面加工)の間に挟み、プレス成形機に投入し、プレス成形を行った。プレス成形温度は300℃、プレス成形圧は0.5MPa、プレス成形時間は3分とした。次に試験片を2枚のステンレス板で挟んだ状態のままプレス成形機から取り出し、室温まで冷却後試験片とステンレス板を分離した。以上の操作を1ショットとし、ステンレス板のみ再利用して、複数ショット成形を行い、成形加工サイクル時のブリード性を評価した。評価は10ショット目と30ショット目で行い、ステンレス板の表面の曇りの有無を判断基準とし、以下の3段階で評価し、excellentまたはgoodを合格とした。
excellent:30ショット目でもステンレス板の表面に曇りは無かった。
good:10ショット目時点ではステンレス板の表面に曇りが無く、30ショット目時点でステンレス板の表面に曇りが見られた。
bad:10ショット目時点でステンレス板の表面に曇りが見られた。
ASTM D638に準拠し、Type‐I試験片を用い、試験機として、“インストロン(登録商標)”万能試験機(インストロン社製)を用いた。引張伸度とは、ひずみゲージを用いて測定した破断点ひずみのことを指す。
試験機として熱重量分析装置(パーキンエルマー社製TGA7)を用いた。なお、試料は2mm以下の粒状物を用いた。試料10mgを用いて、空気雰囲気下で30℃から400℃まで昇温速度20℃/分で加熱し、試料の質量変化を測定した。この操作において、試料の質量が30℃時点から5質量%減少した際の温度を耐熱温度とした。
工程(V)において、射出成形した際の成形金型の表面を観察することにより、成形加工サイクル時の金型汚染性を評価した。工程(III‐1)、(III‐2)または(III‐3)で得られた複合体または工程(IV)を経た複合体を、射出成形機のシリンダー内で溶融状態とし、次いでこの溶融状態の複合体を成形金型内に射出し、冷却、固化することで所定の形状の射出成形品として取り出すまでの操作を1ショットとし、成形金型を再利用して、複数ショット成形を行い、成形加工サイクル時の金型汚染性を評価した。評価は10ショット目と30ショット目で行い、成形金型の表面の曇りの有無を判断基準とし、以下の3段階で評価し、excellentまたはgoodを合格とした。
excellent:30ショット目でも成形金型の表面に曇りは無かった。
good:10ショット目時点では成形金型の表面に曇りが無く、30ショット目時点で成形金型の表面に曇りが見られた。
bad:10ショット目時点で成形金型の表面に曇りが見られた。
(PPS‐1)融点285℃、ガラス転移温度90℃、質量平均分子量30,000、酸末端品、クロロホルム抽出量0.5質量%のポリフェニレンスルフィド
(CDI‐1)脂肪族ポリカルボジイミド「“カルボジライト(登録商標)”HMV‐8CA(日清紡ケミカル社製)」(カルボジイミド基当量278、質量平均分子量3,000、軟化点70℃)
(CDI‐2)N,N’-ジシクロヘキシルカルボジイミド(和光純薬工業社製)(カルボジイミド基当量206、質量平均分子量206)
(CF‐1)ポリアクリロニトリルを主成分とする共重合体を用いて、紡糸、焼成処理、および表面酸化処理を行うことによって、総単糸数12,000本の連続した炭素繊維ストランドを得た。この炭素繊維の特性は次に示す通りであった。
引張強度:4,900MPa
引張弾性率:240GPa
引張伸度:2%
比重:1.8
単糸直径:7μm
表面酸素濃度比[O/C]:0.12
(E‐1)グリセロールトリグリシジルエーテル(和光純薬工業社製)
質量平均分子量:260
1分子当たりのエポキシ基数:3
質量平均分子量を1分子当たりのカルボキシル基、水酸基、エポキシ基、水酸基の総数で除した値:87
(E‐2)ポリアクリル酸(SIGMA‐ALDRICH社製)
質量平均分子量:2,000
1分子当たりのカルボキシル基数:27
質量平均分子量を1分子当たりのカルボキシル基、水酸基、エポキシ基、水酸基の総数で除した値:74
(E‐3)ポリビニルアルコール(和光純薬工業社製)
質量平均分子量:22,000
1分子当たりの水酸基数:500
質量平均分子量を1分子当たりのカルボキシル基、水酸基、エポキシ基、水酸基の総数で除した値:44
CF‐1をカートリッジカッターで長さ6mmにカットし、チョップド炭素繊維を得た。水と界面活性剤(ナカライテクス社製、ポリオキシエチレンラウリルエーテル(商品名))からなる濃度0.1質量%の分散液を作製し、この分散液にチョップド炭素繊維を添加し、攪拌することで炭素繊維濃度0.05質量%の炭素繊維分散液を得た。この炭素繊維分散液を底部に直径500mmのメッシュ構造を有する円筒形状容器に移し、吸引ろ過を行い、次に残渣を200℃の乾燥炉で30分加熱乾燥させることにより、不織布形状の炭素繊維基材(CFM‐1)を得た。得られたCFM‐1の目付けは50g/m2であった。
