WO2015053181A1 - Composition de résine renforcée par des fibres de carbone, pellets, objet moulé et boîtier pour dispositif électronique - Google Patents

Composition de résine renforcée par des fibres de carbone, pellets, objet moulé et boîtier pour dispositif électronique Download PDF

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Publication number
WO2015053181A1
WO2015053181A1 PCT/JP2014/076517 JP2014076517W WO2015053181A1 WO 2015053181 A1 WO2015053181 A1 WO 2015053181A1 JP 2014076517 W JP2014076517 W JP 2014076517W WO 2015053181 A1 WO2015053181 A1 WO 2015053181A1
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Prior art keywords
acid
carbon fiber
weight
resin composition
parts
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PCT/JP2014/076517
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English (en)
Japanese (ja)
Inventor
服部公彦
玉井晃義
歌崎憲一
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東レ株式会社
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Priority to JP2014549236A priority Critical patent/JP6554792B2/ja
Priority to KR1020167008530A priority patent/KR20160070062A/ko
Priority to CN201480046695.5A priority patent/CN105492537B/zh
Publication of WO2015053181A1 publication Critical patent/WO2015053181A1/fr

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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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • 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
    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • 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
    • B29B9/12—Making granules characterised by structure or composition
    • B29B9/14—Making granules characterised by structure or composition fibre-reinforced
    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the present invention relates to a carbon fiber reinforced resin composition, a pellet formed by molding the carbon fiber, a molded product obtained by injection molding the pellet, and an electronic device casing.
  • Polyamide resins are used in a wide variety of applications such as electrical / electronics, automobiles, machinery, and building materials because they have excellent mechanical properties such as rigidity and strength, and heat resistance.
  • resin has progressed, and mechanical properties such as rigidity and strength equivalent to metals are required for resins.
  • it is required to have excellent surface appearance, low water absorption, and thinning for home appliance parts such as housings of electronic devices represented by OA devices such as personal computers and mobile phones.
  • OA devices such as personal computers and mobile phones.
  • mechanical properties it has excellent surface appearance, water absorption properties and fluidity, and is required to reduce warpage.
  • a fibrous filler such as glass fiber or carbon fiber is blended as a means for improving the mechanical properties of the polyamide resin.
  • a technique of obtaining a fiber-reinforced resin composition by melt-kneading chopped strands (short fibers) of a polyamide resin and a fibrous filler in an extruder is used.
  • glass fiber it is necessary to add a considerably large amount, and it is a reality to achieve rigidity equivalent to metal. Is difficult.
  • carbon fiber when carbon fiber is used, mechanical properties such as rigidity are remarkably improved compared to glass fiber.
  • carbon fiber reinforced resin obtained by blending 20 to 160 parts by weight of carbon fiber having a tensile strength of 5.1 GPa or more with 100 parts by weight of thermoplastic polyamide resin. 10 to 300 parts by weight of carbon fiber is blended with 100 parts by weight of the composition (see Patent Document 1), a thermoplastic polyamide resin having a difference between the melting point and the exothermic peak temperature of temperature-falling crystallization of 0 ° C. or more and 50 ° C. or less A carbon fiber reinforced resin composition (see Patent Document 2) is proposed.
  • a polyamide resin having a specific amount of heat of crystal fusion 0.01 to 100 parts by weight of a liquid crystalline resin, and 0.01 to 5 parts by weight of an acid anhydride 5 to 200 parts by weight of a fibrous filler is blended with 100 parts by weight of a resin composition formed by blending a polyamide resin composition (see Patent Document 3) and a thermoplastic resin and a dendritic polyester.
  • a long fiber reinforced resin pellet is proposed.
  • a dicarboxylic acid component whose main component is terephthalic acid and 1,8-octanediamine, 1,10-decanediamine, and 1,1 Conductivity comprising 100 parts by mass of a polyamide having a supercooling degree of 40 ° C. or less and 5 to 50 parts by mass of a conductivity-imparting agent, comprising at least one diamine component selected from the group consisting of 12-dodecanediamine.
  • a polyamide resin composition (see Patent Document 5) has been proposed, and an example using 1,9-nonanediamine as a diamine component is described in Comparative Examples. JP 2012-255063 A JP 2013-64106 A JP 2000-313803 A JP 2012-92303 A JP 2013-60580 A
  • the present invention solves the above-mentioned problems, is excellent in thermal stability, retention stability, fluidity and thin-wall formability, has a metal equivalent level rigidity and excellent surface appearance and water absorption characteristics, while reducing warpage.
  • An object of the present invention is to provide a carbon fiber reinforced resin composition capable of obtaining a molded article and a thin molded article for an electronic device casing obtained by injection molding the same.
  • the carbon fiber reinforced resin composition of the present invention has the following constitution. That is, (A) A dicarboxylic acid containing 60 to 100 mol% of terephthalic acid in the total amount of dicarboxylic acid and a total of 60 to 100 mol% of 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine in the total amount of diamine To 100 parts by weight of a semi-aromatic polyamide resin obtained by polycondensation with a diamine, and having a melting point of 220 to 300 ° C., (B) 60 to 200 parts by weight of carbon fiber and (C) dendritic polyester. A carbon fiber reinforced resin composition containing 01 to 10 parts by weight.
  • the pellet of the present invention has the following configuration. That is, A pellet formed by molding the carbon fiber reinforced resin composition, wherein the weight average fiber length of the carbon fiber in the pellet is 0.1 to 0.5 mm.
  • the molded product of the present invention has the following configuration. That is, A molded product obtained by injection molding of pellets.
  • the electronic device casing of the present invention has the following configuration. That is, It is the electronic device housing
  • the carbon fiber reinforced resin composition of the present invention is preferably formed by further blending 0.01 to 5 parts by weight of (D) acid anhydride with respect to 100 parts by weight of (A) semi-aromatic polyamide resin.
  • the intrinsic viscosity of (A) semi-aromatic polyamide resin measured at 30 ° C. in 0.2 g / dL concentrated sulfuric acid is in the range of 0.5 to 1.3 dL / g. Is preferred.
  • the terminal amino group concentration per kg of (A) semi-aromatic polyamide resin in the carbon fiber reinforced resin composition is preferably 0.1 to 30 meq / kg.
  • the weight average fiber length of carbon fibers in the molded product is preferably 0.01 to 0.5 mm.
  • the ratio of the weight average fiber length to the number average fiber length (Lw / Ln) of the carbon fibers in the molded product is preferably 1.0 or more and less than 1.3.
  • the average thickness of the electronic device casing of the present invention is preferably 0.5 to 1.0 mm.
  • the carbon fiber reinforced resin composition of the present invention is excellent in thermal stability, retention stability, fluidity and thin-wall moldability, has the same level of rigidity as metal, and has excellent surface appearance and water absorption characteristics, while reducing warpage.
  • a molded product can be obtained. Therefore, it can be suitably used for an electronic device casing such as a personal computer or a mobile phone that requires light weight, high rigidity, thin-wall moldability, good surface appearance, and the like.
  • resin composition of the present invention (hereinafter sometimes referred to as “resin composition”) will be specifically described.
