WO2006077818A1 - 熱可塑性樹脂組成物 - Google Patents
熱可塑性樹脂組成物 Download PDFInfo
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- WO2006077818A1 WO2006077818A1 PCT/JP2006/300504 JP2006300504W WO2006077818A1 WO 2006077818 A1 WO2006077818 A1 WO 2006077818A1 JP 2006300504 W JP2006300504 W JP 2006300504W WO 2006077818 A1 WO2006077818 A1 WO 2006077818A1
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
- C08L21/00—Compositions of unspecified rubbers
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Definitions
- the present invention relates to a resin composition comprising polyamide reinforced with a plate-like inorganic filler and polyphenylene ether. Furthermore, the present invention relates to a thermoplastic resin composition in which the balance between fluidity (particularly, thin wall fluidity), surface impact strength, and tensile elongation is remarkably improved while maintaining excellent dimensional stability.
- Polyphenylene ether is excellent in mechanical properties, electrical properties, and heat resistance, and is excellent in dimensional stability and is used in a wide range of applications.
- Polyphenylene ether alone has the major disadvantage of being inferior in oil resistance and molding cache.
- Patent Document 1 a technique of blending polyamide with polyphenylene ether has been proposed, and it is now a material used for a wide variety of applications.
- a small plate-like inorganic filler having an average particle size of 8 xm or less, particularly 5 zm or less, is used as a polyamide-polyphenylene. Attempts have been made to blend into ether resin compositions.
- a technique of blending talc having an average particle diameter of 5 or less and an aspect ratio of 5 or more Patent Document 2
- a technique of blending a plate-like inorganic filler having an average particle diameter of 5 / m or less and an aspect ratio of 3 or more Patent Document 3
- Technology for combining plate-like inorganic fillers with an average particle size of 3 ⁇ m or less and a specific particle size distribution Patent Document 4
- average particle size of 1.2 to 5 / m, L / D of 3 or more Plate-like filler and / or fibrous inorganic filler with a fiber length of 2 ⁇ m or more, carbon black and fine Technology for blending fibrous carbon and hydrogenated block copolymer having a number average molecular weight of 80,000 or less Patent Document 5
- Technology for blending talc and carbon Patent Document 6
- Inorganic having an average particle size of 8 / m or less A technology for blending a filler and a hydrogenated block
- Patent Document 1 Japanese Patent Publication No. 45-997 (corresponding to US Pat. Nos. 3,379, 792)
- Patent Document 2 JP-A-2-163158 (corresponding to US Pat. No. 5,086, 105)
- Patent Document 3 JP-A-6-145499 (corresponding to US Pat. No. 5,475,049)
- Patent Document 4 JP-A 2002- No. 194206
- Patent Document 5 Japanese Patent Laid-Open No. 2002-194207
- Patent Document 6 Special Table 2003-528941 (corresponding to European Patent 1,232,218)
- Patent Document 7 JP 2004-285136
- Patent Document 8 Japanese Patent Laid-Open No. 5-220826
- An object of the present invention is to provide a thermoplastic resin that simultaneously satisfies contradictory fluidity and surface impact characteristics in a polyamide polyphenylene ether alloy resin composition reinforced with an inorganic filler. It is to provide a functional resin composition, and a molded article molded from the composition, particularly an automotive exterior part.
- the present inventors have intensively studied to solve the above problems. As a result, and an average particle child size 9 ⁇ 20 ⁇ ⁇ , particle size of 25% from the smallest particle diameter and (d25./ 0) 75.
- an average particle child size 9 ⁇ 20 ⁇ ⁇ particle size of 25% from the smallest particle diameter and (d25./ 0) 75.
- a plate-like inorganic filler with a particle diameter (d75%) ratio (d75% / d25%) of 1.0 / 2.5 between 1.0 and 2.5 it is excellent in surface impact strength and tensile elongation, and more fluid We found that it is excellent in performance, and reached the present invention.
- the present invention is as follows.
- thermoplastic resin composition as described in 1 above, wherein (D) the plate-like inorganic filler has an average particle diameter of more than 10 ⁇ and 20 / im or less.
- thermoplastic resin composition according to any one of 1 to 4 above, wherein the plate-like inorganic filler is talc.
- thermoplastic resin composition as described in 5 above which is talc having a solid apparent density of (D) a plate-like inorganic filler of 0.5 to 0.8 g / cm 3 .
- thermoplastic resin composition as described in 5 above, wherein (D) the plate-like inorganic filler is talc, and the crystallite diameter of the (002) diffraction plane of talc by wide-angle X-ray diffraction is 600 A or more.
- (C) rubbery polymer is the sum of (A) polyamide resin and (B) polyphenylene ether resin 2.
- the thermoplastic resin composition according to 1 above which is 5 to 40 parts by mass with respect to 100 parts by mass.
- thermoplastic resin composition according to any one of the above:! To 9, which is a conjugation compound block copolymer and a z- or hydrogenated block copolymer.
- the number average molecular weight of one polymer block mainly composed of aromatic bur compound in the mixture is not less than 10,000 and less than 30,000, and the number average of one polymer block mainly composed of a conjugated diene compound 11.