成分(E)としてE‐1を用い、成分(E)を2質量%含む水系の分散母液に、参考例1で作製したCFM‐1を浸漬させ、次いで230℃で乾燥することで、成分(E)で表面処理をした炭素繊維(D)からなる基材(CFM‐2)を得た。乾燥後の成分(E)の付着量は、炭素繊維(D)100質量部に対して1質量部であった。
成分(E)としてE‐2を用い、成分(E)を2質量%含む水系の分散母液に、参考例1で作製したCFM‐1を浸漬させ、次いで230℃で乾燥することで、成分(E)で表面処理をした炭素繊維(D)からなる基材(CFM‐3)を得た。乾燥後の成分(E)の付着量は、炭素繊維(D)100質量部に対して1質量部であった。
成分(E)としてE‐3を用い、成分(E)を2質量%含む水系の分散母液に、参考例1で作製したCFM‐1を浸漬させ、次いで230℃で乾燥することで、成分(E)で表面処理をした炭素繊維(D)からなる基材(CFM‐4)を得た。乾燥後の成分(E)の付着量は、炭素繊維(D)100質量部に対して1質量部であった。
表1に示す成分、条件を用いて、以下の手順による本発明の一実施形態に係る第1の製造方法で炭素繊維強化ポリアリーレンスルフィドを製造し、評価を行った。
工程(I‐1):PAS(A)とポリカルボジイミド(B)をドライブレンドさせた混合物を得て、これをラボプラストミル装置(東洋精機製作所 4C150型、R‐60型ミキサー)に投入し、溶融混練することで溶融混練物を得た。
工程(II‐1):得られた溶融混練物を溶融状態のままプレス成形機に移し、ポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)からなるフィルムを得た。
工程(III‐1):得られたフィルムを不織布形状の炭素繊維基材(CFM‐2)と交互に積層し、プレス成形機に投入することで炭素繊維強化ポリアリーレンスルフィドを製造した。
工程(I‐1)における、溶融混練時間を3,600秒に代え、工程(II‐1)におけるプレス温度を50℃に代え、さらにプレス時間を300秒に代えた以外は、実施例1と同様の方法で、試験片を作製しようとしたところ、工程(III‐1)におけるポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)と炭素繊維(D)との複合化が困難であり、炭素繊維強化ポリアリーレンスルフィドを得ることができなかった。評価結果を表1に記載した。
工程(II‐1)におけるプレス時間を1,800秒に代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(II‐1)におけるプレス時間を900秒に代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(II‐1)におけるプレス温度を200℃に代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(II‐1)におけるプレス温度を150℃に代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(II‐1)におけるプレス温度を50℃に代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(I‐1)における、溶融混練時間を45秒に代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
ポリカルボジイミド(B)の量を、PAS(A)100質量部に対して1質量部となるように代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
ポリカルボジイミド(B)を含まない以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
ポリカルボジイミド(B)の量を、PAS(A)100質量部に対して20質量部となるように代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
ポリカルボジイミド(B)の代わりに、モノカルボジイミド(B’)であるCDI‐2を用いた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
成分(E)の付着量を炭素繊維(D)100質量部に対して1質量部としたまま、炭素繊維(D)の量が、PAS(A)100質量部に対して25質量部となるように不織布形状の炭素繊維基材(CFM‐2)の含有量を代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
成分(E)の付着量を炭素繊維(D)100質量部に対して1質量部としたまま、炭素繊維(D)の量が、PAS(A)100質量部に対して100質量部となるように不織布形状の炭素繊維基材(CFM‐2)の含有量を代えた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
