WO2007138743A1 - ポリアミド樹脂組成物および成形品 - Google Patents
ポリアミド樹脂組成物および成形品 Download PDFInfo
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- WO2007138743A1 WO2007138743A1 PCT/JP2007/000562 JP2007000562W WO2007138743A1 WO 2007138743 A1 WO2007138743 A1 WO 2007138743A1 JP 2007000562 W JP2007000562 W JP 2007000562W WO 2007138743 A1 WO2007138743 A1 WO 2007138743A1
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- polyamide resin
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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
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
-
- 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
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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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Definitions
- the present invention relates to a polyamide resin composition and a molded product.
- the polyamide resin composition is excellent in mechanical strength, thin-wall moldability, crystallinity, and warpage, and suitable for a thin flat plate-shaped portable electronic device component.
- Product and molded article are excellent in mechanical strength, thin-wall moldability, crystallinity, and warpage.
- P D A Portable electronic devices such as portable game machines and mobile phones are often dropped for carrying, and drop impact is an important characteristic especially for exterior parts such as housings.
- a resin composition comprising these resins and a small amount of filler is used in addition to non-reinforced polycarbonate resin and ABS resin having excellent impact resistance.
- the back of the keypad may be designed to require a back plate to support the key.
- the circuit board may be used directly.
- the material that satisfies both the electric characteristics such as dielectric constant and dielectric loss tangent, which are required characteristics of the board, and the strength and rigidity of the circuit board. Selection becomes difficult.
- a back plate and a frame may be necessary for the liquid crystal display panel, and a material that is thin but has high rigidity and low warpage is required.
- magnesium thixomolding is an option for die cast metal or steel plate processed products, but it is difficult to use metal when lightening requirements, insulation requirements, and electromagnetic waves need to pass through. It is.
- thermoplastic injection molding materials instead of such metal or steel plate processed products, high-rigidity, high-strength thermoplastic injection molding materials with excellent mass productivity are used.
- a thermoplastic injection molding material for example, Qf, ⁇ _Xylylenediamine-based polyamide resin obtained by polycondensation of linear aliphatic dibasic acid and xylylenediamine (hereinafter referred to as ⁇ polyamide ⁇ ⁇ ) Resin composition based on .
- polyamide MX resin has a slow crystallization rate, and when a thin-walled molded product is molded using the resin composition, the molded product has a low crystallinity.
- polyamide MX used as an example is a polyamide resin obtained from metaxylylenediamine and adipic acid (hereinafter abbreviated as “polyamide MXD 6 J”), and polyamide MXD 6 is compounded with polyamide 6 6
- polyamide MXD 6 J a polyamide resin obtained from metaxylylenediamine and adipic acid
- Polyamide resin obtained from mixed xylylenediamine composed of paraxylylenediamine and metaxylylenediamine and Qf, ⁇ _linear aliphatic dibasic acid (hereinafter abbreviated as “polyamide ⁇ ⁇ ”)
- a resin composition comprising talc as a crystal nucleating agent has been proposed (Patent Document 2).
- Patent Document 2 A resin composition comprising talc as a crystal nucleating agent.
- the heat resistance and water absorption characteristics of the resin composition which is a problem in the above-described proposed technology, are improved. It is possible to increase the crystallization speed of the composition and improve the moldability.
- a resin composition comprising a polyamide resin obtained from xylylenediamine and ⁇ -linear aliphatic dibasic acid and boron nitride as a crystal nucleating agent has been proposed.
- the ratio of paraxylylenediamine to metaxylylenediamine used for polycondensation of polyamide resin is 0 to 1 OZ 10 0 to 90 mol%
- Polyamide 6 resin and Z or polyamide 6 6 resin 20 to 90% by weight and aromatic polyamide resin 10 to 80% by weight Mixed polyamide resin 10 parts by weight, inorganic filling A polyamide resin composition comprising 0 to 300 parts by weight of a material, and a copper compound and Z or a halide of 0.01 to 5 parts by weight is proposed, and the polyamide resin composition has excellent properties inherent in polyamide. In addition to its properties, it is particularly excellent in light resistance, and it is taught that it can be used for exterior parts for automobiles and railways, building materials and housing equipment (Patent Document 4).
- Examples include a resin composition comprising a mixed polyamide resin comprising a polyamide 6 resin and an aromatic polyamide resin and an inorganic filler, a copper compound and a halide.