- thermoplastic resin composition according to any one of 1 to 12 above, which comprises a conductive material as component (E).
- thermoplastic resin composition according to the above 13 which is at least one selected from the group consisting of conductive carbon black and carbon fibrils.
- thermoplastic resin composition as described in 14 above, wherein (E) a conductive material is added as a conductive masterbatch previously melt-kneaded with (A) polyamide.
- thermoplastic resin composition according to any one of the above 1 to 16:
- thermoplastic resin composition according to any one of the above 1 to 16 items 4.
- thermoplastic resin composition in which the balance of fluidity (particularly thin-walled fluidity), surface impact strength, and tensile elongation is remarkably improved while maintaining excellent dimensional stability. That power S.
- thermoplastic resin composition of the present invention will be described in detail.
- Polyamide is generally obtained by polycondensation of diamine and dicarboxylic acid, ring-opening polymerization of ratatam, polycondensation of aminocarboxylic acid, etc., but is not limited thereto.
- the diamine is roughly classified into aliphatic, alicyclic and aromatic diamines. Specific examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 2, 2, 4-trimethylhexamethylenediamine, 2, 4, 4 trimethylhexamethylenediamine, 5-methylnanomethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4 bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m xylylenediamine, p-xylylenediamine, 1,9 nonanediamine, 2-methyl-1,8-octanediamine, and the like.
- the dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,1,3 tridecanedioic acid, 1,3 cyclohexanedicarboxylic acid, terephthalic acid , Isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like. Specific examples of ratatam include ⁇ -force prolatatam, enantolactam, and ⁇ -laurolactam.
- aminocarboxylic acids include ⁇ -aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 1 1-aminoundecanoic acid, and 12-aminododecanoic acid. , 13-aminotridecanoic acid and the like.
- any of the copolymerized polyamides obtained by polycondensation of these ratatams, diamines, dicarboxylic acids, and ⁇ -aminocarboxylic acids alone or in a mixture of two or more types can be used.
- those obtained by polymerizing these ratatams, diamines, dicarboxylic acids, and ⁇ -aminocarboxylic acids to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight in an extruder or the like can also be used suitably.
- Preferred polyamides are polyamide 6, polyamide 6, 6, polyamide 6/6, 6, polyamide 6, 12, polyamide 6,6 / 6, 1, or mixtures thereof. More preferred is a blend of polyamide 6,6, polyamide 6, or polyamide 6, 6 and polyamide 6, polyamide 6, 6 and polyamide 6, 6 / 6,1, and still more preferred is polyamide 6 or polyamide 6. And polyamide 6, 6 blend.
- the relative viscosity of the polyamide used in the present invention is preferably 2.0 or more. Further, in order to improve the balance between fluidity and surface impact property of the resin composition, the range of relative viscosity of polyamide 2.2 to 2.8 is more preferable, and more preferably 2.2 to 2. The range is 7.
- the relative viscosity is measured by separating the polyamide component contained in the composition or measuring the polyamide component used as a raw material.
- Polyamide end groups generally have amino groups and carboxyl groups, and a preferred ratio is an amino group / carboxyl group ratio (concentration ratio) (hereinafter also referred to as end group ratio). More preferably, it is 1/9 to 5/5, more preferably 2/8 to 4/6, and most preferably 2/8 to 3/7.
- a method for adjusting the terminal group ratio of these polyamide resins a known method that will be apparent to those skilled in the art can be used. For example, it is adjusted by a method of adding diamines, dicarboxylic acids, monocarboxylic acids or the like so that a predetermined end group ratio is obtained at the time of polymerization of the polyamide resin, or by a mixture of two or more kinds of polyamide resins having different end group ratios. And the like.
- metal stabilizers such as those described in JP-A No. 1163262, which are known for the purpose of improving the heat resistance stability of polyamide resins, can be used without problems.
- metal stabilizers Cu I, CuCl, copper acetate, cerium stearate, and the like are particularly preferable.
- Alkali metal halide salts represented by potassium and the like can also be suitably used. Of course, these may be added together.
- a preferred blending amount of the metal stabilizer and the halogen salt of Z or alkali metal is 0.001 to:! Parts by mass with respect to 100 parts by mass of the polyamide resin as a total amount.
- polyamide 1 It may be added in an amount less than 10 parts by mass with respect to 00 parts by mass.
- the (B) polyphenylene ether that can be used in the present invention is a homopolymer and / or copolymer comprising the structural unit of the formula (1).
- O is an oxygen atom
- R to R are each independently hydrogen, no, rogen, primary or
- polyphenylene ether of the present invention examples include, for example, poly (2,6-dimethylolene 1,4_phenylene etherenole), poly (2-methinore_6-ethinolone 1,4_fuel). Ether), poly (2-methylolene 6_phenyl-1,1,4_phenylene ether), poly (2,6-dichloro 1,4_phenylene ether) and the like.