  • the resin composition of the present invention comprises (A) a dicarboxylic acid containing 60 to 100 mol% of terephthalic acid in the total amount of dicarboxylic acid, and 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine in the total amount of diamine.
  • a semi-aromatic polyamide resin having a melting point of 220 to 300 ° C. obtained by polycondensation with a diamine containing a total of 60 to 100 mol% hereinafter referred to as “(A) semi-aromatic polyamide resin”). Is blended).
  • a carbon fiber reinforced resin composition having excellent fluidity and thin-wall moldability, and capable of improving mechanical properties such as rigidity and strength of molded products and water absorption properties is provided. can get.
  • terephthalic acid As the dicarboxylic acid constituting the semi-aromatic polyamide resin, terephthalic acid is used. It is necessary to contain 60 to 100 mol% of terephthalic acid in the total amount of dicarboxylic acid, and other dicarboxylic acids may be contained in an amount of 40 mol% or less in the total amount of dicarboxylic acid. When the terephthalic acid component is less than 60 mol%, the thermal stability, retention stability, fluidity and thin-wall moldability of the resin composition, water absorption characteristics, surface appearance, chemical resistance of the molded product obtained from the resin composition Properties such as stability and dimensional stability are reduced.
  • the content of terephthalic acid is preferably 75 mol% or more, more preferably 90 mol% or more in the total amount of dicarboxylic acid.
  • dicarboxylic acids examples include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3- Aliphatic dicarboxylic acids such as diethyl succinic acid, azelaic acid, sebacic acid and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2,6- Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4'-oxydibenzoic acid Acid, diphenylmethane-4,4'-
  • polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can also be used within the range where melt molding is possible.
  • (A) As the diamine constituting the semi-aromatic polyamide resin 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine is used.
  • a so-called even-odd effect appears in a polyamide resin. That is, when the number of carbon atoms of the diamine constituting the polyamide resin is an even number, a more stable crystal structure is obtained and the crystallinity tends to be higher than in the case of an odd number.
  • the crystallization rate of the resin composition is adjusted to an appropriate range, and the characteristics of the semi-aromatic polyamide resin are adjusted.
  • the warpage of the molded product can also be reduced.
  • the total amount of 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine is 60 to 100 mol% in the total amount of diamine, and 40 mol of other diamines are contained in the diamine. % Or less.
  • the content thereof is 60 to 100 mol%. The content may be 60 to 100 mol%.
  • the total content of 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine is less than 60 mol%, the thermal stability, fluidity and thin moldability of the resin composition are reduced, Any of the chemical resistance, water absorption characteristics and mechanical characteristics of the molded product obtained from the resin composition is lowered.
  • the total content of 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine is preferably at least 70 mol%, more preferably at least 80 mol%, based on the total amount of diamine.
  • the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine (1,9-nonanediamine: 2-methyl-1,8-octanediamine) is preferably 30:70 to 90:10. More preferably, it is 40:60 to 70:30.
  • the resin composition is excellent in fluidity, thermal stability and residence stability, and can be obtained from the resin composition. The balance with the surface appearance of the molded product can be further improved.
  • Examples of other diamines include ethylene diamine, propylene diamine, 1,4-butane diamine, 1,6-hexane diamine, 1,8-octane diamine, 1,10-decane diamine, 1,12-dodecane diamine, 3- Methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, etc.
  • Aliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine; p-phenylenediamine, m-phenylenediamine, xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether
  • aromatic diamines Two or more of these may be used.
  • the (A) semi-aromatic polyamide resin preferably has its molecular chain end sealed with an end-capping agent from the viewpoint of improving retention stability, and 40% or more of the end groups are sealed. It is more preferable that 60% or more of the end groups are sealed, and 70% or more of the end groups are more preferably sealed.
  • the end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, and is monocarboxylic acid, monoamine, acid anhydride, monoisocyanate, monoacid halide, monoester. Examples include esters and monoalcohols. Two or more of these may be used. A monocarboxylic acid or a monoamine is preferable from the viewpoint of reactivity and the stability of the sealing end, and a monocarboxylic acid is more preferable from the viewpoint of ease of handling.
  • the monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group.
  • acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid Aliphatic monocarboxylic acids such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid And aromatic monocarboxylic acids such as acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid.
  • Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, benzoic acid are included in terms of reactivity, stability at the end of the seal, and price. preferable.
  • the monoamine used as a terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group.
  • methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine Aliphatic monoamines such as stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine. Two or more of these may be used.
  • butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred.
  • the semi-aromatic polyamide resin in the present invention can be obtained by polycondensing the above dicarboxylic acid and diamine by any known method. More specifically, for example, a diamine and a dicarboxylic acid and, if necessary, a catalyst and a terminal blocking agent are mixed to produce a nylon salt, and the resulting nylon salt is heated at a temperature of 200 to 250 ° C. Examples thereof include a method of obtaining a polymer and further increasing the degree of polymerization of the prepolymer.
  • the blending amount of the end-blocking agent depends on the ultimate viscosity of the semi-aromatic polyamide resin finally obtained and the sealing rate of the end group. Can be adjusted accordingly.
  • the specific blending amount varies depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-capping agent used, but is usually in the range of 0.5 to 10 mol% with respect to the total number of moles of dicarboxylic acid and diamine. Blended in.
  • the semi-aromatic polyamide resin in the present invention has a melting point of 220 to 300 ° C.
  • the melting point is less than 220 ° C.
  • the mechanical properties and water absorption properties of the molded product obtained from the resin composition are lowered.
  • 230 degreeC or more is preferable and 240 degreeC or more is more preferable.
  • the melting point exceeds 300 ° C.
  • the fluidity, thermal stability and retention stability of the resin composition are lowered, and the thin-wall moldability and surface appearance of the molded product are lowered.
  • 290 ° C. or lower is preferable, and 280 ° C. or lower is more preferable.
  • the melting point of the (A) semi-aromatic polyamide resin in the present invention can be measured using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • EXSTAR 6000 manufactured by Seiko Instruments Inc.
  • the endothermic peak is taken as the melting point.
  • the method for adjusting the melting point of the semi-aromatic polyamide resin to the above range includes, for example, a method of appropriately adjusting the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and other diamines. And the like.
  • the (A) semi-aromatic polyamide resin in the present invention preferably has an intrinsic viscosity in the range of 0.5 to 1.3 dL / g measured in 0.2 g / dL concentrated sulfuric acid at 30 ° C.
  • the intrinsic viscosity is 0.5 dL / g or more, the mechanical properties of the molded product can be further improved. 0.6 dL / g or more is more preferable, and 0.7 dL / g or more is more preferable.
  • the intrinsic viscosity is 1.3 dL / g or less
  • the fluidity of the resin composition, the thin-wall moldability, and the surface appearance of the molded product can be further improved, and the warpage of the molded product can be further reduced.
  • 1.2 dL / g or less is more preferable, and 1.1 dL / g or less is more preferable.
  • Examples of means for setting the intrinsic viscosity of the semi-aromatic polyamide resin in such a range include, for example, a method of appropriately adjusting the polymerization conditions such as pressure, temperature, polymerization time, etc. during production of the semi-aromatic polyamide resin, dicarboxylic acid, diamine, terminal Examples thereof include a method for adjusting a raw material composition such as a blocking agent.