- a resin composition comprising a mixed polyamide resin comprising a polyamide 6 resin and an aromatic polyamide resin and an inorganic filler, a copper compound and a halide.
- Patent Document 1 Japanese Patent Application Laid-Open No. 5 1-6 3 8 60
- Patent Document 2 Japanese Patent Laid-Open No. 7_4 1 6 6 9
- Patent Document 3 Japanese Patent Laid-Open No. 7_4 1 6 70
- Patent Document 4 Japanese Patent Laid-Open No. 2001_106902
- Patent Document 5 Japanese Unexamined Patent Application Publication No. 2004_168849
- the present invention is a polyamide resin excellent in crystallization speed, thin moldability, crystallinity, warpage, and burr properties of a resin composition while maintaining the mechanical strength as polyamide MX.
- Means for solving the problem is to provide a composition and a molded article comprising the same
- the present invention has been completed based on the above findings, and the first gist thereof is a polyamide resin (B) 20 to 30% by weight of polyamide MP (A) and a melting point of 245 ° C or higher. It contains 70% by weight (the total amount of both is 100% by weight).
- filler (C) a fibrous filler (C 1) as an optional component and a plate-shaped filler as an essential component ( C2)
- the content ratio of the fibrous filler (C 1) and the plate-like filler (C2) (C 1): (C2) is 0:10 0-9: 1
- the filler (C) The content is 30 to 250 parts by weight based on 100 parts by weight of the total of the polyamide MP (A) and the polyamide resin (B), and the polyamide MP (A) contains 90 to 90 parts of metaxylylenediamine.
- the second gist of the present invention resides in a molded product obtained by molding the above resin composition, and the third gist is that the mold temperature controller temperature is 90 °.
- the present invention resides in the above-mentioned method for producing a molded product, which includes a step of molding under conditions of less than ° C.
- molding can be performed even at a low mold temperature of 130 ° C or lower by improving the crystallization speed and thin-wall moldability of the resin composition without impairing impact resistance, strength, rigidity, and the like.
- Thin-wall molding is possible without generating burrs on the product, and a polyamide resin composition excellent in mechanical strength, crystallization performance, and warpage, and a thin-wall molded product comprising the same can be obtained.
- the polyamide resin composition of the present invention has an excellent low warpage performance in addition to the high rigidity and impact resistance required for portable electronic device parts. Suitable for use as equipment parts, for example, PDAs, portable game machines, mobile phones, ID cards, and electronic keys for automobiles.
- Polyamide MP (A) used in the present invention is obtained by polycondensation of mixed diamine mainly composed of xylylenediamine with Of, ⁇ -linear aliphatic dibasic acid and Z or aromatic dibasic acid.
- aliphatic diamines such as tetramethylene diamine, 2-methylpentamethylene diamine, hexamethylene diamine, aromatic diamines such as metaphenylene diamine, para phenylene diamine, 1,3_bisaminomethyl It may contain alicyclic diamines such as cyclohexane and 1,4_bisaminomethylcyclohexane, and the ratio of diamines other than the above xylylenediamine (ratio in total diamines) is usually 1 It is 0 mol% or less, preferably 5 mol% or less.
- Examples of the Qf, ⁇ _linear aliphatic dibasic acid and Z or aromatic dibasic acid include, for example, dartaric acid, adipic acid, azelaic acid, sebacic acid, suberic acid, dodecanedioic acid, isophthalic acid. (I), terephthalic acid ( ⁇ ), and the like.
- adipic acid, sebacic acid, suberic acid, dodecanedioic acid and the like are preferable, and adipic acid is more preferable.
- the relative viscosity of the polyamide MP (A) used in the present invention is usually 2.
- the relative viscosity means a viscosity measured at a temperature of 23 ° C. using a solution having a resin concentration of 1 gZ1 OOm I prepared using 96% sulfuric acid as a solvent.
- the content of polyamide MP (A) is 30 to 80% by weight, preferably 30 to 70%, based on 100% by weight of the total of polyamide MP (A) and polyamide resin (B) having a melting point of 245 ° C or higher. Weight is 0 / o.
- the content of polyamide MP (A) is less than 30% by weight, the elastic modulus decreases, and when it exceeds 80% by weight, the crystallization speed during molding decreases.