- copolymers of 2,6-dimethylphenol and other phenols for example, copolymers of 2,3,6-trimethylphenol as described in JP-B-52-17880
- Polyphenylene ether copolymers such as 2-methyl-6-butylphenol
- polyphenylene ether is particularly preferred as poly (2, 6-dimethyl-1, 4 —Phenylene ether), a copolymer of 2,6 dimethylenophenol and 2, 3, 6 trimethylphenol, or a mixture thereof.
- the method for producing the polyphenylene ether used in the present invention is not particularly limited, and known methods can be used. For example, as described in U.S. Pat.Nos. 3,306,874, 3,068,753, 3,257,357 and 3,257,358, Japanese Patent Laid-Open Nos. 50-51197 and 63-152628, etc. It is possible to list the manufacturing methods that have been used.
- the reduced viscosity (sp / c: 0.5 g / dl, black mouth form solution, measured at 30 ° C) of the polyphenylene ether that can be used in the present invention is in the range of 0.15 to 0.70 dlZg. More preferably, it is in the range of 0.20 to 0.60 dl / g, and more preferably in the range of 0.40 to 0.55 dl / g.
- two or more kinds of polyphenylene ethers having different reduced viscosities can be used without any problem.
- a force S including, but not limited to, a mixture of polyphenylene ether of 50 dl / g or more.
- polyphenylene ether that can be used in the present invention may be a polyphenylene ether modified in whole or in part.
- modified polyphenylene ether refers to at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycine. It refers to polyphenylene ether modified with at least one modifying compound having a dinole group.
- the method for producing the modified polyphenylene ether is as follows: (1) Polyphenylene at a temperature in the range of 100 ° C. or higher and lower than the glass transition temperature of polyphenylene ether in the presence or absence of a radical initiator. A method in which the ether is reacted with the modifying compound without melting; (2) in the presence or absence of a radical initiator, at a temperature in the range of the glass transition temperature of the polyphenylene ether to 360 ° C. or less. Ren ether and modifying compounds And (3) a solution of polyphenylene ether and the modifying compound in the presence or absence of a radical initiator at a temperature below the glass transition temperature of the polyphenylene ether. The method of making it react in is mentioned. Any of these methods may be used, but the methods (1) and (2) are preferred.
- the molecular structure has at least one carbon-carbon double bond or triple bond, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group.
- the at least one modified compound will be specifically described.
- modified compounds having a carbon-carbon double bond, a carboxylic acid group, and an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis_4-cyclohexene_1,2-dicarboxylic acid and These acid anhydrides are mentioned. Fumaric acid, maleic acid, and maleic anhydride are particularly preferable, and fumaric acid and maleic anhydride are particularly preferable. In addition, one in which one or two of the carboxyl groups of the unsaturated dicarboxylic acid is an ester can be used.
- Examples of the modified compound having both a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl atylate, glycidyl metatalylate, and epoxidized natural oil. Of these, glycidyl acrylate and glycidyl methacrylate are particularly preferred.
- modified compounds having both a carbon-carbon double bond and a hydroxyl group in the molecule include those of the general formula CH OH (where n is a positive integer) such as aryl alcohol, 4-pentene 1-ol, 1,4-pentagen 3-ol. Saturated alcohol, general formula CH OH, C n 2n-3 n 2n-5 n
- Examples thereof include unsaturated alcohols such as H OH (n is a positive integer).
- the modifying compounds described above may be used alone or in combination of two or more.
- the amount of the modified compound added in the production of the modified polyphenylene ether is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyphenylene ether, and more preferably. 0.3 to 5 parts by mass.
- a preferable amount of the radical initiator in producing the polyphenylene ether modified with the radical initiator is 0.00 :! to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether.
- the addition ratio of the modifying compound in the modified polyphenylene ether is preferably 0.01 to 5% by mass. More preferably, the content is 0.1 to 3% by mass. In the modified polyphenylene ether, an unreacted modified compound and / or a polymer of the modified compound may remain.
- a styrenic thermoplastic resin may be blended in an amount of less than 50 parts by mass with respect to 100 parts by mass of the total polyphenylene ether.
- examples of the styrenic thermoplastic resin referred to in the present invention include homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin). Etc.
- known additives that can be added to the polyphenylene ether may be added in an amount of less than 10 parts by mass with respect to 100 parts by mass of the polyphenylene ether.
- the (C) rubber-like polymers contained in the thermoplastic resin composition of the present invention preferred are a polymer block mainly composed of at least one aromatic vinylic compound and at least one conjugated gene.
- a polymer block mainly composed of at least one aromatic vinylic compound and at least one conjugated gene preferred are one or more selected from the group consisting of an aromatic vinyl compound-conjugated conjugated compound block copolymer composed of a polymer block mainly composed of a compound, a hydrogenated product thereof, and an ethylene ⁇ -olefin copolymer. is there.
- mainly in a polymer block mainly composed of an aromatic bull compound refers to a block in which at least 50% by mass or more of the block is an aromatic bull compound. More preferably, it is 70% by mass or more, more preferably 80% by mass or more, and most preferably 90% by mass or more.
- the aromatic bur compound that can be used in the aromatic bur compound-conjugated conjugated compound block copolymer in the present invention include styrene, a-methyl styrene, vinyl toluene, and the like. One or more compounds selected from these are used, and styrene is particularly preferable among them.