  • the resin composition of the present invention comprises (B) carbon fiber.
  • the carbon fiber (B) in the present invention is not particularly limited, and carbon fibers produced using various known carbon fibers such as polyacrylonitrile (PAN), pitch, rayon, lignin, hydrocarbon gas, etc. Examples thereof include graphite fibers. You may use the fiber which coat
  • the carbon fibers are usually in the form of chopped strands, roving strands, milled fibers, etc., and the diameter is generally 15 ⁇ m or less, preferably 5 to 10 ⁇ m.
  • the form of the (B) carbon fiber in the present invention is not particularly limited, but a carbon fiber bundle composed of several thousand to several hundred thousand carbon fibers and a milled form obtained by pulverizing the carbon fiber bundle are preferable.
  • the carbon fiber bundle it is possible to use a carbon fiber bundle obtained by a roving method using continuous fibers directly or a chopped strand cut to a predetermined length.
  • the (B) carbon fiber in the present invention is preferably a chopped strand, and the number of filaments of the carbon fiber strand that is a precursor of the chopped carbon fiber is preferably 1,000 to 150,000. If the number of filaments of the carbon fiber strand is 1,000 to 150,000, the manufacturing cost can be suppressed and the stability in the production process can be ensured.
  • the strand elastic modulus of the (B) carbon fiber in the present invention is preferably 150 GPa or more, and more preferably 220 GPa or more. On the other hand, the strand elastic modulus is preferably 1,000 GPa or less, and more preferably 500 GPa or less. If the strand elastic modulus of the carbon fiber is within this preferable range, the fluidity and thin moldability of the resin composition can be further improved, the rigidity and surface appearance of the molded product can be further improved, and warpage can be further reduced. .
  • the strand strength of the (B) carbon fiber in the present invention is preferably 1 GPa or more, and more preferably 3 GPa or more. On the other hand, the strand strength is preferably 10 GPa or less, and more preferably 5 GPa or less. If the strand strength of the carbon fiber is within this preferable range, the mechanical properties of the molded product can be further improved, and the undulations on the surface of the molded product can be reduced, and the surface appearance can be further improved.
  • the strand elastic modulus and strand strength refer to the elastic modulus and strength of a strand produced by impregnating and curing an epoxy resin on a continuous fiber bundle composed of 1,000 to 150,000 carbon fiber single strands. It is a value obtained by subjecting the test piece to a tensile test according to JIS R 7601.
  • the carbon fiber in the present invention may be subjected to a surface oxidation treatment in order to improve adhesion with the (A) semi-aromatic polyamide resin.
  • a surface oxidation treatment examples include surface oxidation treatment by energization treatment, oxidation treatment in an oxidizing gas atmosphere such as ozone, and the like.
  • the carbon fiber may have a coupling agent or sizing agent attached to the surface thereof, and (A) the wettability and handling of the semi-aromatic polyamide resin can be improved.
  • the coupling agent include amino-based, epoxy-based, chloro-based, mercapto-based, and cationic-based silane coupling agents, and amino-based silane coupling agents can be suitably used.
  • the sizing agent include maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, phenol compounds, derivatives of these compounds, and the like, and sizing agents containing urethane compounds and epoxy compounds. Can be suitably used.
  • the content of the coupling agent and sizing agent in the carbon fiber is preferably 0.1 to 10% by weight.
  • the content of the sizing agent is 0.1 to 10% by weight, it is possible to obtain carbon fibers that are superior in the wettability and handleability of the (A) semi-aromatic polyamide resin. More preferably, it is 0.5 to 6% by weight.
  • the blending amount of (B) carbon fiber in the resin composition of the present invention is 60 to 200 parts by weight with respect to 100 parts by weight of (A) semi-aromatic polyamide resin.
  • (B) When the blending amount of the carbon fiber is less than 60 parts by weight, the rigidity (bending elastic modulus), strength and impact resistance of the molded product are lowered, and it is not suitable for use in an electronic device casing. 70 parts by weight or more is preferable, and 80 parts by weight or more is more preferable.
  • the blending amount of (B) the carbon fiber exceeds 200 parts by weight, the thermal stability is remarkably impaired, a carbon fiber reinforced resin composition having excellent surface appearance and fluidity cannot be obtained, and the productivity is also significantly reduced. . 180 parts by weight or less is preferable, and 150 parts by weight or less is more preferable.
  • the resin composition of the present invention comprises (C) a dendritic polyester.
  • C) a dendritic polyester By adding dendritic polyester, the decomposition of (A) aromatic polyester resin during the production of the resin composition is suppressed, and the fluidity, thin moldability and thermal stability of the resin composition are greatly improved. Can do. In addition, warping of the molded product can be reduced.
  • the (C) dendritic polyester in the present invention comprises an aromatic oxycarbonyl unit (P), an aromatic and / or aliphatic dioxy unit (Q), an aromatic dicarbonyl unit (R), and an organic residue having three or more functional groups.
  • the aromatic oxycarbonyl unit (P), the aromatic and / or aliphatic dioxy unit (Q), and the aromatic dicarbonyl unit (R) are structures represented by the following general formula (3), respectively. Preferably it is a unit.
  • R 1 and R 3 are each an aromatic residue.
  • R 2 is an aromatic residue or an aliphatic residue.
  • R 1 , R 2 and R 3 may each include a plurality of structural units.
  • Examples of the aromatic residue include a substituted or unsubstituted phenylene group, naphthylene group, and biphenylene group.
  • Examples of the aliphatic residue include ethylene, propylene, and butylene.
  • R 1 , R 2 and R 3 are each preferably at least one selected from structural units represented by the following structural formula (4).
  • Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group.
  • the alkyl group an alkyl group having 1 to 4 carbon atoms is preferable.
  • n is an integer of 2 to 8.
  • the dendritic polyester according to the present invention trifunctional or higher functional organic residues (S) are directly linked to each other by an ester bond and / or an amide bond, or via a structural unit composed of the above-mentioned P, Q and R which are branch structure parts.
  • the basic skeleton is a branched structure of three or more branches connected together. It is not necessary for all of the polymers to be composed of the basic skeleton, and other structures may be included at the ends, for example, for end capping.
  • the dendritic polyester may contain a structure in which all the functional groups of (S) are reacted, a structure in which only two are reacted, and a structure in which only one is reacted.
  • the structure in which all the functional groups of (S) have reacted is preferably 15 mol% or more, more preferably 30 mol% or more, based on the entire (S).
  • Dendritic polyester in the present invention preferably exhibits molten liquid crystallinity.
  • the term “showing molten liquid crystallinity” means that the liquid crystal state is exhibited in a certain temperature range when the temperature is raised from room temperature.
  • the liquid crystal state is a state showing optical anisotropy under shear.
  • the trifunctional organic residue (S) is preferably an organic residue of a compound having a carboxyl group, a hydroxyl group or an amino group. It may be an organic residue of a compound having two or more of these groups.
  • aliphatic compounds such as glycerol, 1,2,3-tricarboxypropane, diaminopropanol, diaminopropionic acid, trimesic acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, Residues of aromatic compounds such as resorcinic acid, tricarboxynaphthalene, dihydroxynaphthoic acid, aminophthalic acid, 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid and melamine are preferably used.
