WO2006057254A1 - シート成形に適した樹脂組成物 - Google Patents
シート成形に適した樹脂組成物 Download PDFInfo
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- WO2006057254A1 WO2006057254A1 PCT/JP2005/021476 JP2005021476W WO2006057254A1 WO 2006057254 A1 WO2006057254 A1 WO 2006057254A1 JP 2005021476 W JP2005021476 W JP 2005021476W WO 2006057254 A1 WO2006057254 A1 WO 2006057254A1
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- polyamide
- resin composition
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- mixture
- relative viscosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7466—Combinations of similar mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/465—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using rollers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/10—Forming by pressure difference, e.g. vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
- B29K2071/12—PPO, i.e. polyphenylene oxide; PPE, i.e. polyphenylene ether
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0008—Anti-static agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0032—Pigments, colouring agents or opacifiyng agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0038—Plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0047—Agents changing thermal characteristics
- B29K2105/005—Heat sensitisers or absorbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/253—Preform
- B29K2105/256—Sheets, plates, blanks or films
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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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 realizes both of the contradictory properties of good sheet extrudability (significantly suppressing the occurrence of meshing in the die during sheet extrusion) and extremely excellent vacuum formability, and high impact.
- the present invention relates to a resin composition having strength.
- the present invention further relates to a molded body comprising the resin composition and a production method in which the resin temperature during processing of the composition is significantly suppressed. Background art
- Polyamide-polyphenylene ether alloy resin compositions have excellent fluidity and impact resistance, and are therefore polymer alloys used in a very wide range of applications. In other words, it is used not only for injection molding but also for extrusion molding as represented by sheet extrusion.
- melt viscosity is low! /
- pre-heating is performed.
- the phenomenon called “draw down” occurs excessively, causing problems such as the fact that vacuum forming cannot be performed, and wrinkles are generated on the formed piece.
- a sheet with a composition strength of normal melt viscosity is not appropriate.
- melt viscosity is lower and the processability is better, and in secondary processing such as vacuum forming, the higher the melt viscosity is, the better the processability is.
- the point of melt viscosity requires contradictory properties.
- polyamides having high relative viscosity have low terminal amino group concentrations (active terminal group concentrations required for reaction with polyphenylene ether), so polyamide and polyphenylene ether It can be estimated that the amount of the polyamide poly (phenylene ether) grafted product necessary for stabilizing the interface is insufficient.
- the composition itself has a high melt viscosity. For this reason, in the extrusion process for producing the resin pellets, the temperature of the resin during processing increases abnormally, the resin decomposes thermally, the strands coming out from the die of the extruder change color, There was also a problem of reducing the impact property. It is estimated that the pyrolysate generated at this time is not only a decrease in impact resistance, but also one of the factors that cause near the T-die during sheet extrusion! / The
- Patent Document 1 Japanese Patent Laid-Open No. 8-34917
- the present invention relates to a resin composition
- a resin composition comprising polyamide, polyphenylene ether, elastomer and an inorganic filler having a specific particle size. Further, by making the polyamide a mixture of two or more polyamides having different relative viscosities, the occurrence of meshing during extrusion processing, a reduction in impact resistance, and the suppression of drawdown during vacuum forming and the like are suppressed. To improve the impact strength and to suppress the discoloration of the strands and the generation of decomposition products. Is.
- the inventors of the present invention consisted of a polyamide mixture having a specific viscosity, a polyphenylene ether and an elastomer, and a polyamide having a high viscosity as the polyamide mixture.
- the inventors have found that the above-mentioned problems can be achieved by using a low-viscosity polyamide in a specific ratio or through a specific production method, and have reached the present invention.
- the present invention is a resin composition
- a resin composition comprising polyamide, polyphenylene ether, elastomer, and an inorganic filler having an average particle size of 0.05 m to lm, wherein the polyamide has two or more different relative viscosities.
- the relative viscosity of the polyamide mixture in which the amount of the polyamide having a higher relative viscosity is higher than the amount of the polyamide having a lower relative viscosity among the polyamides in the polyamide mixture is 3.3 to 5.0. It is related with the resin composition characterized by being.
- the present invention also relates to a sheet comprising the resin composition and a method for producing the resin composition.
- a resin composition having good sheet extrudability (significantly suppressing the occurrence of meshing in the die during sheet extrusion), high impact strength, and extremely excellent vacuum formability. It is possible to obtain a product, and a sheet and a molded body comprising the product.
- the present invention provides a production method capable of suppressing decomposition products during processing, and makes it possible to obtain a resin composition having higher impact resistance, which is extremely useful.
- the present invention is a resin composition
- a resin composition comprising a polyamide, a polyphenylene ether, an elastomer, and an inorganic filler having an average particle size of 0.05 m to lm, wherein the polyamide has a different relative viscosity.
- Two or more kinds of polyamide mixtures, and among the polyamides in the polyamide mixture, the relative viscosity of the polyamide mixture in which the amount of the polyamide having a higher relative viscosity is larger than the amount of the polyamide having a lower relative viscosity is 3.3 to 5
- the present invention relates to a resin composition characterized by being zero.
- the polyamide needs to be a mixture of two or more polyamides having different relative viscosities (7? R), and moreover, among all the polyamides in the resin composition, It is necessary that the amount of polyamide with high r? R is greater than the amount of polyamide with low r? R.
- the relative viscosity (7? R) in the present invention is a value measured according to JIS K6920-1: 2000. Specifically, polyamide was dissolved in 98% concentrated sulfuric acid at a concentration of lgZlOOcm 3 and the flow time measured at 25 ° C with an Ostwald viscometer was t. Let time be t
- R of the polyamide mixture needs to be in the range of 3.3 to 5.0. More preferably, it is 3.8 to 4.8, and most preferably 4.0 to 4.5.
- the ⁇ r of the polyamide mixture in the present invention represents the polyamide component contained in the composition. It is possible to know by the method of measuring separately.
- the blending ratio of the low ⁇ r polyamide and the high 7? R polyamide is such that among the polyamides in the polyamide mixture, the 7? R high polyamide amount is less than the 7? R low polyamide amount. There needs to be a lot.
- the specific power of the amount of the low polyamide of 7r to the amount of the high polyamide of 7r is in the range of 0.1 to 0.9, more preferably in the range of 0.2 to 0.7. is there.
- the definition of the low 7? R polyamide and the high 7? R polyamide in the polyamide mixture in the present invention is defined by the following formula depending on the r? R of each polyamide used and the mass part used. Sort by That is, based on the average ⁇ obtained by the following formula, a polyamide having an average ⁇ r or less is classified as a low r polyamide, and a polyamide exceeding the average 7 to r is classified as a 7 to r high polyamide. To do.
- the mass part W in the polyamide yarn composition is the mass part of all the polyamides used, and r? R is 2
- W of the second polyamide represents the mass part in the composition of the second polyamide
- 7? R is the 7? R of the nth polyamide and W is the quality of the nth polyamide in the molded product.