- conjugated gen compound examples include butadiene, isoprene, piperylene, 1, 3 ⁇ tantagen, and the like.
- One or more compounds selected from these are used, but butadiene, isoprene and combinations thereof are particularly preferable.
- the microstructure of the soft segment of the conjugation compound of the block copolymer is preferably 1,2—bulule content or the total of 1,2-vininole content and 3,4-bule content is 5-80%. 10 to 50% is preferred, and 10 to 40% is most preferred.
- the block copolymer in the present invention is composed of a polymer block [S] mainly composed of an aromatic vinyl compound and a polymer block [B] mainly composed of a conjugated diene compound.
- S—B—S—B is preferably a block copolymer having a bond type selected from the B type. Of course, even a mixture of these is acceptable. Among these, S—B—S type and S—B—S—B type are more preferable. Of course, these may be a mixture.
- the block copolymer of the aromatic vinyl compound and the conjugated diene compound that can be used in the thermoplastic resin composition of the present invention is more preferably a hydrogenated block copolymer.
- a hydrogenated block copolymer refers to an aliphatic dimer of a polymer block mainly composed of a conjugated gen compound by hydrogenating a block copolymer of the above aromatic beer compound and the conjugated gen compound. This means that the double bond is controlled in the range of more than 0 to 100%.
- the preferred hydrogenation rate of the hydrogenated block copolymer is 50. / o or more, more preferably 80% or more, and most preferably 98. / 0 or more.
- the block copolymer of component (C) contains (C1) a polymer block mainly composed of at least one aromatic vinyl compound in an amount of 55% by mass or more and less than 90% by mass.
- the number average molecular weight of one polymer block mainly composed of an aromatic bur compound in the mixture is 10,000 or more and less than 30,000, and one polymer block mainly composed of a conjugation compound.
- the number average molecular weight is preferably in the range of 50,000 or more and less than 100,000. More preferably, the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound in the mixture of block copolymers is 10,000 or more and less than 25,000 and mainly composed of a conjugated diene compound.
- the number average molecular weight of one polymer block is 50,000 or more and less than 80,000.
- the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound of the block copolymer and the number average molecular weight of one polymer block mainly composed of a conjugation compound are (The number average molecular weight of each block copolymer of component (C), the mass% of the polymer block mainly composed of all aromatic bur compounds in the block copolymer, and all the conjugation compounds in the block copolymer It can be calculated from the mass% of the polymer block mainly composed of.
- the number average molecular weight of each block copolymer of the component (C) is determined by using a gel permeation chromatography measuring apparatus [GPC SYSTEM21: manufactured by Showa Denko KK], an ultraviolet spectroscopic detector [UV — 41: Shows the number average molecular weight measured by Showa Denko KK and converted to standard polystyrene.
- Solvent Chloroform form, Temperature: 40 ° C, Column: Samnole side (K—G, K-800RL, K—800R), Reference side (K—805L X 2), Flow rate 10ml / min, Measurement wavelength: 254 nm, pressure 15-: 17 kgZcm 2 ].
- a low molecular weight component due to catalyst deactivation during polymerization may be detected, but in this case, the low molecular weight component is not included in the molecular weight calculation.
- the number average molecular weight of the block copolymer contained in the composition is, for example, that a pellet is sliced with a microtome to a thickness of 20 to 50 ⁇ , and this is immersed in a black mouth form, 80. About C Extract for about 1 hour using a constant-temperature shaker set at the specified temperature, and dissolve the polyphenylene ether and the block copolymer in the black mouth form. This is filtered off, and methanol is added to the filtrate more than 3 times the filtrate to reprecipitate and vacuum dried. The obtained powdery sample is further dissolved in methylene chloride and left to stand at -10 ° C for 12 hours. The deposited component (polyphenylene ether component) is filtered off, and the filtrate can be confirmed by measuring with a gel permeation chromatography measuring device.
- the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound of one type of block copolymer is obtained by the following equation using the number average molecular weight of the block copolymer described above. I can do it.
- Mn is the number average molecular weight of one polymer block mainly composed of the aromatic bur compound of block copolymer n
- Mn is the number average molecular weight of block copolymer n
- a is block copolymer n.
- b is the mass% of the polymer block mainly composed of the conjugation compound in the block copolymer n
- N is in the block copolymer n. This represents the number of polymer blocks mainly composed of aromatic vinyl compounds.
- the block copolymer of component (C) is typically a mixture of two or more block copolymers composed of components (C1) and (C2),
- the number average molecular weight of a single polymer block mainly composed of the aromatic vinyl compound can be determined by the following formula.
- Mn is the number average molecular weight of one polymer block mainly composed of an aromatic bur compound in the mixture of block copolymers
- Mn is one composed mainly of an aromatic vinyl compound of the block copolymer n.
- the number average molecular weight of one polymer block, Cn represents the weight fraction of block copolymer n in the block copolymer mixture.
- Mn is a component mainly composed of the conjugate copolymer of block copolymer n.