  • a residue of an aromatic compound represented by the following general formula (5) is more preferable.
  • trifunctional organic residues include residues such as phloroglucinol, trimesic acid, trimellitic acid, trimellitic anhydride, ⁇ -resorcylic acid, 4-hydroxy-1,2-benzenedicarboxylic acid Is more preferable, and a residue of trimesic acid is more preferable.
  • the aromatic hydroxycarbonyl unit (P), aromatic and / or aliphatic dioxy unit (Q), and aromatic dicarbonyl unit (R) of the dendritic polyester constitute a branch structure portion between branches of the dendritic polyester.
  • the values of p, q, and r are, for example, the respective values in the nuclear magnetic resonance spectrum of the proton nucleus at 40 ° C. of a solution in which the dendritic polyester is dissolved in a mixed solvent of 50% by weight of pentafluorophenol and 50% by weight of deuterated chloroform. It can be determined from the peak intensity ratio derived from the structural unit. The average content is calculated from the peak area intensity ratio of each structural unit, and the three decimal places are rounded off. The average chain length of the branch structure portion is calculated from the area intensity ratio with the peak corresponding to the content f of the branched structure F, and is set as p + q + r. In this case, the three decimal places are rounded off.
  • the ratio of p to q and the ratio of p to r are preferably in the range of 5/95 to 95/5, more preferably 20/80 to 80/20.
  • the melting point of the dendritic polyester can be within an appropriate range.
  • p / q and p / r to be 5/95 or more, it is possible to more effectively express the melt liquid crystallinity of the dendritic polyester.
  • Q and r are preferably substantially equimolar, but either component may be added in excess to control the end group.
  • the ratio q / r is preferably in the range of 0.7 to 1.5, more preferably 0.9 to 1.1. Equimolar here means that the molar amount in the repeating unit is equal and does not include the terminal structure.
  • end structure means the end of the branch structure portion, and when the end is blocked, it means the end of the branch structure portion closest to the end.
  • R 1 is a structural unit derived from an aromatic oxycarbonyl unit, and specific examples thereof include a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. It is done. A structural unit derived from p-hydroxybenzoic acid is preferred, and a structural unit derived from 6-hydroxy-2-naphthoic acid can be partially used together. In addition, a structural unit derived from an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and the like may be contained as long as the effects of the present invention are not impaired.
  • aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and the like may be contained as long as the effects of the present invention are not impaired.
  • R 2 is a structural unit derived from an aromatic and / or aliphatic dioxy unit, for example, 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxy Biphenyl, t-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether, ethylene glycol , 1,3-propylene glycol, 1,4-butanediol and the like. It is preferable from the viewpoint of controlling liquid crystallinity that a structural unit derived from 4,4′-dihydroxybiphenyl and hydroquinone or 4,4′-dihydroxybiphenyl and ethylene glycol is included.
  • R 3 is a structural unit derived from an aromatic dicarbonyl unit such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane- Examples include structural units derived from 4,4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, and the like.
  • a structural unit derived from terephthalic acid or isophthalic acid is preferred, and when both are used in combination, the melting point can be easily adjusted.
  • a part of the structural unit derived from aliphatic dicarboxylic acid such as sebacic acid or adipic acid may be contained.
  • the branch structure portion of the (C) dendritic polyester in the present invention is preferably mainly composed of a polyester skeleton, but it is also possible to introduce a carbonate structure, an amide structure, a urethane structure, etc. to such an extent that the properties are not greatly affected. It is. By introducing such another bond, compatibility with a wide variety of thermoplastic resins can be adjusted. Among them, it is preferable to introduce an amide structure. Examples of the method for introducing an amide bond include a method of copolymerizing an aliphatic, alicyclic, or aromatic amine compound.
  • Examples of the aliphatic amine compound include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, 2-methylpentamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4- / 2, Examples include 4,4-trimethylhexamethylenediamine and 5-methylnonamethylenediamine.
  • Examples of the alicyclic amine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Examples thereof include bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, and aminoethylpiperazine.
  • aromatic amine compound examples include p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine, and m-phenylenediamine. Two or more of these may be used. Of these, p-aminophenol or p-aminobenzoic acid is preferred.
  • branch structure portion of the dendritic polyester include a structural unit derived from p-hydroxybenzoic acid and a structural unit derived from 6-hydroxy-2-naphthoic acid, a structural unit derived from p-hydroxybenzoic acid, 6 A structural unit derived from hydroxy-2-naphthoic acid, a structural unit derived from 4,4′-dihydroxybiphenyl and a structural unit derived from terephthalic acid, a structural unit derived from p-hydroxybenzoic acid, 4,4′-dihydroxy Structural units derived from biphenyl, structural units derived from terephthalic acid and structural units derived from isophthalic acid, structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone Consisting of structural units derived from terephthalic acid and structural units derived from isophthalic acid A structural unit derived from p-hydroxybenz
  • the content p of the structural unit (I) The amount is preferably 30 to 70 mol%, more preferably 45 to 60 mol%, based on the total p + q + r.
  • the content q (II) of the structural unit (II) is preferably 60 to 75 mol%, more preferably 65 to 73 mol% with respect to the total content q of the structural units (II) and (III). is there.
  • the content r (IV) of the structural unit (IV) is preferably 60 to 92 mol%, more preferably 60 to 70 mol%, based on the total content r of the structural units (IV) and (V). More preferably, it is 62 to 68 mol%. In such a case, the fluidity can be further improved.
  • the total content q of the structural units (II) and (III) and the total content r of (IV) and (V) are preferably substantially equimolar. An excess may be added.
  • the content p of the structural unit (I) is 30 to 90 with respect to p + q + r.
  • the mol% is preferable, and 40 to 80 mol% is more preferable.
  • the content q (VI) of the structural unit (VI) is preferably 5 to 70 mol%, more preferably 8 to 60 mol% with respect to the total content q of (II) and (VI).
  • the content r of the structural unit (IV) is preferably substantially equimolar to the total content q of the structural units (II) and (VI). May be added.
  • the terminal of the (C) dendritic polyester in the present invention is preferably a residue of a carboxyl group, a hydroxyl group, an amino group, or a derivative thereof.
  • the hydroxyl group or carboxylic acid derivative include alkyl esters such as methyl ester and aromatic esters such as phenyl ester and benzyl ester.
  • the end-capping method includes adding a monofunctional organic compound in advance when synthesizing the dendritic polyester, or adding a monofunctional organic compound when the dendritic polyster skeleton is formed to some extent. The method etc. are mentioned.
  • benzoic acid 4-t-butylbenzoic acid, 3-t-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4- It is preferable to add methylbenzoic acid, 3-methylbenzoic acid, 3,5-dimethylbenzoic acid and the like.
  • acetoxybenzene When blocking the carboxyl group terminal, acetoxybenzene, 1-acetoxy-4-t-butylbenzene, 1-acetoxy-3-t-butylbenzene, 1-acetoxy-4-chlorobenzene, 1-acetoxy-3 It is preferable to add -chlorobenzene, 1-acetoxy-4-cyanobenzene or the like.