- a preferred 7? R of a polyamide having a high r? R is more than 3.5 and not more than 6.0. More preferably, it is in the range of 4.0 or more and 6.0 or less, and most preferably in the range of 4.0 or more and 5.0 or less. Further, the preferred 7? R of the polyamide having a low 7? R is in the range of 2.0 to 3.5. More preferred Alternatively, it is in the range of 2.0 to 3.0, and more preferably in the range of 2.5 to 3.0.
- melt-mixed polyamide such as a master batch obtained by melt-mixing two or more kinds of different 7? R polyamides.
- polyamide is not limited to the force obtained by ring-opening polymerization of ratatams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like.
- the above diamines are roughly classified into aliphatic, alicyclic and aromatic diamines, and specific examples thereof include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine and dodecamethylene.
- Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids, and specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1, 1, 3 tridecane-acid, 1,3 cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like.
- ratatams include ⁇ -force prolatatam, enantolactam, and ⁇ -laurolactam.
- aminocarboxylic acids include ⁇ -aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecane. An acid etc. are mentioned.
- these latatams, diamines, dicarboxylic acids, and ⁇ -aminocarboxylic acids can be used alone or as a mixture of at least two kinds of copolymerized polyamides obtained by polycondensation. Can be used.
- the polyamide resin that can be usefully used in the present invention includes polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, poly Amide, 6/66, Polyamide, 6/612, Polyamide, MXD (m—Xylylenediamine), 6, Positive Ami 6T, Polyamide, 61, Polyamide, 6 / 6T, Polyamide, 6/61, Polyamide, 6 ⁇ 6/6 ⁇ ⁇ , positive amide 6 ⁇ 6 ⁇ 6 ⁇ ⁇ , polyamide 6 ⁇ 6 ⁇ ⁇ 6 ⁇ ⁇ , polyamide 6'6 6 'Ding 76'1, polyamide 6/12 / 6 ⁇ Ding, Polya ⁇ 6 ⁇ 6/12/6 ⁇ Ding, Polya ⁇ 6/12/6 ⁇ ⁇ , Polya ⁇ 6 ⁇ 6/12 / 6-1, etc.
- Polyamides in which a plurality of polyamides are mixed with an extruder or the like can also be used.
- Preferred polyamide types are polyamide 6, polyamide 66 and polyamide 6 ⁇ 6 ⁇ 6.
- polyamide 6 is most preferable.
- the usable polyamide mixture is preferably a mixture of polyamides having different melting points. Specifically, it is desirable to be a polyamide mixture containing a low melting point polyamide having a melting point of 150 ° C. or more and less than 250 ° C. and a high melting point polyamide having a melting point of 250 ° C. or more and 350 ° C. or less.
- it is a polyamide mixture containing a low melting point polyamide having a melting point of 200 ° C or higher and lower than 250 ° C and a high melting point polyamide having a melting point of 250 ° C or higher and 300 ° C or lower.
- polyamides include, for example, polyamide 6, polyamide 11, polyamide 12 and the like as the low melting point polyamide having a melting point of 150 ° C or higher and lower than 250 ° C.
- high melting point polyamide having a melting point of C or less include polyamide 66, polyamide 46, polyamide 6T, and polyamide 9 ⁇ .
- the low melting point polyamide it is desirable to include at least polyamide 6, and as the high melting point polyamide, it is desirable to include at least polyamide 6, 6.
- melt-mixed polyamide such as a masterbatch obtained by melt-mixing two or more polyamides having different melting points.
- the melting point here can be measured with a differential scanning calorimeter (DSC). Specifically, after holding at 320 ° C for 5 minutes, the temperature is lowered to 40 ° C at a rate of 10 ° CZ and held for 5 minutes. Then, raise the temperature to 320 ° C in 10 ° CZ minutes, and measure the peak top temperature of the endothermic peak obtained. In the present invention, the temperature at the peak top of the endothermic peak is defined as the melting point. In these measurements, it becomes a raw material that is not measured with a polyamide mixture. Measured with respect to polyamide.
- DSC differential scanning calorimeter
- the weight ratio of polyamides having different melting points be a specific quantitative ratio.
- the amount of the high-melting polyamide having a melting point of 250 ° C. or higher and 350 ° C. or lower is in the range of 5% by mass to 18% by mass when the total of all polyamide mixtures is 100% by mass. More preferably, it is 6 mass%-14 mass%, Most preferably, it is 7 mass%-13 mass%.
- the amount of the high melting point polyamide having a melting point of 250 ° C or higher and 300 ° C or lower is 5% by mass or more. This makes it easier to suppress the phenomenon that the amount of drawdown during preheating increases.
- the amount of high-melting polyamide having a melting point of 250 ° C or higher and 300 ° C or lower is suppressed to 18% by mass or lower. I hope that. Specifically, the possibility of adversely affecting the sheet appearance is reduced.
- any combination of two or more types of polyamides having different melting points and polyamides having different ⁇ r capable of forming a polyamide mixture may be used.
- a polyamide having a high 7? R is a high melting point polyamide having a melting point of 250 ° C or higher and 300 ° C or lower, it has a low melting point of 150 ° C or higher and lower than 250 ° C. It may be a melting point polyamide.
- a high 7? R polyamide is a low melting point polyamide having a melting point of 200 ° C or more and less than 250 ° C, and a low 7? R polyamide is a high melting point polyamide having a melting point of 250 ° C or more and 300 ° C or less. In the case of a polyamide mixture, the effect can be maximized.
- the most preferred embodiment of the polyamide mixture constituting the thermoplastic resin composition of the present invention has a melting point of 200 ° C or higher and lower than 250 ° C and a relative viscosity of 3.5 or higher and 6.0.
- the polyamide mixture is a polyamide mixture in which the amount of the high melting point polyamide in the polyamide mixture is 5% by mass to 15% by mass, and the relative viscosity of the polyamide mixture is in the range of 3.3 to 5.0. It is.
- the concentration of the end groups of the polyamide is involved in the reaction between the polyamide and the functionalized polyphenylene ether.
- Polyamide rosin generally has amino and carboxyl groups as end groups. The In general, when the carboxyl group concentration is high, the impact resistance is lowered and the fluidity is improved. Conversely, when the amino group concentration is high, the impact resistance is improved and the fluidity is lowered.
- an amino group Z carboxyl group concentration ratio within the range of 1.0 to 0.1 can be preferably used.
- a more preferred amino group Z carboxyl group concentration ratio is 0.8.
- the concentration ratio of the amino group of the polyamide and the carboxyl group of the polyamide does not substantially exceed 1.0.
- the amino group Z carboxyl group concentration ratio is desirably 0.1 or more.
- the end group concentration of the polyamide mixture in the present invention is desirably the end group concentration within the above-mentioned range as a mixture. Furthermore, the end group concentration ratio of all the polyamides used is within the above-mentioned range. It is preferable to be within.
- a metal stabilizer as described in JP-A-1-163262 which is known for the purpose of improving the heat resistance stability of polyamide resin, It can be used without problems.
- metal stabilizers those that can be particularly preferably used include Cul, CuCl, copper acetate, cerium stearate, and the like.
- Alkali metal halide salts such as um can also be suitably used. Of course, these may be added together.
- the preferred amount of the metal stabilizer and / or alkali metal halide salt is U, and the total amount is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyamide resin.