- Mn is the number average molecular weight of block copolymer ⁇
- a is mass% of the polymer block mainly composed of aromatic vinyl compound in block copolymer n
- b is block copolymer weight
- N is a polymer block mainly composed of the conjugated gen compound in the block copolymer n.
- the block copolymer of component (C) is typically a mixture of two or more block copolymers composed of component (C1) and component (C2),
- the number average molecular weight of one polymer block mainly composed of the conjugated gen compound can be obtained by the following formula.
- Mn is mainly the conjugated diene compound in the block copolymer mixture.
- Mn The number average molecular weight of a single polymer block, Mn is the copolymer of block copolymer n
- the number average molecular weight of one polymer block mainly composed of a role-gen compound, Cn represents the weight fraction of the block copolymer n in the block copolymer mixture.
- the component (C) is made into a mixture of two or more block copolymers composed only of block copolymers having a number average molecular weight of less than 120,000, thereby improving fluidity. Since the balance of surface impact property can further be improved, it is more preferable. Furthermore, it is particularly preferable to make a mixture composed only of a block copolymer having a number average molecular weight of more than 80,000 and less than 120,000.
- the block copolymer used in the thermoplastic resin composition of the present invention may be prepared by previously mixing oil mainly composed of paraffin. Paraffin It is possible to improve the processability of the resin composition by mixing the oil as the main component in advance. In this case, the preferred amount of oil mainly composed of paraffin is:! To 70 parts by mass with respect to 100 parts by mass of the block copolymer. When 70 parts by mass or more is mixed, the handling property is poor.
- the oil mainly composed of paraffin here is a mixture of hydrocarbon compounds having a weight average molecular weight in the range of 500 to 10,000, which is a combination of an aromatic ring-containing compound, a naphthene ring-containing compound, and a paraffinic compound.
- the content of paraffinic compounds is 0% by mass or more. More preferably, the paraffinic compound is 50 to 90% by mass, the naphthene ring-containing compound is 10 to 40% by mass, and the aromatic ring-containing compound is 5% by mass or less.
- These oils mainly composed of nophine are commercially available, such as PW380 manufactured by Idemitsu Kosan Co., Ltd.
- ethylene monoolefin copolymer examples include ethylene ⁇ -age produced with a singolite catalyst as described in JP-A-2001-302911. Refin copolymer is preferably usable
- the rubber-like polymer used in the thermoplastic resin composition of the present invention may be a rubber-like polymer that has been modified in whole or in part.
- the rubber-modified polymer is modified with at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group.
- the method for producing the modified rubbery polymer is as follows: (1) in the presence or absence of a radical initiator, at a temperature in the range from the softening point temperature of the rubbery polymer to 250 ° C or less. A method in which a rubbery polymer and a modifying compound are melt-kneaded and reacted; (2) in the presence or absence of a radical initiator, at a temperature below the softening point of the rubbery polymer, the rubbery polymer and the modified compound. (3) melting the rubbery polymer and the modifying compound at a temperature below the soft point of the rubbery polymer in the presence or absence of a radical initiator. The method of making it react without mentioning is mentioned.
- any of these methods may be used, but the method (1) is preferable, and the method (1) in the presence of a radical initiator is most preferable.
- At least one modification having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure here.
- the same modified compounds described for the modified polyphenylene ether can be used.
- the (D) plate-like inorganic filler of the present invention has an average particle size of 9 to 20 ⁇ m, a small particle size, 25% particle size (d25%) and 75% particle size.
- the ratio (d75% / d25%) of (d75%) is 1.0 or more and 2.5 or less.
- the average particle diameter of the preferred plate-like inorganic filler is more than 10 zm and not more than 20 zm, more preferably 11 to 17 zm, still more preferably 12 to 17 xm, and particularly preferably 13 to 17 zm. is there.
- the fluidity can be remarkably improved by using a relatively large particle size plate-like inorganic filler with an average particle size of 9 to 20 ⁇ m, which is smaller than that of a small plate-like inorganic filler with an average particle size of 5 xm or less. Is possible.
- the ratio of the 25% particle size (d25%) to the 75% particle size (d75%) (d75% / d25%) ) Is more preferably 1 ⁇ 2 or more and 2.5 or less, more preferably 1.5 or more and 2.5 or less, and particularly preferably 1.5 or more and 2.0 or less. That is, by using a plate-like inorganic filler having a d75% / d25% value of 1.0 or more and 2.5 or less, it is possible to significantly improve the surface impact strength and tensile elongation of the resin composition. Become.
- the ratio of the particle diameter of 10 / m or less is 50% or less and the ratio of the particle diameter of 20 ⁇ or more is 25% or less.
- the ratio force of the particle diameter of 10 ⁇ m or less is 3 ⁇ 40% or less.
- the ratio of the particle diameter of 20 ⁇ m or more is 20% or less.
- the average particle size and particle size distribution referred to here are based on the volume-based particle size measured using a laser diffraction / scattering particle size distribution measuring apparatus. Moreover, it is a value measured using ethanol as a dispersion medium for the plate-like inorganic filler. Specifically, using a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by HORIBA, Ltd.), a blank measurement was performed with an ethanol dispersion medium, and then the measurement sample was subjected to a specified transmittance (95 % ⁇ 70%) and can be obtained by measuring. The sample is dispersed in the dispersion medium by irradiating with ultrasonic waves for 1 minute.