  • the end-capping is possible by adding the organic compound used for the end-capping to an amount corresponding to the end group to be capped.
  • the organic compound used for terminal blocking it is preferable to use 1.005 times equivalent or more, more preferably 1.008 times equivalent or more, of the organic compound used for terminal blocking with respect to the equivalent amount of the terminal group to be blocked.
  • the amount of organic compound used for end-capping is preferably 1.5 times equivalent or less.
  • the content of the organic residue (S) is 7.5 mol% or more, preferably 20 mol% or more, based on the content of all monomers constituting the dendritic polyester. In such a case, the chain length of the branch structure portion is preferable because the dendritic polyester is suitable for taking a dendritic form.
  • the (C) dendritic polyester in the present invention may partially have a crosslinked structure as long as the properties are not affected.
  • the manufacturing method in particular of (C) dendritic polyester is not restrict
  • a monomer containing a structural unit represented by the R 1, monomer containing a structural unit represented by the R 2, monomers and trifunctional a structural unit represented by R 3 A method of reacting monomers, and a method in which the addition amount (mol) of the trifunctional monomer is 7.5 mol% or more with respect to the total monomer (mol) constituting the dendritic polyester.
  • the addition amount of the trifunctional monomer is more preferably 20 mol% or more.
  • a trifunctional monomer is reacted after acylating a monomer containing at least one selected from structural units represented by R 1 , R 2 and R 3 is also preferred. Also preferred is an embodiment in which a monomer containing at least one selected from structural units represented by R 1 , R 2 and R 3 and a trifunctional monomer are acylated and then subjected to a polymerization reaction.
  • a preferable production method will be described by taking as an example the production of a dendritic polyester composed of the structural units (I), (II), (III), (IV) and (V) and a trimesic acid residue. .
  • trimesic acid was synthesized.
  • a method of producing by dephenol polycondensation reaction is also possible.
  • the production methods (1) to (5) are preferred, and the production method (3) is more preferred from the viewpoint of chain length control and steric regulation.
  • the blending amount of acetic anhydride is preferably 0.95 equivalents or more and 1.10 equivalents or less, and 1.02 equivalents or more and 1.05 equivalents of the total phenolic hydroxyl group from the viewpoint of chain length control.
  • the following is more preferable. It is possible to adjust the terminal group by adjusting the amount of acetic anhydride, adding an excess of either a dihydroxy monomer or a dicarboxylic acid monomer, or the like.
  • an amount of dihydroxy monomer such as hydroquinone or 4,4′-dihydroxybiphenyl is added to the dicarboxylic acid monomer in an amount corresponding to the amount of carboxylic acid of trimesic acid, so The acid and the hydroxyl equivalent are preferably combined.
  • the carboxylic acid is intentionally left in the terminal group, it is preferable not to add the dihydroxy monomer as described above excessively.
  • the hydroxyl group is intentionally left at the terminal, the dihydroxy monomer is added in excess of the carboxylic acid equivalent of trimesic acid, and the amount of acetic anhydride used is less than 1.00 equivalent of the phenolic hydroxyl group. preferable.
  • the (C) dendritic polyester in the present invention can be selectively provided with a terminal group structure rich in reactivity with the (A) semi-aromatic polyamide resin in the present invention.
  • the structure of the (A) semi-aromatic polyamide resin in order to suppress excessive reactivity, it may be easier to control the dispersion state by blocking the end with a monofunctional epoxy compound or the like.
  • a melt polymerization method in which the reaction is carried out at a temperature at which the dendritic polyester melts, sometimes under reduced pressure, to distill a predetermined amount of acetic acid to complete the polycondensation reaction, is preferable.
  • the following method is mentioned, for example.
  • a predetermined amount of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid and acetic anhydride are charged into a reaction vessel equipped with a stirring blade and a distillation pipe and having a discharge port at the bottom. .
  • the mixture in the reaction vessel is heated with stirring under a nitrogen gas atmosphere to acetylate the hydroxyl group, and then heated to 200 to 350 ° C. to conduct a deacetic acid polycondensation reaction to distill acetic acid.
  • acetic acid is distilled to 50% of the theoretical distillation amount, a predetermined amount of trimesic acid is added, and acetic acid is distilled to 91% of the theoretical distillation amount to complete the reaction.
  • the reaction temperature is preferably in the range of 130 to 170 ° C, more preferably in the range of 135 to 155 ° C.
  • the reaction time is preferably 0.5 to 6 hours, more preferably 1 to 2 hours.
  • the polycondensation reaction temperature is a temperature at which the dendritic polyester is melted, and is preferably a melting point of the dendritic polyester + 10 ° C. or higher. Specifically, for example, it is in the range of 200 to 350 ° C., preferably 240 to 280 ° C.
  • the atmosphere for polycondensation is satisfactory even under atmospheric pressure nitrogen, but a reduced pressure is preferable because the reaction proceeds faster and the residual acetic acid in the system decreases.
  • the degree of reduced pressure is preferably 0.1 mmHg (13.3 Pa) to 200 mmHg (26,600 Pa), more preferably 10 mmHg (1,330 Pa) to 100 mmHg (13,300 Pa).
  • acetylation and polycondensation may be performed continuously in the same reaction vessel, or acetylation and polycondensation may be performed in different reaction vessels.
  • the reaction vessel is maintained at a temperature at which the dendritic polyester melts, and is pressurized to, for example, 0.01 to 1.0 kg / cm 2 (0.001 to 0.1 MPa), It is preferable to discharge the dendritic polyester in the form of strands from the discharge port provided in.
  • a mechanism that opens and closes intermittently is provided at the discharge port, and it is also possible to discharge liquid droplets.
  • the discharged dendritic polyester is cooled by passing through air or water, and then cut or pulverized as necessary.
  • the dendritic polyester obtained above is melted at a melting point of ⁇ 5 ° C. to a melting point of ⁇ 50 ° C. (for example, 200 to 300 ° C.) under a nitrogen stream or under reduced pressure. A method of heating in the temperature range for 1 to 50 hours can be mentioned.
  • the polycondensation reaction of the dendritic polyester proceeds even without catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.
  • the (C) dendritic polyester used in the present invention preferably has a number average molecular weight of 1,000 to 40,000, more preferably 1,000 to 5,000.
  • a column uses Shodex KG, Shodex K-806M ⁇ 2, Shodex K-802, flow rate 0.8 mL / min, temperature 23 ° C., detector is a differential refractometer (RI), Multi-angle light scattering (MALS).
  • RI differential refractometer
  • MALS Multi-angle light scattering
  • the melt viscosity of the dendritic polyester in the present invention is preferably 0.01 to 30 Pa ⁇ s, more preferably 1 to 10 Pa ⁇ s.
  • this melt viscosity is a value measured by a Koka flow tester under the condition of a shear rate of 100 / s under the condition of the liquid crystal starting temperature of the dendritic polyester + 10 ° C.
  • the blending amount of (C) dendritic polyester is 0.01 to 10 parts by weight with respect to 100 parts by weight of (A) semi-aromatic polyamide resin.