成分(E)をE‐2とするために、不織布形状の炭素繊維基材(CFM‐3)を用いた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
成分(E)をE‐3とするために、不織布形状の炭素繊維基材(CFM‐4)を用いた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
成分(E)を含まないように、不織布形状の炭素繊維基材(CFM‐1)を用いた以外は、実施例1と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(I‐1)において、ラボプラストミル装置のミキサー部分を、真空ゲージと真空ポンプを備えた真空容器で覆い、溶融混練中の真空容器内の減圧度が-0.1MPaとなるように調節した以外は、実施例3と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(III‐1)で得られた炭素繊維強化ポリアリーレンスルフィドを、工程(IV)として再度プレス成形機に投入し、プレス温度250℃、プレス圧力0.5MPa、プレス時間3600秒の条件で加熱を行った以外は、実施例3と同様の方法で、試験片を作製し、各評価に供した。評価結果を表1に記載した。
工程(I‐2)として、表2に記載の加熱温度と加熱時間で、熱風オーブン内でポリカルボジイミド(B)を加熱することにより、ポリカルボジイミド反応物(B‐2)としてCDI‐3を得た。得られたCDI‐3の耐熱温度を熱重量分析装置により測定し、評価結果を表2に記載した。
加熱温度を200℃とし、加熱時間を2時間に代えた以外は、参考例5と同様の方法で、ポリカルボジイミド(B)を加熱することにより、ポリカルボジイミド反応物(B‐2)としてCDI‐4を得た。得られたCDI‐4の耐熱温度を熱重量分析装置により測定し、評価結果を表2に記載した。
加熱温度を300℃とし、加熱時間を0.5時間に代えた以外は、参考例5と同様の方法で、ポリカルボジイミド(B)を加熱することにより、ポリカルボジイミド反応物(B‐2)としてCDI‐5を得た。得られたCDI‐5の耐熱温度を熱重量分析装置により測定し、評価結果を表2に記載した。
熱風オーブンに代えて真空オーブンと真空ポンプを用い、前記真空オーブン内の減圧度が-0.1MPaのとなるように調節した以外は、参考例5と同様の方法で、ポリカルボジイミド(B)を加熱することにより、ポリカルボジイミド反応物(B‐2)としてCDI‐6を得た。得られたCDI‐6の耐熱温度を熱重量分析装置により測定し、評価結果を表2に記載した。
加熱温度を100℃とし、加熱時間を1時間に代えた以外は、参考例5と同様の方法で、ポリカルボジイミド(B)を加熱することにより、ポリカルボジイミド反応物(B‐2)としてCDI‐7を得た。得られたCDI‐7の耐熱温度を熱重量分析装置により測定し、評価結果を表2に記載した。
表2に記載の通り、ポリカルボジイミド(B)であるCDI‐1に代えて、モノカルボジイミド(B’)であるCDI‐2を用いた以外は、参考例5と同様の方法で、加熱操作を試みたところ、CDI‐2が揮発してしまい、モノカルボジイミドからなる反応物は得られなかった。
ポリカルボジイミド(B)であるCDI‐1の耐熱温度を熱重量分析装置により測定し、評価結果を表2に記載した。
表3に示す成分、条件を用いて、以下の手順による本発明の一実施形態に係る第2の製造方法で炭素繊維強化ポリアリーレンスルフィドを製造し、評価を行った。
工程(II‐2):PAS(A)とポリカルボジイミド反応物(B‐2)を二軸押出機(JSW社 TEX‐30α、(スクリュー長さ)/(スクリュー直径)=31.5)にメインフィードして溶融混練を行った。溶融混練はシリンダー温度300℃で行い、各成分をメインフィードしてから吐出するまでに要した時間(溶融混練時間)は150秒であった。溶融混練物は二軸押出機先端に取り付けたTダイから吐出し、冷却ロールで冷却することで、ポリカルボジイミド変性ポリアリーレンスルフィド(C‐2)からなるフィルムを得た。
工程(III‐2):得られたフィルムを所定のサイズにカットし、不織布形状の炭素繊維基材(CFM‐2)と交互に積層し、プレス成形機に投入することで炭素繊維強化ポリアリーレンスルフィドを製造した。
ポリカルボジイミド反応物(B‐2)としてCDI‐4を用いた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
ポリカルボジイミド反応物(B‐2)としてCDI‐5を用いた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
ポリカルボジイミド反応物(B‐2)としてCDI‐6を用いた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
ポリカルボジイミド反応物(B‐2)としてCDI‐7を用いた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