- the polyphenylene ether that can be used in the present invention is a homopolymer, Z, or copolymer that also has the structural unit force of formula (1).
- O is an oxygen atom
- R is independently hydrogen, halogen, primary or secondary lower alkyl, phenol, haloalkyl, aminoalkyl, hydrocarbonoxy, or Represents a halohydrocarbonoxy (provided that at least two carbon atoms separate the halogen and oxygen atoms).
- polyphenylene ether of the present invention examples include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2,6-dimethyl-1,4-phenylene ether).
- a copolymer with 2, 3, 6 trimethylphenol or a copolymer with 2-methyl-6-butylphenol as described in JP-B-52-17880 also included are -len ether copolymers.
- polyphenylene ethers are poly (2,6 dimethyl-1,4 phenylene ether), a copolymer of 2,6 dimethylphenol and 2,3,6 trimethylphenol. It is a polymer or a mixture thereof.
- the method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method.
- US Pat. 3306875, 3257357 and 3257358, JP-A-50-51197, JP-B 52-17880, 63-152628, etc. Is mentioned.
- the reduced viscosity (7? Sp / c: 0.5 g Zdl, Klo-form solution, measured at 30 ° C) of the polyphenylene ether that can be used in the present invention is 0.15 to 0.70 dlZg.
- the range is preferably, more preferably in the range of 0.20 to 0.60 dlZg, and still more preferably in the range of 0.40 to 0.55 dl / g.
- modified polyphenylene ether refers to at least one carbon-carbon-heavy bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group in the molecular structure. Or a polyphenylene ether modified with at least one modified compound having a glycidyl group. All modified polyphenylene ethers described in WO02Z094936 can be used.
- the amount ratio of the modified polyphenylene ether in the mixed polyphenylene ether in this case is not particularly limited, but is preferably 10 to 95% by mass (100% of all the polyphenylene ethers). and a the case), more preferably 30 to 90 weight 0/0, most preferably from 45 to 85 wt%.
- the styrene-based 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 of polyamide and polyphenylene ether.
- the styrene-based thermoplastic resin means homopolystyrene, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer.
- HIPS rubber-modified polystyrene
- AS resin styrene-acrylonitrile copolymer
- styrene-rubber polymer-acrylonitrile copolymer examples include coalescence (ABS oil).
- a known organic stabilizer can be used without any problems in addition to the metal stabilizer detailed as the stabilizer for the polyamide.
- Organic stabilizers include hindered phenolic acid / antioxidant typified by Ilganox 1098, phosphorus-based processing heat stabilizers typified by Ilgaphos 168, and rataton-based processing typified by HP-136.
- Heat stabilizer, heat-resistant stabilizer, hinder Examples thereof include a dodamine light stabilizer.
- a hindered phenolic acid oxidizer, a phosphorus processing heat stabilizer, or a combination thereof is more preferable.
- a preferable blending amount of these organic stabilizers is 0.001 to 10 parts by mass with respect to 100 parts by mass of the total of polyamide and polyphenylene ether. More preferably, it is 0.1 to 2 parts by mass.
- the elastomer that can be used in the present invention is not particularly limited, but it is preferable to use at least one polymer block mainly composed of an aromatic vinyl compound and at least one conjugated gene. It is a block copolymer (hereinafter simply abbreviated as a block copolymer) having a polymer blocking force mainly composed of a compound.
- “mainly” in a polymer block mainly composed of an aromatic beryl compound is a block in which at least 50% by mass of the block is an aromatic vinyl compound. Point to lock. 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 same applies to “mainly” in a polymer block mainly composed of a conjugated genie compound, and refers to a block in which at least 50% by mass or more is a conjugated genie compound. More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.
- aromatic bur compound examples include styrene, a-methylstyrene, vinyl toluene, and the like.
- styrene is particularly preferable among the forces in which one or more selected compounds are used.
- conjugation compound examples include butadiene, isoprene, piperylene, 1,3-pentagene, and the like.
- One or more compounds selected from these forces are used, and among them, butadiene, isoprene, and these compounds. A combination is preferred! /.
- a polymer block (a) mainly composed of an aromatic vinyl compound and a polymer block (b) mainly composed of a conjugated diene compound are ab type, ab — Type a And a—b—a—b block copolymer having a bonding type selected from the following types. Of course, these may be a mixture.
- the a-b-a type, the a-b-a-b type are more preferable, and the a-b-a type is most preferable.
- the preferred mixing form of the block copolymer mixture having different bonding types is a-b—a type block copolymer and a—b type block copolymer, a—b—a type and a— Examples thereof include a mixture of b—a—b type block copolymer and a mixture of a—b—a—b type and a—b type block copolymer.
- the block copolymer that can be used in the present invention is more preferably a hydrogenated block copolymer.
- a hydrogenated block copolymer is mainly composed of a conjugated genie compound by subjecting the block copolymer of the aromatic aromatic compound and the conjugated genie compound to a hydrogenation treatment.
- the amount of the aliphatic double bond in the polymer block (that is, the hydrogenation rate) is controlled in the range of more than 0 to 100%.
- the hydrogenation rate of the hydrogenated block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more.
- block copolymers can be used as a mixture of the block copolymer and the hydrogenated block copolymer without any problem after being hydrogenated.
- the respective ratios of polyamide, polyphenylene ether and elastomer are 30 to 60 parts by mass of polyamide and 30 to 60 parts of polyamide ether when the total of these three components is 100 parts by mass.
- the mass and elastomer range from 5 to 30 parts by mass. More preferably, it is in the range of 35 to 60 parts by weight of polyamide, 35 to 60 parts by weight of polyphenylene ether and 5 to 20 parts by weight of elastomer, and most preferably 40 to 60 parts by weight of polyamide and 40 to 40 parts of polyurethane. The range is ⁇ 60 parts by mass and the elastomer is 5 to 20 parts by mass.
- an inorganic filler having an average particle size of 0.05 ⁇ m to l ⁇ m is added. It is essential to do.
- the main purpose of adding the fine inorganic filler in the present invention is to improve the melt viscosity of the resin composition rather than to improve the mechanical properties.
- the type of inorganic filler includes an inorganic filler that is at least one of an oxide or a sulfate of a metal selected from titanium, iron, copper, zinc, aluminum, and silicon. It is done. More specifically, the inorganic filler is at least one selected from the group consisting of titanium oxide, titanium oxide, silica, alumina, zinc oxide and zinc sulfate.
- titanium dioxide and zinc oxide preferred are titanium dioxide and zinc oxide, and most preferred is titanium oxide.
- -Titanium oxide may be a treated titanium oxide / silicone compound and / or polysiloxane surface-treated.
- the content as titanium dioxide is in the range of 90 to 99% by mass, and more preferably in the range of 93 to 98% by mass.
- the surface treatment agent is not included as the amount of titanium dioxide.
- the average particle size of the inorganic filler needs to be in the range of 0.05 m to l m.
- the average particle diameter exceeds 1 ⁇ m, the effect of improving the melt viscosity of the resin composition is reduced and the appearance of the sheet is liable to deteriorate.