  • (C) When the compounding amount of the dendritic polyester is less than 0.01 parts by weight, the fluidity, thin moldability and thermal stability of the resin composition are lowered. Further, the warpage of the molded product increases. 0.05 weight part or more is preferable and 0.5 weight part or more is more preferable.
  • the blending amount of (C) the dendritic polyester exceeds 10 parts by weight, the rigidity of the molded product is lowered.
  • the amount is preferably 8 parts by weight or less, and more preferably 5 parts by weight or less.
  • An acid anhydride may be further blended with the carbon fiber reinforced resin composition of the present invention.
  • acid anhydrides By blending acid anhydrides, while maintaining the mechanical properties of the molded product, the fluidity and thin moldability of the resin composition and the rigidity during thin molding are improved, and the effect of further reducing the warpage of the molded product is obtained. It is done.
  • acid anhydrides examples include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethylmaleic anhydride, decanoic anhydride, and trimellitic anhydride. 1,8-naphthalic anhydride, phthalic anhydride, maleic anhydride and the like. Two or more of these may be used. Of these, succinic anhydride, 1,8-naphthalic anhydride, phthalic anhydride and the like are preferable, and succinic anhydride and phthalic anhydride are particularly preferable.
  • the blending amount of (D) acid anhydride is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of (A) semi-aromatic polyamide resin.
  • (D) By setting the blending amount of the acid anhydride within this preferable range, the fluidity of the resin composition is improved while maintaining the mechanical properties of the molded product, and the rigidity at the time of thin-wall molding is improved. The warp can be further reduced. 0.05 parts by weight or more is more preferable, and 0.1 parts by weight or more is most preferable. Moreover, 2.5 weight part or less is more preferable, and 2 weight part or less is the most preferable.
  • the resin composition of the present invention preferably has a terminal amino group concentration per kg of (A) semi-aromatic polyamide in the resin composition of 0.1 to 30 meq / kg.
  • (A) terminal amino group concentration per 1 kg of semi-aromatic polyamide in the present invention is obtained by dissolving 0.2 g of the resin composition in 10 mL of hexafluoroisopropanol, and using a 0.02N aqueous hydrochloric acid solution as a sample solution. Measure by performing potentiometric titration.
  • the terminal amino group concentration within this preferable range, it is possible to obtain a resin composition that is excellent in thermal stability and water absorption properties and in which residence stability is remarkably improved.
  • 0.2 meq / kg or more is more preferable, and 0.3 meq / kg or more is most preferable. It is more preferably 15 meq / kg or less, and most preferably 10 meq / kg or less.
  • polymerization conditions such as pressure, temperature, polymerization time, etc. at the time of semi-aromatic polyamide resin production are appropriately selected.
  • examples thereof include a method for adjusting, a method for adjusting a raw material composition such as dicarboxylic acid, diamine, and end-capping agent, and a method for adding an arbitrary amount of the (D) acid anhydride during melt kneading.
  • a flame retardant can be blended with the carbon fiber reinforced resin composition of the present invention within a range that does not impair the purpose and effect of the present invention.
  • the flame retardant is not particularly limited as long as it improves the flame retardancy of the composition. Bromine compound, chlorine compound, fluorine compound, phosphorus compound, red phosphorus, nitrogen compound, silicon compound, boron compound, And antimony compounds.
  • the resin composition of the present invention includes a stabilizer, a mold release agent, an ultraviolet absorber, a colorant, a flame retardant aid, an anti-drip agent, a lubricant, a fluorescent whitening agent, and a phosphorescent substance as long as the effects of the present invention are not impaired.
  • Additives such as pigments, fluorescent dyes, flow modifiers, impact modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents, infrared absorbers and photochromic agents, fillers other than carbon fibers
  • C) a thermoplastic resin other than a dendritic polyester, a thermosetting resin, and the like can be blended.
  • the method for producing the resin composition of the present invention is not particularly limited as long as the requirements specified in the present invention are satisfied.
  • a polyamide resin, carbon fiber, dendritic polyester, and other components as needed are simply added.
  • a method of uniformly melting and kneading with a screw or twin screw extruder or a method of removing the solvent after mixing in a solution is preferably used. From the viewpoint of productivity, a method of uniformly melting and kneading with a single-screw or twin-screw extruder is preferable, carbon fibers are easily dispersed, and a resin composition having excellent mechanical properties and surface appearance of a molded product can be obtained.
  • a method of uniformly melt-kneading with a twin screw extruder is more preferable.
  • the screw length is L and the screw diameter is D
  • a melt kneading method using a twin screw extruder with L / D> 30 is particularly preferable.
  • the screw length here refers to the length from the position where the screw base material is supplied to the tip of the screw.
  • the melt-kneaded strand is cut and pelletized.
  • each component for example, an extruder having two charging ports is used, and (A) a semi-aromatic polyamide resin from a main charging port installed on the screw base side , (B) carbon fiber, (C) dendritic polyester, a method of supplying other components as needed, and (A) semi-aromatic polyamide resin, (C) dendritic polyester and other components are supplied from the main inlet And (B) a method of supplying carbon fiber and other components as needed from a sub-inlet installed between the main inlet and the tip of the extruder, and (A) a semi-aromatic polyamide resin and other components from the main inlet.
  • (B) carbon fiber and, if necessary, other components are supplied from both the main input port and the sub input port.
  • (A) Semi-aromatic polyamide resin, (C) Dendritic polyester and other components are supplied from the main inlet in terms of excellent production stability and mechanical properties of the molded product, and between the main inlet and the tip of the extruder.
  • (B) The method of supplying carbon fiber from the sub-inlet installed in is preferable.
  • the weight average fiber length of the carbon fibers in the pellet obtained from the resin composition of the present invention is not particularly limited, but is preferably in the range of 0.1 to 0.5 mm. When the weight average fiber length of the carbon fibers is within this preferred range, sufficient impact strength and flexural modulus can be obtained, and there is no possibility that fluidity, surface appearance, and thin-wall formability will deteriorate.
  • the weight average fiber length of the carbon fibers in the pellet was determined by firing the pellet at 500 ° C. for 1 hour, dispersing the resulting ash in water, filtering, and observing the residue with an optical microscope. It can be obtained by converting the result of measuring the length of 1,000 fibers into a weight average fiber length.
  • Li is the fiber length of the carbon fiber
  • ni is the number of carbon fibers of the fiber length Li
  • Wi is the weight of the carbon fiber of the fiber length Li
  • ri is the fiber diameter of the carbon fiber of the fiber length Li
  • ⁇ is the carbon fiber Density
  • ⁇ indicates a circular ratio, and the cross-sectional shape of the carbon fiber is approximated to a perfect circle having a fiber diameter ri.
  • the above equation (1) is approximated as follows, and the weight average fiber length can be obtained from the equation (2).
  • Weight average fiber length (Lw) ⁇ (Li 2 ⁇ ni) / ⁇ (Li ⁇ ni) Equation (2) (B)
  • a means for adjusting the weight average fiber length of the carbon fiber to the above range for example, a method using a carbon fiber having an arbitrary fiber length distribution as a raw material according to the target fiber length, and a thermoplastic resin to be used Examples thereof include a method for adjusting the shearing of the carbon fiber by adjusting the melt viscosity, and a method for adjusting the screw rotation speed, the cylinder temperature, and the discharge amount during melt kneading of the resin composition described later.