工程(III‐2)で得られた炭素繊維強化ポリアリーレンスルフィドを、工程(IV)として再度プレス成形機に投入し、プレス温度250℃、プレス圧力0.5MPa、プレス時間3600秒の条件で加熱を行った以外は、実施例19と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
ポリカルボジイミド反応物(B‐2)を含まない以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
ポリカルボジイミド反応物(B‐2)の代わりに、モノカルボジイミド(B’)であるCDI‐2を用いた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
成分(E)の付着量を炭素繊維(D)100質量部に対して1質量部としたまま、炭素繊維(D)の量が、PAS(A)100質量部に対して25質量部となるように不織布形状の炭素繊維基材(CFM‐2)の含有量を代えた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
成分(E)の付着量を炭素繊維(D)100質量部に対して1質量部としたまま、炭素繊維(D)の量が、PAS(A)100質量部に対して100質量部となるように不織布形状の炭素繊維基材(CFM‐2)の含有量を代えた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
成分(E)を含まないように、不織布形状の炭素繊維基材(CFM‐1)を用いた以外は、実施例15と同様の方法で、試験片を作製し、各評価に供した。評価結果を表3に記載した。
表4に示す成分、条件を用いて、以下の手順による本発明の一実施形態に係る第3の製造方法で炭素繊維強化ポリアリーレンスルフィドを製造し、評価を行った。
工程(I‐3):PAS(A)とポリカルボジイミド(B)をドライブレンドさせた混合物を得た。
工程(II‐3):得られた混合物を、二軸押出機(JSW社 TEX‐30α、(スクリュー長さ)/(スクリュー直径)=31.5)にメインフィードして溶融混練を行った。溶融混練はシリンダー温度350℃で行い、各成分をメインフィードしてから吐出するまでに要した時間(溶融混練時間)は300秒であった。溶融混練物は二軸押出機先端に取り付けたTダイから吐出し、冷却ロールで冷却することで、ポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)からなるフィルムを得た。
工程(III‐3):得られたフィルムを所定のサイズにカットし、不織布形状の炭素繊維基材(CFM‐2)と交互に積層し、プレス成形機に投入することで炭素繊維強化ポリアリーレンスルフィドを製造した。
工程(II‐3)における二軸押出機のシリンダー温度を330℃に代えた以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
工程(III‐3)で得られた炭素繊維強化ポリアリーレンスルフィドを、工程(IV)として再度プレス成形機に投入し、プレス温度250℃、プレス圧力0.5MPa、プレス時間3600秒の条件で加熱を行った以外は、実施例25と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
工程(II‐3)における二軸押出機のシリンダー温度を300℃に代えて、さらに工程(III‐3)におけるプレス温度を350℃に代えた以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
工程(III‐3)におけるプレス温度を420℃に代えた以外は、実施例24と同様の方法で、試験片を作製しようとしたところ、工程(III‐3)におけるポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)と炭素繊維(D)との複合化が困難であり、炭素繊維強化ポリアリーレンスルフィドを得ることができなかった。評価結果を表4に記載した。
ポリカルボジイミド(B)を含まない以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
ポリカルボジイミド(B)の量を、PAS(A)100質量部に対して20質量部となるように代えた以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
ポリカルボジイミド(B)の代わりに、モノカルボジイミド(B’)であるCDI‐2を用いた以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
成分(E)の付着量を炭素繊維(D)100質量部に対して1質量部としたまま、炭素繊維(D)の量が、PAS(A)100質量部に対して25質量部となるように不織布形状の炭素繊維基材(CFM‐2)の含有量を代えた以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