- the average particle diameter in the present invention is a measured value obtained by a centrifugal sedimentation method, and refers to a weight median diameter.
- the solvent in which the inorganic filler is dispersed is a force that should be appropriately selected according to the type of the inorganic filler. For example, in the case of titanium oxide, a sodium hexametaphosphate solution is used.
- the preferred amount of the inorganic filler added is desirably an amount sufficient to increase the melt viscosity of the resin composition.
- Melt viscosity is a characteristic required when vacuum forming a sheet or the like, for example. Unlike injection molding, a melt having a relatively high melt viscosity tends to be excellent in vacuum moldability. That is, when used for applications such as vacuum forming, a higher melt viscosity is preferred.
- the melt viscosity of the resin composition is, for example, a melt viscosity measured at a temperature equal to or higher than the melting point of the resin composition with a shear flow rate of 30 (sec. ⁇ ] Refers to that.
- An increase in melt viscosity is the [7?] Of a resin composition containing no inorganic filler.
- the amount of the inorganic filler added is not particularly limited as long as it is an amount sufficient to increase the melt viscosity of the resin composition. It is desirable that the amount be in the range of about 1 to about 20 parts by mass with respect to 100 parts by mass of the total of lyamide, polyphenylene ether and elastomer. More preferably, it is 1.5-15 mass parts, More preferably, it is 2-10 mass parts, Most preferably, it is 3-6 mass parts. In order to show the effect of improving the melt viscosity, an addition amount of at least about 1 part by mass is desired, and an addition amount of about 20 parts by mass or less is desirable in order to maintain the desired impact characteristics.
- a compatibilizing agent may be used.
- the compatibilizer that can be used in the present invention is not particularly limited as long as it improves the physical properties of the polyamide-polyphenylene ether mixture.
- the compatibilizing agent that can be used in the present invention refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. This interaction can be chemical (eg, grafting) or physical (eg, changing the surface properties of the dispersed phase)! /.
- the polyamide polyphenylene ether mixture obtained in any case exhibits improved compatibility.
- compatibilizers that can be used in the present invention are described in detail in JP-A-8-8869 and JP-A-9-124926. All of these known compatibilizers can be used and can be used in combination.
- compatibilizing agents examples include maleic acid or a derivative thereof, cuenic acid or a derivative thereof, fumaric acid or a derivative thereof, and the like. And modified polyphenylene ether pellets.
- a preferred amount of the compatibilizing agent in the present invention is 0.01 to 25 parts by mass with respect to 100 parts by mass of a mixture of polyamide and polyphenylene ether. More preferably, 0.05 force is 10 parts by mass, and most preferably is 0.1 to 5 parts by mass.
- a conductive carbon-based filler may be further included.
- a conductive carbon filler usable in the present invention is a conductive carbon black.
- conductive carbon black include Ketjen Black (EC, EC-600JD) available from Ketjen Black International.
- Examples of carbon nanotubes include carbon fibrils (BN fibrils) available from Hyperion Catalysis International. Of the carbon fibrils, carbon fibrils as disclosed in International Publication No. W094Z23433 are particularly preferable.
- the method for adding these conductive carbon-based fillers is not particularly limited, but a method in which the conductive carbon-based fillers are preferentially added in the form of a masterbatch blended in polyamide is preferable.
- the polyamide masterbatch 100% by mass
- the conductive carbon-based filler is conductive carbon black
- the amount is preferably 10-30% by mass. More preferably, when the conductive carbon-based filler is conductive carbon black, the amount is 7 to 12% by mass.
- the conductive carbon-based filler is another conductive carbon-based filler, the amount is S15 to 25% by mass. is there.
- a conductive carbon black is previously uniformly distributed in the polyamide.
- Dispersed masterbatch, or masterbatch in which conductive carbon black is moderately and non-uniformly dispersed in polyamide as described in International Patent Application JP03Z9104 filed by the present applicant, or Hyperion ⁇ the turbocharger data list International, Inc. force is also available polyamide 66Z carbon fibril master batch (trade name: Poly am ide66 with fibril TM Nanotubes RMB4620- 00: carbon fibrils of 20%) Ru carbon fibril master batch, and the like, such as.
- the master batch in which the conductive carbon black is moderately non-uniformly dispersed in the polyamide is most preferred.
- a master batch is preferred. More preferably, continuous using an optical microscope When the surface of 3 mm 2 is observed, this is a master batch in which there are 2 to 30 aggregated particles of conductive conductive carbon black having a major axis of 20 to LOO / zm.
- the master notch pellet is cut into a mirror surface with a microtome equipped with a glass knife. Then, the cut surface is observed with reflected light at a magnification of 50 times using an optical microscope (PME3: Olympus) and photographed. It is possible to visually count the number of conductive carbon black aggregated particles having a major axis of 20 / zm or more and 100 ⁇ m or less present in an area of 3 mm 2 .
- the shape of the master pellet is usually cylindrical, so cut it into a cross section almost perpendicular to the long side and observe it, and cut out at least three cross sections from separate pellets. Observe and use the average value as the number of aggregated particles.
- a twin-screw extruder having one supply port on the upstream side and one or more supply ports on the downstream side is used.
- a manufacturing method in which a conductive carbon-based filler is added and melt-kneaded from the downstream side, a part of the polyamide and the conductive carbon-based filler are supplied from the upstream side, and the remaining polyamide is supplied from the downstream side.
- the production method include addition and melt-kneading, and production method in which a part of the polyamide is supplied from the upstream side, and the conductive carbon-based filler and the remaining polyamide are added from the downstream side and melt-kneaded.
- the production method is preferred in which a part of the polyamide is supplied from the upstream side, and the conductive carbon-based filler and the remaining polyamide are added from the downstream side and melt kneaded.
- the amount of carbon is 0.5 to 4 parts by mass when the total amount of polyamide, polyphenylene ether and elastomer is 100 parts by mass. More preferably, it is 1-3 mass parts.
- additional components may be added as necessary within a range not impairing the effects of the present components.
- the amount of these additional components added is Desirably, the range should not exceed 15 parts by mass, when the total amount of polyamide, polyphenylene ether, elastomer and inorganic filler is 100 parts by mass.
- attached components include other thermoplastic resins such as polyester and polyolefin, other inorganic fillers (talc, kaolin, zonotlite, wollastonite, potassium titanate, glass fiber, etc.), inorganic Known silane coupling agents and flame retardants to increase the affinity between fillers and resins (halogenated resins, silicone-based flame retardants, magnesium hydroxide, aluminum hydroxide, aluminum phosphates, organic phosphate compounds , Polyphosphate ammonium, red phosphorus, etc.), fluorine-based polymers showing anti-dripping effect, plasticizers (oil, low molecular weight polyolefin, polyethylene glycol, fatty acid esters, etc.) and antimony trioxide Colorants such as carbon black for coloring flame retardant aids, antistatic agents, various peroxides, antioxidants, UV absorbers, light stabilizers, and the like.
- thermoplastic resins such as polyester and polyolefin
- other inorganic fillers talc, kaolin,
- thermoplastic resin composition of the present invention desirably has a large difference in melt viscosity depending on temperature.