- the plate-like inorganic filler of the present invention has the above shape, for example, kaolinite, talc, Mica such as sericite, muscovite, and phlogopite; layered clay minerals such as chlorite, montmorillonite, halosite, etc .; obtained by pulverizing and / or sieving artificial plate-like fillers such as glass flakes and metal plate-like particles Can be used.
- talc obtained by purifying, pulverizing and classifying natural minerals mainly composed of magnesium silicate is preferable. Artificially synthesized materials can also be used. One or more of these fillers can be blended.
- the plate-like inorganic filler used in the present invention preferably has a firm apparent density in the range of 0.5 to 0.8 g / cm 3 . More preferably, the apparent apparent density is in the range of 0.5 to 0.75 g / cm 3 .
- a plate-like inorganic filler having a firm apparent density of 0.5 to 0.8 g / cm 3 is excellent in supply stability during production and can provide a composition with little variation in physical properties.
- the apparent density of the solid inorganic filler is in the range of 0.5 to: 1.3 gZcm 3 in many cases.
- talc having a hard apparent density of 0.5 to 0.8 g / cm 3 , and at the same time, linear expansion coefficient, fluidity, surface impact property and tensile elongation are simultaneously used. Can be satisfied.
- the solid apparent density as used in the present invention is one of the apparent densities of powders determined by a powder tester (for example, manufactured by Hosokawa Micron Corporation). Specifically, it is a value measured from the weight of talc in a 100 cm 3 volume after a predetermined vibration is applied to a 100 cm 3 container, and the unit is g / cm 3 . Normally, the number of applied vibrations (vertical movement) is 180 times, and the amplitude does not exceed 5 cm.
- the apparent apparent density is an index indicating the ease with which the specimen is compressed. The higher this value, the more likely it is to be compressed and hardened.
- the loose apparent density of talc that can be used in the present invention is not particularly limited, but is preferably 0.4 g / cm 3 or less.
- the loose apparent density is a density value derived from the weight of talc contained in a volume of 100 cm 3 before measuring the vibration at the time of measuring the above-mentioned solid apparent density.
- the plate-like inorganic filler of the present invention is talc and the crystallite diameter of the (0 0 2) diffraction plane of talc by wide-angle X-ray diffraction is 600A or more. More preferably, the (0 0 2) diffraction plane has a crystallite size of 620 A or more, and more preferably 650 A or more.
- the (0 0 2) diffracting surface of talc here is a Tanorek Mg Si using a wide-angle X-ray diffractometer (specifically, RAD-RX type wide-angle X-ray diffractometer (manufactured by Rigaku Corporation)). O (OH) identified It can be confirmed that the distance between the layers coincides with about 9 ⁇ 39A, which is the lattice spacing by the (0 0 2) diffraction plane of talc. The crystallite diameter of the (0 0 2) diffraction plane of talc is calculated from the half-value width of the peak.
- the plate-like inorganic filler of the present invention may contain a surface treatment agent such as a silane coupling agent added for the purpose of improving the affinity with the resin.
- the amount is not limited, but is generally in the range not exceeding 5 parts by mass with respect to 100 parts by mass of the plate-like inorganic filler.
- the thermoplastic resin composition of the present invention preferably contains (E) a conductive material.
- the conductive material that can be used in the present invention is at least one selected from the group consisting of conductive carbon black and carbon fibrils.
- Examples of the conductive carbon black that can be used in the present invention include carbon black described as a conductive carbon black in WO01 / 081473. ⁇ Examples of commercially available conductive carbon blacks include Ketjen Black EC and Ketjen Black EC600JD, which are also available from Ketjen Black International. Examples of carbon fibrils that can be used in the present invention include fine carbon fibers described in International Publication No. WO 94/023433. Commercially available carbon fibrils include BN fibrils available from Hyperion Catalyst International.
- a preferred addition form of the conductive material used in the present invention is a master batch form premixed in one or more resins selected from polyphenylene ether, polyamide, and block copolymer. It is to add in.
- it is a method of adding in the form of a masterbatch premixed to polyamide.
- melt kneading using an extruder is most preferable.
- a co-rotating twin screw extruder having two or more supply ports set to 250 to 350 ° C, the resin is supplied from the upstream supply port, melted and kneaded, and then supplied downstream.
- the resin temperature is more preferably less than 340 ° C.
- a preferable blending amount of the conductive material in the master batch is 5 to 30% by mass. More preferably, it is 8 to: 15% by mass.
- the master batch may be a commercially available one.
- Commercially available master bag An example of H is Polyamide 66 / Carbon fibril masterbatch (trade name: Polyamide 66 with Fibril ⁇ ⁇ Nanotubes RMB4620-00: Carbon fibril content 20%) available from Hyperion Catalyst International.
- thermoplastic resin composition of the present invention is (A) a polyamide resin.