  • the carbon fiber reinforced resin composition of the present invention can be molded by any known method such as injection molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc., and is processed and used for various molded products. be able to.
  • the molded products include injection molded products, extrusion molded products, blow molded products, various films such as uniaxially drawn and biaxially drawn, sheets, various fibers such as undrawn yarn, drawn yarn, and superdrawn yarn.
  • the resin composition of the present invention preferably produces various molded products by injection molding the pellets produced as described above.
  • Injection molding methods include, for example, injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by supercritical fluid injection), insert molding, in-mold coating molding, heat insulating mold molding, and rapid heating. Cooling die molding, two-color molding, sandwich molding, ultra-high speed injection molding, and the like can be mentioned, and can be appropriately selected according to the purpose. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for forming.
  • the weight average fiber length of carbon fibers in a molded product obtained by molding the resin composition of the present invention is not particularly limited, but is preferably in the range of 0.01 to 0.5 mm.
  • the weight average fiber length of the carbon fibers is within this preferable range, sufficient impact strength and bending elastic modulus can be obtained, and the surface appearance does not deteriorate.
  • the weight average fiber length of the carbon fiber in the molded product is obtained by baking a sample cut out from the molded product at a predetermined amount at 500 ° C. for 1 hour, dispersing the obtained ash in water, and then filtering the residue. It can obtain
  • weight average fiber length of (B) carbon fibers in the molded product for example, a method using pellets having an arbitrary fiber length distribution according to the target fiber length, melting such as injection molding Examples thereof include a method of appropriately adjusting the screw rotation speed, cylinder temperature, injection pressure, and back pressure during processing.
  • the molded product obtained by molding the resin composition of the present invention has a ratio (Lw / Ln) of weight average fiber length to number average fiber length of carbon fibers in the molded product of 1.0 or more and less than 1.3. Preferably there is. When Lw / Ln is within this preferred range, a molded product with excellent surface appearance and reduced warpage can be obtained.
  • the molded product obtained by molding the resin composition of the present invention can be widely used in various applications such as automobile parts, electric / electronic parts, building members, various containers, daily necessities, daily goods and hygiene goods.
  • the molded product obtained by using the resin composition of the present invention is particularly high in rigidity, excellent in surface appearance and water absorption characteristics, and thus can be suitably used for a housing of an electric / electronic component.
  • it is excellent in fluidity and thin-wall moldability and can reduce warpage, it is suitable for a thin-walled electronic device casing having an average wall thickness of 0.5 to 1.0 mm or less.
  • the average thickness of a thin-walled electronic device casing refers to the number average value of the thicknesses of 20 locations randomly selected in the electronic device casing.
  • the wall thickness can be measured using a micrometer.
  • Specific examples of the thin electronic device casing include casings such as notebook computers, electronic notebooks, mobile phones, PDAs, digital cameras, and projectors. Larger area and more suitable for notebook PC housings that require fluidity.
  • Intrinsic viscosity of polyamide resin 0.1 g of polyamide resin was dissolved in 50 mL of 98% sulfuric acid solution, and the number of seconds that the sample solution flowed down was measured at 30 ° C ⁇ 0.05 ° C using an Ubbelohde viscometer. The intrinsic viscosity was calculated based on the following formula.
  • [ ⁇ ] is the intrinsic viscosity (dL / g)
  • ⁇ SP is the specific viscosity
  • C is the sample concentration (g / dL)
  • t is the flow down time (second) of the sample solution
  • t 0 is the sulfuric acid Indicates the number of seconds (seconds) for the flow down.
  • Fluidity of the resin composition The resin composition pellets obtained in each of the examples and comparative examples were subjected to a cylinder temperature of 320 ° C and gold using a 75-ton injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. Injection molding was performed under conditions of a mold temperature of 130 ° C., an injection pressure of 55 MPa, an injection time of 5 seconds, and a molded product thickness of 0.7 mm. After the first 20 shots were molded, the flow lengths of 10-shot molded products that were subsequently molded were averaged, and the value was taken as the bar flow flow length. The larger this value, the better the fluidity.
  • the height of the lift is 0.5 mm or less.
  • the height of lifting is more than 0.5 mm and 1.0 mm or less.
  • the floating height is more than 1.0 mm and not more than 3.0 mm.
  • a molded product can be obtained and warpage is small.
  • the obtained prepolymer was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a particle size of 2 mm or less, solid-phase polymerized at 230 ° C. and 13 Pa (0.1 mmHg) for 8 hours, and a melting point of 262 ° C.
  • a white polyamide resin (A-1) having an intrinsic viscosity of 0.91 dL / g was obtained.
  • the obtained dendritic polyester (C-1) was subjected to nuclear magnetic resonance spectrum analysis.
  • the content p of p-oxybenzoate units was 2.66, 4,4′-di with respect to the trimesic acid residue.
  • the content q of oxybiphenyl units and ethylene oxide units was 0.66
  • the content r of terephthalate units was 0.66
  • p + q + r 4.
  • carboxylic acid and acetyl groups were present in a ratio of 64:36.
  • the nuclear magnetic resonance spectrum was obtained by analyzing the nuclear magnetic resonance spectrum of the proton nucleus at 40 ° C. using a solution of dendritic polyester (C-1) dissolved in a mixed solvent of 50% pentafluorophenol: 50% deuterated chloroform. 7.44 ppm and 8.16 ppm peaks derived from p-oxybenzoate units, 7.04 ppm and 7.70 ppm peaks derived from 4,4′-dioxybiphenyl units, 8.31 ppm peaks derived from terephthalate units, ethylene oxide units A peak at 4.75 ppm derived from 9.25 ppm derived from trimesic acid was detected.
  • the content ratio of each structural unit was calculated from the area intensity ratio of each peak, and the three decimal places were rounded off. From the ratio of the peak area intensity derived from the branch structure portions P, Q, and R and the peak area intensity derived from the organic residue S, the contents p, q, r, and the content of the branch point S were calculated. Further, the presence or absence of the reaction of carboxylic acid was determined from the peak shift of the three protons of trimesic acid, and the degree of branching was calculated to be 0.68 (rounded to the third decimal place). The degree of branching was determined by calculating the ratio of those in which all three functional groups of trimesic acid were reacted.
  • the obtained dendritic polyester (C-1) had a melting point Tm of 185 ° C., a liquid crystal starting temperature of 159 ° C., and a number average molecular weight of 2,300.
  • the melting point (Tm) is an observation of the endothermic peak temperature (Tm 1 ) observed when the dendritic polyester (C-1) is measured at room temperature to 20 ° C./min in differential calorimetry. Thereafter, the temperature is maintained at a temperature of Tm 1 + 20 ° C. for 5 minutes, once cooled to room temperature under a temperature decrease condition of 20 ° C./min, and again measured with a temperature increase condition of 20 ° C./min, an endothermic peak temperature (Tm ).
  • the liquid crystal start temperature is the temperature at which the entire field of view starts to flow with a shear stress heating device (CSS-450) under the conditions of a shear rate of 100 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens 60 times. It was.