- a polyamide resin (B) having a melting point of 245 ° C. or higher is blended with polyamide MP (A) in order to obtain a resin composition with improved crystallization speed and crystallinity of a thin molded article. To do.
- the melting point in the present invention is observed by a differential scanning calorimetry (DSC) method. This is the peak top temperature of the endothermic peak.
- the endothermic peak is the endothermic peak that is observed when the sample is heated and melted once to eliminate the effect of thermal history as much as possible, and then the temperature is raised again. Specifically, it can be obtained in the following manner. Increase the temperature from 30 to 300 ° C at a rate of 10 ° CZmin, hold at 300 ° C for 2 minutes, and then decrease the temperature to 200 ° C at a rate of 20 ° CZmin.
- the temperature is raised to 300 ° C at a rate of 10 ° CZmin, and the melting point is obtained from the peak of the endothermic peak observed at the time of temperature rise.
- the melting point of 245 ° C or higher means that the melting point measured by DSC is always 245 ° C or higher in the relative viscosity range of 2.0 to 4.0.
- polyamide resin (B) having a melting point of 245 ° C or higher examples include polyamide
- the relative viscosity of the polyamide resin (B) having a melting point of 245 ° C or higher is usually in the range of 2.0 to 4.0, preferably 2.0 to 2.7.
- the relative viscosity is too low, the physical properties of the resin are insufficient.
- the relative viscosity is too high, the moldability tends to decrease.
- the content of the polyamide resin (B) having a melting point of 245 ° C or higher is 20 to 70% with respect to the total 100% by weight of the polyamide MP (A) and the polyamide resin (B) having a melting point of 245 ° C or higher. %, Preferably 30-70 weight 0 / o.
- the content of the polyamide resin (B) having a melting point of 245 ° C or higher is less than 20% by weight, the crystallization speed at the time of molding is lowered, and when it exceeds 70% by weight, the elastic modulus is lowered.
- polyamide resins may be added to the resin composition of the present invention.
- examples of other polyamide resins include polyamide 6Z66, 66Z6 I, 6Z 6 TZ 6 I and the like from the viewpoint of improving the surface appearance. Also other heat It is good also as a polymer alloy by mix
- examples of other thermoplastic resins include modified polypropylene resins, polyethylene resins, and PPS resins from the viewpoint of improving the chemical resistance and slidability of the main polyamide resin. Also, from the viewpoint of improving impact properties, PPE resin, AS resin, ABS resin, PET resin and the like can be mentioned.
- the content of the other polyamide resin and the other thermoplastic resin is usually 50% by weight or less, preferably 40% by weight as a ratio in the total of the polyamide MP (A) and the polyamide resin (B). % Or less.
- a filler (C) is blended in order to improve the warp performance, mechanical strength and rigidity of the molded product. That is, the plate-like filler (C2) is used alone or in combination with the fiber-like filler (C 1) and the plate-like filler (C2), and preferably, both are mixed at a specific ratio as described later. . That is, the fibrous filler (C 1) is a preferable optional component, and the plate-like filler (C 2) is an essential component.
- the fibrous filler (C 1) is a filler having a fibrous appearance, and specific examples thereof include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, and stainless steel fibers. Metal fibers such as brass fibers, and organic fibers such as liquid crystal Kevlar.
- a powdery filler having an aspect ratio of 5 or more is also preferably used.
- specific examples include inorganic compounds whiskers such as potassium titanate, aluminum borate, titanium oxide, calcium carbonate, and minerals such as oolathinaite, with a ratio of 5 or more. Etc. Since the aspect ratio changes during the compounding process, the ⁇ aspect ratio mentioned here is the “aspect ratio of the raw material”. These fibrous fillers may be used in combination of two or more.
- the composition of the glass fiber is arbitrary, but a composition capable of forming glass fiber is better than molten glass.
- Preferred compositions are E glass composition, C glass composition, S glass composition, alkali resistant glass Etc.
- the tensile strength of the glass fiber is arbitrary, but is preferably 2900 kg Z mm 2 or more. Usually, E glass is preferred because it is easily available.
- the glass fiber may be surface-treated with a silane coupling agent such as monomethacryloxypropyl trimethoxysilane, r-glycidoxypropyl trimethoxysilane, or r-aminoprovirtriethoxysilane. preferable.
- a silane coupling agent such as monomethacryloxypropyl trimethoxysilane, r-glycidoxypropyl trimethoxysilane, or r-aminoprovirtriethoxysilane.