- the component (A) is 50 to 80 parts by mass and the component (B) is 20 to 50 parts by mass, for a total of 100 parts by mass, the component (C) is 5 to 30 parts by mass, (D) The component is 10-30 parts by mass.
- the preferred amount of added calories when (E) the conductive material is added to the thermoplastic resin composition of the present invention is 0.5 to 3 when all of the thermoplastic resin composition is 100% by mass. 0% by mass. More preferably, it is 1.0 to 2.0 mass%.
- a compatibilizer may be added to the thermoplastic resin composition of the present invention.
- the main purpose of using compatibilizers is to improve the physical properties of polyamide polyphenylene ether mixtures.
- the compatibilizing agent that can be used in the present invention refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. In any case, it is desirable that the polyamide-polyphenylene ether mixture obtained exhibits improved compatibility.
- compatibilizers that can be used in the thermoplastic resin composition of the present invention are described in detail in JP-A-8-48869 and JP-A-9-124926. All of these known compatibilizers can be used and can be used in combination. Among these various compatibilizers, examples of particularly suitable compatibilizers include maleic acid, maleic anhydride, and citrate. Of these, maleic anhydride is most preferred.
- compatibilizer that can be used in the present invention are polyamide and polyphenylene. It is 0.:! To 20 parts by mass, more preferably 0.:! To 10 parts by mass with respect to 100 parts by mass of the ether in total.
- thermoplastic resins such as polyester and polyolefin, flame retardants (halogenated resins, silicone flame retardants, magnesium hydroxide, aluminum hydroxide, organophosphate ester compounds, ammonium polyphosphate, red phosphorus, etc.), drops Fluoropolymers exhibiting prevention effects, plasticizers (oil, low molecular weight polyolefins, polyethylene glycols, fatty acid esters, montanic acid metal salts, etc.), flame retardant aids such as antimony trioxide, colorants, antistatic agents, various peroxidations Products, zinc oxide, zinc sulfide, antioxidants, phosphite antioxidants, ultraviolet absorbers, and light stabilizers.
- flame retardants halogenated resins, silicone flame retardants, magnesium hydroxide, aluminum hydroxide, organophosphate ester compounds, ammonium polyphosphate, red phosphorus, etc.
- drops Fluoropolymers exhibiting prevention effects
- plasticizers oil, low molecular weight polyolefins
- the specific addition amount of these components is in a range not exceeding 100 parts by mass in total with respect to 100 parts by mass in total of polyamide and polyphenylene ether.
- thermoplastic resin composition of the present invention is not particularly limited, but examples and examples thereof are listed below.
- the plate-like inorganic filler may be added in the form of a masterbatch.
- a method of adding in the form of a masterbatch previously mixed with polyamide may be mentioned.
- the melt kneading temperature is not particularly limited, but the conditions under which a suitable composition can be obtained can be arbitrarily selected from 240 to 360 ° C.
- the thermoplastic resin composition of the present invention has a surface impact strength of 6 J or more at 23 ° C, Menoletov mouth rate (according to ASTM D1238, measured at a load of 5 kg and a set temperature of 280 ° C) of 15 g / l 0 min or more. , And the linear expansion coefficient (measured as JIS K7197, with a heating rate of 5 ° C / min, a load of 10mN, and a temperature of -30 to 80 ° C) of 7.5 X 10_ 5 / ° C or less It is preferable that there is.
- thermoplastic resin composition of the present invention obtained as described above can be molded as molded parts of various parts by various conventionally known methods such as injection molding.
- IC tray materials chassis such as various disc players, electrical and electronic parts such as cabinets, OA parts and machine parts such as various computers and peripheral equipment, motorcycle cowls, and automobiles.
- Fender door 1 / ⁇ ° nenore, front panel nole, rear / ⁇ ° nenore, rocker ⁇ ° nenore, rear / kunno nenore, knocker garnish, emblem garnish, fuel inlet panel, Over fender, outer door hand nore, door mirror housing, bonnette air intake, bumper, bumper guard, roof rail, roof rail redder, pillar, biller bar, wheel cover, spoiler etc.
- Exterior parts such as malls and emblems It can be suitably used for interior parts such as instrument panels, console boxes and trims.
- PA Polyamide
- PPE Polyphenylene ether
- Poly (2,6-dimethyl-1,4_phenylene ether) (manufactured by Asahi Kasei Chemicals Corporation) Reduced viscosity: 0.42dl / g (0.5g / dl, black mouth form solution, 30 ° C measurement) (PPE-2) Maleic anhydride modified polyphenylene ether
- PPE-1 To 100 parts by mass, 0.1 parts by mass of radical initiator and 1.5 parts by mass of maleic anhydride were added and melt-kneaded at a cylinder temperature of 320 ° C using a twin screw extruder. Produced. The addition rate of maleic anhydride was 0.5%.