- the ratio of the melt viscosity at 240 ° C to the melt viscosity at 280 ° C is preferably not less than 10.0, more preferably not less than 20.0 and less than 50.0. Is desirable. By setting the melt viscosity ratio to 10.0 or more, both the extrudability during sheet processing and the vacuum formability can be improved.
- the melt viscosity at 280 ° C is preferably 1 X 10 3 Pa 'sec or more and 1 X 10 4 Pa' sec or less.
- the melt viscosity at 240 ° C is l X 10 4 Pa 'seconds or more and less than 1 X 10 7 Pa' seconds is more desirable, and more preferably 1 X 10 5 Pa 'seconds or more and 1 X 10 6 Pa' seconds or less.
- melt viscosity at 280 ° C and the melt viscosity at 240 ° C are measured differently.
- the melt viscosity at 280 ° C in the present invention is a rotational viscometer rheometer [RDA
- the melt viscosity at 240 ° C in the present invention is a condition in conformity with ISO 1133 using a capillary flow tester [Capillograph 1C: manufactured by Toyo Seiki (Japan) Co., Ltd.] The value of the melt viscosity at an apparent shear rate of 15 seconds— 1 measured at the cylinder temperature of It is.
- the cylinder temperature should be set between 238 ° C and 242 ° C.
- the preheating time (time from filling the cylinder into the cylinder and starting the measurement) can be appropriately selected within 4 to 8 minutes.
- the sample to be measured should be a sample whose moisture content is controlled to about 200 to about 100 ppm. More preferably, it should be measured with a sample controlled to about 300-700 ppm. In particular, when a sample with a water content exceeding lOOOppm is used, its melt viscosity may be measured low.
- Specific processing machines for obtaining the resin composition of the present invention include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, and the like. .
- the twin screw extruder is particularly preferred, and the twin screw extruder having the upstream supply port and one or more downstream supply ports is most preferred.
- the production includes the following steps It is desirable to take a method.
- First step A step in which at least a polyphenylene ether and an elastomer are melt-kneaded to produce a first premix.
- Second step A step of producing a second premix by melt-kneading at least the first premix, a polyamide having a low relative viscosity, and if necessary an inorganic filler.
- Third step a step of melt-kneading at least the second premix, a polyamide having a high relative viscosity, and, if necessary, an inorganic filler.
- the above-described first, second and third steps are continuously carried out in one twin-screw extruder.
- the inorganic filler is more preferably added in the third step from the viewpoint of suppressing the resin temperature.
- the screw diameter of the extruder at this time is not particularly limited, but is preferably about 20 mm or more and about 200 mm or less. More preferably, it is about 40 mm or more and about 125 mm or less. Also preferred is about 50 mm or more and less than about 100 mm.
- the LZD of the extruder is preferably about 30 or more and less than about 60, more preferably about 30 or more and less than about 60, more preferably about 40 or more and less than about 60.
- LZD is the value obtained by dividing the extruder screw length [L] by the screw diameter [D].
- the position of the downstream supply port in the extruder is preferably the following position.
- the first downstream supply port is a position within the range of about 30 to about 60 starting from the position of the upstream supply port of the extruder.
- the second downstream supply port is downstream from the first downstream supply port, and at a position within the range of about 50 to about 80 when the cylinder length of the extruder is 100. is there.
- the melt kneading temperature is not particularly limited, but the conditions under which a suitable composition can be obtained can be arbitrarily selected from about 260 to about 340 ° C. Preferably within the range of about 270 ° C. to about 3 30 ° C., particularly from about 300 ° C. to about 330 ° C. from the upstream supply port to the first downstream supply port, the first downstream supply It is desirable that the distance from the mouth to the front of the die is within a range of about 270 to about 300 ° C. The temperature of the die should be within the range of 300 ° C to 330 ° C, and the temperature difference from the desired resin temperature should be within 15 ° C.
- the temperature may be set slightly higher than the set temperature.
- the cylinder set temperature is a reference value, and it is preferable to manage the temperature at the resin temperature rather than the cylinder set temperature.
- the resin temperature at the time of extrusion of the composition is affected by factors such as the cylinder set temperature 'screw rotation speed', the amount of resin supplied, the screw design, and the like.
- the preferred resin temperature is in the range of 300 to 340 ° C, more preferably 320 to 335 ° C.
- the resin temperature is a temperature obtained by actually measuring the temperature of the molten resin extruded from the die nozzle cover with a thermometer such as a contact-type thermocouple during the extrusion process.
- the method includes a first step of melt-kneading at least polyphenylene ether and an elastomer to produce a first premix, and a second step of melt-kneading at least the first premix and polyamide.
- the screw configuration of the extruder in the second step has at least one kneading block, the kneading block is composed of a plurality of screw elements, and the LZD of the kneading block is 1.0 to 3. It is very important to be within the range of 0. (Here, L represents the length of the screw constituting the kneading block in the screw axial direction, and D represents the diameter of the screw constituting the kneading block.)
- the kneading block length is less than 1.0, problems during extrusion such as surging are likely to occur.
- this LZD exceeds 3.0, for example, when processing a high-viscosity resin, the resin temperature during processing becomes very high (for example, a temperature exceeding 350 ° C), Decomposition of the cocoon occurs, which causes discoloration of the strands.
- Kneading block refers to a block called a kneading disk having a high kneading effect and having a plurality of continuous screw elements.
- the kneading block is configured-there is no particular limitation on one ding disk part, but clock wise knee disk (feed type: R type-one ding disk: R—KD), anti-clock wise one ding A disc (reverse feed: L type-one ding disc: L—KD), neutral kneeling disc (non-conveying type: N type—one ding disc: N—KD), etc. can be selected as appropriate.
- the number of needing blades in each screw element can be selected from 1 to 10 per part. More preferably, 3 to 7 screw elements are used.
- Examples of the arrangement of these singing disk parts in the kneading block include, for example, a combination of a plurality of R-KDs (RR combination), and a plurality of N-KDs connected in series.
- Consecutive combination One or more R—KD and one or more N—KD consecutive combinations (RN combination), One or more R—KD and L KD consecutive Combination (RL combination), one or more N-KD and L-KD consecutive combinations (NL combination), one or more R-KD and one or more N-KD and L KD Consecutive combinations (RNL combinations) and the like.
- At least one screw element having a sealing ability is included in a plurality of screw elements constituting the kneading block.
- L-KD and N-KD are examples of parts that can be preferably used as the screw element having sealing ability, and L-KD is particularly useful.
- the LZD of one part is more preferably 0.8 or less.
- Specifically preferred combinations are one or more consecutive R—KD and LKD combinations (RL combination), and one or more consecutive N—KD and LKD combinations (NL).
- the most preferable combination is a continuous combination of two R—KDs and one LKD.
- LZD in the claims of the present invention means the length (L) in the screw axial direction of the screw constituting the kneading block by the diameter (D) of the screw constituting the kneading block. Divided. For example, in the case of a screw with a screw diameter force of Omm, the screw uniaxial length R-KD is 36 mm, the screw axial length R-KD is 18 mm, and the screw axial length L is 18 mm.
- the LZD of a kneading block consisting of three KD discs is 1.8.