  • the solution was measured as an absolute molecular weight by GPC-LS (gel permeation chromatography-light scattering) method.
  • GPC-LS gel permeation chromatography-light scattering
  • a column uses Shodex KG, Shodex K-806M ⁇ 2, Shodex K-802, flow rate 0.8 mL / min, temperature 23 ° C., detector is a differential refractometer (RI), Multi-angle light scattering (MALS) was used.
  • Examples 1 to 8, Comparative Examples 1 to 8 A twin-screw extruder (TEX30 ⁇ manufactured by Nippon Steel Works) with the cylinder temperature set to the temperature shown in Table 1 and the screw rotation speed set to 200 rpm was used. Polyamide resin, dendritic polyester, acid anhydride and flame retardant were supplied from the main hopper in the formulations shown in Tables 1 and 2, and carbon fibers were supplied from the side feeder into the molten resin and melt kneaded. The strand discharged from the die was cooled in water, cut into a length of 3.0 mm by a strand cutter, and pelletized to obtain a carbon fiber reinforced resin composition pellet. Various characteristics evaluation was performed by the method mentioned above using the produced pellet. The results are shown in Tables 1-2.
  • the carbon fiber reinforced resin compositions shown in Examples 1 to 8 are excellent in thermal stability, residence stability, fluidity and thin-wall moldability, have very high rigidity (flexural modulus), strength and impact resistance. Further, it is possible to obtain a molded article having excellent water absorption characteristics (low water absorption) and surface appearance and having reduced warpage. On the other hand, since the carbon fiber reinforced resin composition shown in Comparative Examples 1 and 7 does not contain the dendritic polyester (C), it is inferior in fluidity, thin moldability, and thermal stability (gas generation situation). The warp reduction was insufficient.
  • the carbon fiber reinforced resin compositions shown in Comparative Examples 2 to 5 do not use the semi-aromatic polyamide resin specified in (A), fluidity, water absorption, water absorption characteristics, warpage, thin moldability, and thermal stability ( It was inferior to any of the characteristics of gas generation status.
  • the carbon fiber reinforced resin composition shown in Comparative Example 6 is inferior in flexural modulus because the blending amount of the carbon fiber (B) is as small as 44 parts by weight with respect to 100 parts by weight of the semi-aromatic polyamide resin (A). It was.
  • the amount of the carbon fiber (B) is as large as 212 parts by weight with respect to 100 parts by weight of the semi-aromatic polyamide resin (A). A large amount of gas was generated and pelletization was difficult.
  • the carbon fiber reinforced resin composition of the present invention is excellent in thermal stability, retention stability, fluidity and thin-wall moldability, has the same level of rigidity as metal, and has excellent surface appearance and water absorption characteristics, while reducing warpage.
  • a molded product can be obtained. Therefore, it can be suitably used for an electronic device casing such as a personal computer or a mobile phone that requires light weight, high rigidity, thin-wall moldability, good surface appearance, and the like.

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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
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Abstract

　L'invention concerne une composition de résine renforcée par des fibres de carbone, formée par le mélange de (B) 60-200 parties en poids de fibres de carbone et de (C) 0,01-10 parties en poids de polyester dendritique dans (A) 100 parties en poids d'une résine de polyamide semi-aromatique qui présente un point de fusion de 220-300°C et qui est obtenue par la polycondensation d'un acide dicarboxylique contenant 60-100 % en mole d'acide téréphtalique dans la quantité totale d'acide dicarboxylique et d'une diamine contenant un total de 60-100 % en mole de 1,9-nonanediamine et/ou de 2-méthyl-1,8-octanediamine dans la quantité totale de diamine. L'invention concerne des pellets. L'invention concerne un objet moulé. L'invention concerne un boîtier pour un dispositif électronique. L'invention concerne une composition de résine renforcée par des fibres de carbone, des pellets et un objet finement moulé obtenu par moulage par extrusion de pellets et destiné à être utilisé dans un boîtier pour un dispositif électronique, qui permettent d'obtenir des objets moulés présentant moins de déformation, tout en présentant une excellente stabilité thermique, une excellente stabilité de rétention, une excellente fluidité et une excellente adéquation pour le moulage d'objets fins ainsi qu'une excellente rigidité d'un niveau équivalent à celui d'un métal, un aspect attractif et des caractéristiques d'adsorption d'eau.
PCT/JP2014/076517 2013-10-11 2014-10-03 Composition de résine renforcée par des fibres de carbone, pellets, objet moulé et boîtier pour dispositif électronique WO2015053181A1 (fr)

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CN201480046695.5A CN105492537B (zh) 2013-10-11 2014-10-03 碳纤维强化树脂组合物、粒料、成型品以及电子设备壳体

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US20200109283A1 (en) * 2017-03-21 2020-04-09 Solvay Specialty Polymers Usa, Llc Thermoplastic composites and corresponding fabrication methods and articles
WO2020218209A1 (fr) * 2019-04-26 2020-10-29 ユニチカ株式会社 Composition de résine de polyamide et article moulé obtenu par moulage de celle-ci
WO2021029275A1 (fr) * 2019-08-09 2021-02-18 住友化学株式会社 Pastille de résine de polyester à cristaux liquides, son procédé de production, et procédé de production d'un article moulé
EP3974469A4 (fr) * 2019-05-20 2022-07-06 Toyobo Co., Ltd. Composition de résine à base de polyamide pour moulage par injection et composant coulissant formé à partir de celle-ci

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JP7091660B2 (ja) * 2016-09-26 2022-06-28 東レ株式会社 電子機器筐体およびその製造方法
JP7147740B2 (ja) 2017-02-21 2022-10-05 三菱瓦斯化学株式会社 非晶性ポリアミド樹脂および成形品
EP4052894A4 (fr) * 2019-12-17 2024-02-14 Fukuvi Chemical Industry Co., Ltd. Feuille composite de résine renforcée par des fibres, matériau composite de résine renforcée par des fibres, et article moulé en résine les comportant
CN116568744B (zh) * 2020-12-09 2024-09-17 三菱化学株式会社 树脂组合物、粒料、成型品和树脂组合物的制造方法
CN113651956B (zh) * 2021-08-23 2022-09-16 安徽农业大学 超高韧性支化聚酰胺共聚物的制备方法、制得的聚酰胺共聚物

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WO2016098403A1 (fr) * 2014-12-19 2016-06-23 オリンパス株式会社 Cadre de miroir, barillet d'objectif et dispositif optique
US20200109283A1 (en) * 2017-03-21 2020-04-09 Solvay Specialty Polymers Usa, Llc Thermoplastic composites and corresponding fabrication methods and articles
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WO2020218209A1 (fr) * 2019-04-26 2020-10-29 ユニチカ株式会社 Composition de résine de polyamide et article moulé obtenu par moulage de celle-ci
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WO2021029275A1 (fr) * 2019-08-09 2021-02-18 住友化学株式会社 Pastille de résine de polyester à cristaux liquides, son procédé de production, et procédé de production d'un article moulé
JP2021028373A (ja) * 2019-08-09 2021-02-25 住友化学株式会社 液晶ポリエステル樹脂ペレット、及びその製造方法、並びに成形体の製造方法

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