成分(E)の付着量を炭素繊維(D)100質量部に対して1質量部としたまま、炭素繊維(D)の量が、PAS(A)100質量部に対して100質量部となるように不織布形状の炭素繊維基材(CFM‐2)の含有量を代えた以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
成分(E)を含まないように、不織布形状の炭素繊維基材(CFM‐1)を用いた以外は、実施例24と同様の方法で、試験片を作製し、各評価に供した。評価結果を表4に記載した。
表5に示す成分、条件を用いて、以下の手順による本発明の一実施形態に係る第1の製造方法で炭素繊維強化ポリアリーレンスルフィドを製造し、評価を行った。
実施例3の工程(III‐1)で得られた複合体を用いた以外は、実施例30と同様の方法で、試験片を作製し、各評価に供した。評価結果を表5に記載した。
工程(V)における射出成形のシリンダー温度を290℃に代えた以外は、実施例31と同様の方法で、試験片を作製し、各評価に供した。評価結果を表5に記載した。
工程(V)における射出成形のシリンダー温度を350℃に代えた以外は、実施例31と同様の方法で、試験片を作製し、各評価に供した。評価結果を表5に記載した。
実施例14の工程(IV)で得られた複合体を用いた以外は、実施例30と同様の方法で、試験片を作製し、各評価に供した。評価結果を表5に記載した。
表6に示す成分、条件を用いて、以下の手順による本発明の一実施形態に係る第2の製造方法で炭素繊維強化ポリアリーレンスルフィドを製造し、評価を行った。
実施例19の工程(III‐2)で得られた複合体を用いた以外は、実施例35と同様の方法で、試験片を作製し、各評価に供した。評価結果を表6に記載した。
工程(V)における射出成形のシリンダー温度を290℃に代えた以外は、実施例36と同様の方法で、試験片を作製し、各評価に供した。評価結果を表6に記載した。
工程(V)における射出成形のシリンダー温度を350℃に代えた以外は、実施例36と同様の方法で、試験片を作製し、各評価に供した。評価結果を表6に記載した。
実施例20の工程(IV)で得られた複合体を用いた以外は、実施例35と同様の方法で、試験片を作製し、各評価に供した。評価結果を表6に記載した。
表7に示す成分、条件を用いて、以下の手順による本発明の一実施形態に係る第3の製造方法で炭素繊維強化ポリアリーレンスルフィドを製造し、評価を行った。
実施例25の工程(III‐3)で得られた複合体を用いた以外は、実施例40と同様の方法で、試験片を作製し、各評価に供した。評価結果を表7に記載した。
工程(V)における射出成形のシリンダー温度を290℃に代えた以外は、実施例41と同様の方法で、試験片を作製し、各評価に供した。評価結果を表7に記載した。
工程(V)における射出成形のシリンダー温度を350℃に代えた以外は、実施例41と同様の方法で、試験片を作製し、各評価に供した。評価結果を表7に記載した。
実施例26の工程(IV)で得られた複合体を用いた以外は、実施例40と同様の方法で、試験片を作製し、各評価に供した。評価結果を表7に記載した。
Claims (13)
- 下記(I‐1)~(III‐1)の工程を含む、炭素繊維強化ポリアリーレンスルフィドの製造方法。
(I‐1)ポリアリーレンスルフィド(A)100質量部とカルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)0.1~10質量部を混合し、得られた混合物を加熱して溶融混練することで溶融混練物を得る工程
(II‐1)工程(I‐1)で得られる溶融混練物を、ポリアリーレンスルフィド(A)のガラス転移温度以上かつ融点以下の温度で加熱することで、溶融混練物内のカルボジイミド基の反応を促進してポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)を得る工程
(III‐1)工程(II‐1)で得られるポリカルボジイミド変性ポリアリーレンスルフィド(C‐1)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程 - 工程(I‐1)において、混合物を加熱開始してからポリアリーレンスルフィド(A)およびポリカルボジイミド(B)が溶融し終えるまでに要した時間をt1(秒)、ポリアリーレンスルフィド(A)およびポリカルボジイミド(B)が溶融し終えてから溶融混練物を取り出すまでに要した時間をt2(秒)とすると、t1<t2である、請求項1に記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 下記(I‐2)~(III‐2)の工程を含む、炭素繊維強化ポリアリーレンスルフィドの製造方法。