- kneading blocks having an LZD of 1.0 to 3.0 as described above, and at least a conveying block having an LZD of 2.0 or more between each kneading block.
- the state is separated. More preferably, the kneading blocks are separated by a conveying block having at least LZD of 4.0 or more.
- the transport block here is basically composed of a feed-type screw element.
- D does not have a kneading block with 1.0 or more! /, Indicates a block.
- the total LZD of the plurality of kneading blocks in the step of melt-mixing the polyphenylene ether and the polyamide is more preferably in the range of 3.0 to 6.0. More desirably, it is within the range of 3.0 to 5.0.
- the screw configuration in the step of melting the polyphenylene ether also has a specific kneading block as in the step of melting and mixing the polyphenylene ether and the polyamide.
- the kneading block is composed of a plurality of screw elements, and its length (LZD) is 1.0 to 8. It is preferable to be within the range of 0. More preferably, it is in the range of 1.5 to 6.0, and most preferably in the range of 2.0 to 4.0.
- LZD of the kneading block it is desirable to set to 1.0 or more. Is preferably 8.0 or less.
- preferable conditions regarding the extrusion discharge amount, the screw rotation speed, and the like include an operating condition parameter P value force of 0.20 to 0.40 [kg-cm 3 ] represented by the following formula: It is desirable to manufacture under such conditions. More preferably, it is in the range of 5 ⁇ 10 _5 to 5 ⁇ 10 _4 [kg ′ cm 3 ].
- the extrusion discharge of the extruder is performed so that the discharge amount per unit opening area-unit time of the die hole represented by the following formula is 100 kgZcm 2 to 300 kgZcm 2. It is necessary to select an appropriate die and an extruder discharge amount corresponding to the amount.
- O (hole) is the die hole unit opening area ⁇ discharge rate per unit time [kg / hr'cm 2 ]
- O (total) is the total discharge rate of the extruder [kgZhr]
- N ( die) is the number of die holes in the extruder [pieces]
- r is the die hole radius [cm]
- ⁇ is the circumference.
- the discharge rate per unit opening area of the die hole should be lOOkgZhr'cm 2 or more. discharge amount is desirably not exceed 300kgZhr 'cm 2. More preferably, the discharge amount per unit opening area of the die hole is 120 kg / hr ⁇ cm 2 to 280 kgZhr ⁇ cm 2 , and most preferably 150 kg / hr ⁇ cm 2 to 250 kg / hr′cm.
- the resin composition obtainable from the production method of the present invention can be used for secondary forces such as injection molding, extrusion molding, blow molding and inflation molding. Among these, it is particularly suitable for injection molding and extrusion molding, and is most suitable for extrusion molding.
- extrusion molding it is particularly suitable for sheet extrusion and film extrusion.
- a single-screw extruder or a twin-screw extruder that is not particularly limited to the extruder used for sheet extrusion and film extrusion may be used. It is also suitable for multi-layer laminate film extrusion of 2 to 7 layers using multiple extruders.
- the cylinder set temperature in the extrusion molding is not particularly problematic as long as it is higher than the melting temperature of the resin, but specifically, it is in the range of 250 ° C to 320 ° C. More preferably, the temperature is sufficient for the polyamide to have a suitable melt viscosity such as sheet extrusion within a range of 250 ° C. to 300 ° C. In order to maintain productivity, it is desirable to extrude at a set temperature of 250 ° C or higher. It is desirable to extrude at a set temperature of 320 ° C or less in order to suppress the appearance of films and sheets.
- the melted resin temperature at the time of sheet extrusion molding be a temperature of 270 ° C or higher and 320 ° C or lower. More preferably, it is 280 ° C or more and 310 ° C or less, and most preferably 280 ° C or more and 300 ° C or less.
- the temperature of melted resin is T Die force The temperature of the molten resin measured by a thermometer such as a contact thermocouple.
- the sheet sheet has a thickness of 50 ⁇ m to 3 mm. More preferably, it is 100 ⁇ m to 1 mm, more preferably 100 ⁇ m to 700 ⁇ m, and most preferably 200 to 500 ⁇ m.
- the width of the sheet or film is not particularly limited.
- the resin composition of the present invention is particularly suitable for wide sheet applications having a width greater than 60 cm. Particularly suitable for very large sheets of more than 80cm and less than 200cm.
- Film sheets prepared from the thermoplastic resin composition of the present invention can be cast into various shapes by vacuum forming, pressure forming, press forming and the like.
- the temperature setting at this time is not particularly limited, but it is desirable that the temperature of the resin during processing is 200 ° C or higher and lower than 280 ° C. More preferably, it is within the range of 220 ° C to 250 ° C.
- downstream first supply port was closed, and the downstream second supply port was used as the downstream supply port.
- the following raw materials were supplied from the upstream and downstream supply ports in the proportions shown in Table 1, respectively.
- PPE Polyphenylene ether
- SEBS elastomer
- MAH compatibilizer
- PA6c Sodium hexoxametaphosphate-rutile diacid titanium with a weight median diameter of 240nm measured by centrifugal sedimentation method with 0.020gZcm 3 concentration in an aqueous solution of 0.05% by weight of sodium hexoxametaphosphate] (hereinafter, simply referred to as filler 1) and and at 0. 02gZcm 3 concentrations in Kisakisametarin sodium 0.05 wt% aqueous solution to talc [as an inorganic filler dispersed talc, far Talc wt media Ann diameter measured by sedimentation method 3. is 2 m] (hereinafter, simply filler 2 hereinafter)
- the mixture was melt-kneaded, and the strand was cooled with water and pelletized.
- the screw rotation speed during melt-kneading was 300 rpm and the amount of supplied grease was 45 kg / h. Vacuum suction was performed to remove volatile components from the 5th and 10th barrels.
- a piece and a 150 mm XI 50 mm X 2 mm flat plate-shaped formed piece were formed and allowed to stand at 23 ° C for 48 hours in an aluminum moisture-proof bag.
- AAA Even after 30 minutes from the start of sheet extrusion, the occurrence of eye damage is not confirmed. AA: After 20 to 30 minutes from the start of sheet extrusion, occurrence of eye damage is observed. A: After 10 to 20 minutes from the start of sheet extrusion, occurrence of eye damage is observed. B: Immediately after the start of sheet extrusion, the occurrence of meshing is observed.
- Example 1 When the molten resin temperature in the T-die part during this sheet extrusion process was measured using a contact-type thermocouple, the molten resin temperature of Example 1 was 298 ° C, and Example 3 was 333 ° C. It showed the same tendency as the trend of melted resin temperature in the process of manufacturing the resin pellets.
- the die part was scraped to remove the eyes, and then the rotational speed of the take-up roller was adjusted to obtain a sheet having a thickness of about 0.4 mm and a length of about 300 mm.
- the width of the sheet at this time was about 140 to 145 mm.
- the obtained sheet was cut into a length of 200 mm and actually formed with a vacuum forming machine.
- the mold of the vacuum forming machine consists of a 70 mm wide, 80 mm long, 30 mm deep square cup-shaped molded piece and a 70 mm wide, 80 mm long, 35 mm deep square force-shaped molded piece. It is a mold that can be molded, and the heat projection area of the sheet is 240 cm 2 (200 mm x 120 mm).