- SEBS— 1 Polystyrene monohydrogenated polybutadiene polystyrene
- Number average molecular weight of hydrogenated polybutadiene 167, 500
- Average particle diameter 8. 89 zm, median diameter: 8. 38 ⁇ m
- Average particle diameter 11 ⁇ 85 / im, median diameter: 10 ⁇ 68
- Average particle size 13. 62 ⁇ Median size: 12. 31 xm
- Average particle size 17. 67 zm, median diameter: 12.41 xm
- PA_ 2 polyamide 6, 6
- conductive carbon black Ketjen Black EC600—JD: manufactured by Ketjen Black International
- the obtained resin composition pellets were dried at 80 ° C. for 3 hours, and the amount of effluent per 10 minutes under the conditions of a temperature of 280 ° C. and a load of 5 kg was determined according to ASTM D1238.
- the obtained resin composition pellets were measured for a spiral flow (SFD) with a thickness of 2 mm using a FE120 molding machine manufactured by Nissei Plastic Industry Co., Ltd.
- the molding conditions were as follows: cylinder temperature: 300 ° C., mold temperature: 110 ° C., injection pressure: 118 MPa.
- the obtained resin composition pellets are dried at 80 ° C for 3 hours, and then injected with a Toshiba IS-80EPN molding machine (cylinder temperature 290 ° C, mold temperature set to 80 ° C), injection time 20 seconds, cooling time A plate test piece of 50 ⁇ 90 ⁇ 2.5 mm was prepared in 20 seconds, and the test was performed.
- a 10 x 4 x 2.5 mm test piece was cut out from the center of the flat plate, and in accordance with JIS K7197, TMA-7 (manufactured by Perkin Elma Co., Ltd.) was used, and the heating rate was 5 ° C / min.
- the obtained resin composition pellets were dried at 80 ° C for 3 hours, and then the IS IS 80EPN molding machine (cylinder temperature set to 280 ° C, mold temperature set to 80 ° C) was used as a dumbbell. Molded as described in 0294. Both ends of the test piece were broken to obtain a test piece having a uniform cross-sectional area of 10 X 4 mm, a length of 70 mm, and a fracture surface at both ends.
- the average particle size is 9 ⁇ m or more and 20 ⁇ m or less, and the ratio (d75% / d25%) of 25% particle size (d 25%) to 75% particle size (d75%) from the smallest particle size is By using a torque of 1 ⁇ 0 or more and 2 ⁇ 5 or less, it is possible to obtain a composition with improved balance between surface impact strength, tensile elongation and fluidity while maintaining excellent dimensional stability. all right.
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Abstract
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JP2015199959A (ja) * | 2014-04-08 | 2015-11-12 | エムス−パテント アクチエンゲゼルシャフト | 導電性ポリアミド成形材料 |
JP2016524021A (ja) * | 2013-07-03 | 2016-08-12 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | 導電性ポリアミド組成物および物品 |
WO2021080010A1 (ja) | 2019-10-24 | 2021-04-29 | 旭化成株式会社 | ポリアミド-セルロース樹脂組成物 |
JP7505276B2 (ja) | 2020-06-10 | 2024-06-25 | 三菱瓦斯化学株式会社 | 樹脂組成物の製造方法、組成物およびペレット |
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US20080152885A1 (en) * | 2004-11-25 | 2008-06-26 | Takaaki Miyoshi | Resin Composition Suitable For Sheet Formation |
WO2011085224A1 (en) | 2010-01-08 | 2011-07-14 | Abs Materials, Inc. | Modified sol-gel derived sorbent material and method for using same |
WO2011085235A1 (en) | 2010-01-08 | 2011-07-14 | Abs Materials, Inc. | Porous, swellable, sol-gel derived sensor material and method for using same |
WO2011100532A1 (en) | 2010-02-12 | 2011-08-18 | Abs Materials, Inc. | Sol-gel derived sorbent material containing a sorbate interactive material and method for using the same |
WO2011162836A1 (en) | 2010-02-17 | 2011-12-29 | Abs Materials, Inc | Method for extracting a metal particulate from an aqueous solution using a sol-gel derived sorbent |
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WO2011156663A1 (en) | 2010-06-10 | 2011-12-15 | Abs Materials,Inc | Method of treating a material using a sol-gel derived composition |
CN102229737B (zh) * | 2011-06-09 | 2013-01-16 | 孙国林 | 高阻断性有机电子器件用封装材料 |
CN103804883A (zh) * | 2012-11-15 | 2014-05-21 | 常熟市沈氏塑业有限公司 | 磷酸酯阻燃剂改性的聚苯醚材料的制备方法 |
KR102227119B1 (ko) * | 2018-09-28 | 2021-03-11 | 롯데첨단소재(주) | 폴리아미드/폴리페닐렌 에테르 수지 조성물 및 이를 이용한 성형품 |
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JP7505276B2 (ja) | 2020-06-10 | 2024-06-25 | 三菱瓦斯化学株式会社 | 樹脂組成物の製造方法、組成物およびペレット |
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JP4053075B2 (ja) | 2008-02-27 |
US7786206B2 (en) | 2010-08-31 |
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US20080146722A1 (en) | 2008-06-19 |
EP1840169A4 (en) | 2011-11-16 |
JPWO2006077818A1 (ja) | 2008-06-19 |
EP1840169A1 (en) | 2007-10-03 |
EP1840169B1 (en) | 2012-10-03 |
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