(I‐2)カルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)を、該成分(B)の軟化点以上の温度で加熱することで、カルボジイミド基同士の反応を促進してポリカルボジイミド反応物(B‐2)を得る工程
(II‐2)ポリアリーレンスルフィド(A)100質量部と前記ポリカルボジイミド反応物(B‐2)0.1~10質量部を混合し、得られた混合物を加熱して溶融混練することでポリカルボジイミド変性ポリアリーレンスルフィド(C‐2)を得る工程
(III‐2)工程(II‐2)で得られるポリカルボジイミド変性ポリアリーレンスルフィド(C‐2)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程 - 工程(I‐2)において、成分(B)の軟化点以上の温度が、50~250℃の温度である、請求項3に記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 工程(I‐2)において、成分(B)の軟化点以上の温度で加熱する時間が、1~48時間の間である、請求項3または4に記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 下記(I‐3)~(III‐3)の工程を含む、炭素繊維強化ポリアリーレンスルフィドの製造方法。
(I‐3)ポリアリーレンスルフィド(A)100質量部とカルボジイミド基を1分子中に少なくとも2個以上有するポリカルボジイミド(B)0.1~10質量部を混合した混合物を得る工程
(II‐3)工程(I‐3)で得られる混合物を、ポリアリーレンスルフィド(A)の融点以上の温度で加熱して溶融混練することで、カルボジイミド基の反応を促進してポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)を得る工程
(III‐3)工程(II‐3)における溶融混練時以下の温度で前記ポリカルボジイミド変性ポリアリーレンスルフィド(C‐3)を溶融させ、ポリアリーレンスルフィド(A)100質量部に対して10~300質量部の炭素繊維(D)と複合化させて複合体を得る工程 - 工程(II‐3)において、ポリアリーレンスルフィド(A)の融点以上の温度が330~400℃であり、工程(III‐3)において、工程(II‐3)における溶融混練時以下の温度が、280~330℃である、請求項6に記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- さらに、工程(I‐1)、(II‐2)または(II‐3)において、溶融混練の少なくとも一部を-0.05MPa以下の減圧条件下で行う、請求項1~7のいずれかに記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 工程(III‐1)、(III‐2)または(III‐3)が、溶融させた前記成分(C‐1)、(C‐2)または(C‐3)を炭素繊維(D)からなる基材に含浸させる工程である、請求項1~8のいずれかに記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 工程(III‐1)、(III‐2)または(III‐3)で得られる複合体を、ポリアリーレンスルフィド(A)のガラス転移温度以上かつ融点以下の温度で加熱することで、複合体内のカルボジイミド基の反応を促進する工程(IV)を含む、請求項1~9のいずれかに記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 工程(III‐1)、(III‐2)または(III‐3)において得られる複合体または工程(IV)を経た複合体を、射出成形またはプレス成形する工程(V)を含む、請求項1~10のいずれかに記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 工程(V)において射出成形またはプレス成形する際の成形加工温度を、工程(III‐1)、(III‐2)または(III‐3)において複合体を得る際の温度よりも低温で行う、請求項11に記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
- 成分(D)が、カルボキシル基、水酸基およびエポキシ基からなる群より選択される少なくとも1種の官能基を1分子中に3個以上有する化合物(E)で表面処理されている、請求項1~12のいずれかに記載の炭素繊維強化ポリアリーレンスルフィドの製造方法。
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KR20220043077A (ko) * | 2019-07-31 | 2022-04-05 | 도레이 카부시키가이샤 | 섬유 강화 폴리아릴렌설파이드 공중합체 복합 기재, 그 제조 방법, 그것을 포함하는 성형품 |
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