- Fig. 1 shows a schematic view of a cup-shaped vacuum formed piece.
- Wrinkles Wrinkles occur in molded products.
- FIG. 2 shows a schematic diagram explaining the drawdown.
- Example 1 Example 1
- Example 3 Comparative Example
- the 7r of the polyamide is almost the same. There is a clear difference. Further, the temperature of the resin at the time of extrusion is different by about 30 ° C., and it can be seen that the composition of the present invention is excellent in productivity and physical properties.
- Example 1 Comparative Example
- Example 2 Comparative Example
- Example 4 is a modification of the inorganic filler. [Examples 5-7 (Invention), Examples 9-12 (Invention) and Example 8 (Comparative Example)]
- the extruder was set in the same manner except that the downstream second supply port of the same extruder as Example 1 was closed and the downstream first supply port was changed to the downstream supply port.
- the following raw materials were supplied from the upstream and downstream supply ports in the proportions shown in Table 2.
- the mixture was melt-kneaded, and the strand was cooled with water and pelletized.
- the screw speed during melt-kneading was 300 rpm and the amount of supplied grease was 45 kgZh. Vacuum suction was performed to remove volatile components from the 5th and 10th barrels.
- Example 2 the obtained pellets were subjected to sheet extrusion in the same manner as in Example 1, and according to the same evaluation criteria, the state of formation of the eyes near the die was confirmed, and the obtained sheets were used. Then, vacuum formability and drawdown were evaluated. The results are listed in Table 2. In Examples 10 and 11, 24 The melt viscosity at o ° c was a force that could not be measured because a load exceeding the measurement limit of the Kabilary Flow Tester was applied.
- Example 5 when the molten resin temperature in the T-die part during sheet extrusion was measured using a contact-type thermocouple, the molten resin temperature of Example 5 was 294 ° C. In Example 8, it was 332 ° C.
- PA6b 25 30 30 30 30 30 30 30 30 30 30 30 Polyamide average ⁇ ⁇ 3.91 4.05 4.03 4.88 4-04 4.03 Izod strength 72 79 80 58 68 32 Melt viscosity (2403 ⁇ 4) p a .s 199500 174S00 31820 94000 35000 Unmeasureable viscosity (2803 ⁇ 4) Pa-second 6540 5680 2670 7700 2700 6300 Strain occurrence-AAA AA AA B AA A Draw-down property mm 4.1 5.0 22 4.2 20 3.9 Vacuum formability Good Good Good Good Good Good Good Good Good-Holes No presence of cracks None None None None None ⁇
- Example 6 and 7 which are the thermoplastic resin compositions of the present invention, can be produced by adding a small amount of high-melting polyamide. The fact that the draw-down performance without deteriorating the second occurrence has been greatly improved, and the vacuum formability has been significantly improved.
- ZSK40S C [made by Coperion (Germany)] with 48 LZDs, which has one supply port on the upstream side and two supply ports on the downstream side, was used.
- the number of barrels is 12 barrels (LZ D per barrel is 4) force, upstream supply port: 1st barrel, 1st downstream supply port: 6th barrel, 2nd downstream supply port: 8th barrel, decompression Vent ports for removing volatile components by suction: installed in the 5th and 10th barrels, respectively.
- the maximum cylinder temperature was set to 320 ° C.
- the following raw materials were supplied from the upstream, first downstream, and second downstream supply ports in the proportions shown in Table 3, respectively.
- the mixture was melt-kneaded, and the strand was cooled with water and pelletized.
- the screw speed during melt-kneading was 300 rpm and the amount of supplied grease was 45 kgZh. Vacuum suction was performed to remove volatile components from the 5th and 10th barrels.
- the temperature of the molten resin coming out of the die was measured using a contact thermocouple, and the torque of the motor at the time of extrusion was recorded.
- Each motor torque is expressed as a relative value with a motor rated capacity of 100%. The lower the motor torque when compared at the same discharge rate, the larger the production per hour.
- the resin temperature and motor torque obtained at this time are listed in Table 3 as “the resin temperature during extrusion” and “the torque during extrusion”, respectively.
- the obtained pellets were injection-molded in the same manner as in Example 1, and the multipurpose test piece described in IS0294-1 and the flat plate-shaped piece of 150mm XI 50mm X 2mm were formed and Izod in the edgewise direction.
- the impact strength was measured, and the melt viscosity at 280 ° C. was measured using a rheometer in the same manner as in Example 1.
- the melt viscosity obtained at this time is described in Table 3 as “melt viscosity (280 ° C.)”.
- Example 16 Example 16 (Example) and Example 15 (Comparative Example)
- the melt temperature of 13 was 297 ° C
- that of Example 16 was 286 ° C
- that of Example 15 was 327 ° C.
- This example is shown as an example using a high discharge-compatible extruder (mega compound one type extruder) that assumes actual production.
- Downstream second supply port 25 parts by weight of PA6b and filler 1
- the strands were cooled with a water spray type conveyor belt !, cut with a strand cutter and pelletized.
- the screw rotation speed was 500 rpm, and the supplied slag rate was 150 kgZh.
- Operating condition parameter P at this time 7. an 8 X 10 _5 kg'cm 3.
- Unit opening area of die hole 'Die was selected so that the discharge rate per unit time was 198kg / hr'cm 2 .
- vacuum suction was performed from the 5th and 10th barrels to remove volatile components.
- the screw of the extruder at this time has three kneading blocks.
- the first kneading block (the process of melting the polyphenylene ether) is located in the 4th barrel of the extruder, and its configuration is that from the upstream side, one R-KD with 36 mm L and 36 mm L One N-KD and one L-KD with L 18mm.
- the L / D of this first kneading block is 2.25.
- the second kneading block is located in the 6th barrel of the extruder, and its configuration is that from the upstream side, L is one 36 mm R-KD, L is 18 mm L-KD, and L is One 18mm R—KD.
- the LZD of this second kneading block is 1.8.
- the third kneading block is located in the ninth barrel of the extruder, and is composed of one R—KD with 36 mm L and one L—KD with 18 mm L from the upstream side.
- the L / D of this third kneading block is 1.35.
- L-KDs each having an L of 18 mm were arranged at positions between the fourth barrel and the fifth barrel and between the fifth barrel and the sixth barrel.
- Example 17 The procedure was the same as Example 17 except that the screw speed of the extruder was changed to 750 rpm. Incidentally, operating conditions parameters P at this time 5. was 2 X 10 _5 kg'cm 3. As in Example 17, the presence or absence of surging, the temperature of the resin at the die exit, the discoloration of the pellets and the occurrence of eye cracks were evaluated. The results are shown in Table 4.
- Example 17 Except for changing the extruder discharge rate of about 220KgZh, operating condition parameters at this time was carried out in the same manner as all Example 17 1. was 2 X 10 _4 kg'cm 3. In addition, when changing the discharge amount, the die was forced to change, so the discharge amount per unit opening area / unit time of the die hole was 289 kgZhr 'cm 2 . In the same manner as in Example 17, the presence or absence of surging, the resin temperature at the die exit, the discoloration of the pellets, and the occurrence of meshing were evaluated. The results are shown in Table 4. A slight surging phenomenon was confirmed during extrusion.
- the LZD of the first kneading block of the screw of the extruder was set to 4.5 (configuration: from the upstream side, one R-KD with 54 mm L, two R-KD with 36 mm L, 36 mm L All were carried out in the same manner as in Example 17, except that one N-KD and one L-KD with an L of 18 mm were changed. The results are shown in Table 4.
- the LZD of the second kneading block of the screw of the extruder was set to 4.5 (Composition: From the upstream side, one R-KD with 54 mm L, two R-KD with 36 mm L, 36 mm L Except for the third kneading block, PA6b was supplied from the same first downstream supply port, except for the third kneading block. The same as 17 was carried out. The results are shown in Table 4.
- Example 17 and Example 21 were melted at a resin temperature of 290 ° C and a mold temperature of 90 ° C using an injection molding machine (Toshiba Machine Co., Ltd .: IS80EP N).
- the multi-purpose test piece described in (1) and a flat-plate shaped piece of 150 mm x 150 mm x 2 mm are molded. It was allowed to stand at 23 ° C for 48 hours in an anti-nore, wet bag, and the Izod impact strength in the edge direction at 23 ° C according to ISO 179-1993 was measured.
- Example 17 The Izod impact strength of the sample in Example 17 is 763jZm, while that in Example 21 is
- sheet extrusion was performed using a single-axis sheet extruder capable of forming a sheet having a width of about 15 cm. At this time, the cylinder set temperature and die set temperature of the sheet extruder are 280 ° C. When sheet extrusion was performed using the pellets of Example 17, a good sheet having a width of about 140 to 145 mm, a thickness of about 0.4 mm, and a length of about 300 mm was obtained.
- FIG. 1 is a schematic view of a cup-shaped vacuum formed piece used in an example of the present invention.
- FIG. 2 is a schematic diagram for explaining the drawdown in the present invention.
- a resin composition having good sheet extrudability and extremely excellent vacuum formability, and further having high impact strength, and a molded article (film, sheet, etc.) comprising the resin composition Can be obtained.
- a production method can be obtained in which the temperature of the resin during processing of the composition is greatly suppressed. Molded bodies obtained by vacuum forming 'pressure forming' or press forming can be used for various purposes.
- housings for electronic devices such as various machines and computers, vehicle interior / exterior parts (front grill, headlight, winging, rear spoiler, side spoiler, dashboard, etc.), engine room parts (battery cover, etc.)
- vehicle interior / exterior parts front grill, headlight, winging, rear spoiler, side spoiler, dashboard, etc.
- engine room parts battery cover, etc.
- vehicle interior and exterior parts front grill, headlight housing, rear boiler, side boiler, dashboard, etc.
- engine room parts battery room parts
- paint masking parts for paint masking parts.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2006547796A JP4079334B2 (ja) | 2004-11-25 | 2005-11-22 | シート成形に適した樹脂組成物 |
EP05809499A EP1816166A4 (en) | 2004-11-25 | 2005-11-22 | RESIN COMPOSITION SUITABLE FOR SHEET FORMATION |
CN2005800405793A CN101065449B (zh) | 2004-11-25 | 2005-11-22 | 适于片材成型的树脂组合物 |
US11/791,467 US20080152885A1 (en) | 2004-11-25 | 2005-11-22 | Resin Composition Suitable For Sheet Formation |
Applications Claiming Priority (2)
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JP2004-340396 | 2004-11-25 | ||
JP2004340396 | 2004-11-25 |
Publications (1)
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WO2006057254A1 true WO2006057254A1 (ja) | 2006-06-01 |
Family
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PCT/JP2005/021476 WO2006057254A1 (ja) | 2004-11-25 | 2005-11-22 | シート成形に適した樹脂組成物 |
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Country | Link |
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US (1) | US20080152885A1 (ja) |
EP (1) | EP1816166A4 (ja) |
JP (1) | JP4079334B2 (ja) |
CN (1) | CN101065449B (ja) |
WO (1) | WO2006057254A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2008075699A1 (ja) * | 2006-12-20 | 2008-06-26 | Toyo Boseki Kabushiki Kaisha | 結晶性ポリアミド系樹脂組成物 |
US7902287B2 (en) * | 2008-01-21 | 2011-03-08 | Basf Aktiengesellschaft | Polyamide resin composition and method of preparing |
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US8178610B2 (en) | 2008-06-10 | 2012-05-15 | Sabic Innovative Plastics Ip B.V. | Polyamide/poly(arylene ether) composition, method, and article |
US8129454B2 (en) * | 2008-06-26 | 2012-03-06 | Sabic Innovative Plastics Ip B.V. | Profile extrusion method with reduced die build-up and extruded article prepared thereby |
FR2958796B1 (fr) * | 2010-04-13 | 2012-04-13 | Rhodia Operations | Garniture d'etancheite en polyamide pour piles alcalines. |
KR101301661B1 (ko) * | 2012-11-13 | 2013-09-03 | 윤성윤 | 내구성이 우수한 정전기 방지 시트의 제조 방법 |
RU2703239C2 (ru) * | 2014-12-12 | 2019-10-15 | Родиа Операсьон | Полиамидные композиции, содержащие полиамид 6,6 и смесь длинноцепочечных полиамидов, их применение, а также получаемые из них изделия |
US10066104B2 (en) | 2014-12-26 | 2018-09-04 | Asahi Kasei Kabushiki Kaisha | Polyamide resin composition, polyamide resin composition pellet group, molded article, and method for producing a polyamide resin composition |
CN105038207A (zh) * | 2015-06-18 | 2015-11-11 | 颜红兵 | 一种具有阻燃性、耐高温、高光泽的灯饰配件的聚酰胺增强配方 |
JP7107756B2 (ja) * | 2018-06-05 | 2022-07-27 | ポリプラ・エボニック株式会社 | シート及びシートの製造方法 |
CN111117216B (zh) * | 2019-12-19 | 2021-09-17 | 金发科技股份有限公司 | 一种聚酰胺组合物及其制备方法 |
TW202323431A (zh) * | 2021-10-21 | 2023-06-16 | 大陸商東麗纖維研究所(中國)有限公司 | 高濃度無機粒子母粒及其製備方法 |
CN115678268B (zh) * | 2022-09-29 | 2024-03-26 | 珠海万通特种工程塑料有限公司 | 一种聚酰胺模塑组合物及其制备方法和应用 |
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- 2005-11-22 EP EP05809499A patent/EP1816166A4/en not_active Withdrawn
- 2005-11-22 WO PCT/JP2005/021476 patent/WO2006057254A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
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CN101065449B (zh) | 2010-10-13 |
JP4079334B2 (ja) | 2008-04-23 |
JPWO2006057254A1 (ja) | 2008-06-05 |
EP1816166A1 (en) | 2007-08-08 |
EP1816166A4 (en) | 2010-01-06 |
CN101065449A (zh) | 2007-10-31 |
US20080152885A1 (en) | 2008-06-26 |
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