- the adhesion amount of the surface treatment agent is usually not less than 0.01% by weight of the glass fiber weight.
- a lubricant mixture such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin mixture having a film forming ability such as an epoxy resin, an acrylic resin, or a urethane resin, It is also possible to use glass fibers that have been surface-treated with a combination of a resin having a film-forming ability, a heat stabilizer, a flame retardant, and the like.
- Examples of the plate-like filler (C 2) include glass flake, my strength, talc, clay, graphite, sericite, montmorillonite, plate-like calcium carbonate, and plate-like alumina. Two or more of these may be used in combination. Among these, glass flakes, strength, and talc are preferable from the viewpoint of the balance of bending characteristics, impact resistance, dimensional stability, fluidity, and product appearance. Since portable electronic device parts are often required to have particularly high impact resistance, it is most preferable to use glass flakes having the highest impact resistance.
- glass flakes suitable as the plate-like filler (C 2) those having E glass composition and C glass composition are available as general commercial products.
- the average particle size varies depending on the grade of each company, but it is a flat glass, preferably about several tens // m to 1 mm, more preferably about 50 to 80 m. Two or more kinds of glass flakes having different average particle diameters may be used in combination.
- the surface treatment is carried out with a silane coupling agent such as —methacryloxypropyl trimethoxysilane, r-glycidoxypropyl trimethoxysilane, r-aminominovir triethoxysilane, etc.
- My strength suitable as the plate-like filler (C2) may be natural strength or synthetic strength.
- My strength (mica) is broadly divided into muscovite and phlogopite, and both can be used in the present invention.
- the average particle size is from 1 000 m for large ones to about 5 m for small ones. If it is a synthetic My power, the thing of about several // m is also available. Any size can be used in the present invention. From the viewpoint of surface appearance and dimensional stability, the size is usually 5 to 1 OO Zm. Two or more my strengths with different average particle sizes may be used in combination.
- the surface-treated one and the one that has been converged to reduce the bulk density can be used.
- Talc suitable as the plate-like filler (C2) is a mineral crystal mainly composed of magnesium silicate.
- the average particle size there is no limitation on the average particle size, and any particle size can be used.
- those having an average particle diameter of 3 to 100 m are preferred.
- Two or more kinds of talc having different average particle diameters may be used in combination.
- those that have been surface treated and those that have been converged to reduce bulk density can be used.
- Talc exhibits an effect as a nucleating agent in addition to a reinforcing effect, and can improve the moldability by increasing the crystallization speed of the resin composition.
- a part of the component (C2) (for example, about 0.3 to 5% by weight in the component (C2)) is mixed with talc having a small average particle size (for example, an average particle size of about 1 to 10 m).
- talc having a small average particle size (for example, an average particle size of about 1 to 10 m).
- the filler (C) content is 30-250 to 100 parts by weight of the total of polyamide KM P (A) and polyamide resin (B) having a melting point of 245 ° C or higher. Parts by weight, preferably 60 to 200 parts by weight, more preferably 70 to 1 60 parts by weight. When the content is less than 30 parts by weight, mechanical properties such as rigidity and the effect of improving warpage are insufficient, and when the content exceeds 250 parts by weight, it becomes difficult to produce a resin composition.
- the content ratio of the fibrous filler (C 1) and the plate-like filler (C2) is 0:10 to 9: 1 as a weight ratio of (C 1) :( C2), Depending on the required balance between low warpage level and strength, preferably 1: 9 to 8: 2, more Preferably, it is in the range of 3: 7 to 7: 3. It is preferable that the content ratio of the component (C 1) and the component (C2) is within the above range because both the mechanical properties and warpage of the molded product can be effectively improved.
- a nucleating agent is preferably added to the resin composition of the present invention in order to increase the crystallization rate and improve the moldability.
- the average particle size of the inorganic nucleating agent is usually from 0.01 to 20 m, preferably from 0.1 to 7 m.
- the content of the nucleating agent is usually from 0.001 to 8 parts by weight, preferably from 0.01 to 4 parts by weight, based on 100 parts by weight of the total of component (A) and component (B). When the content of the nucleating agent is less than 0.001 part by weight, the expected effect may not be obtained. When the content is more than 8 parts by weight, the effect as a foreign substance is expressed and the strength and impact are reduced. The value may decrease.
- a release agent is preferably added to the resin composition of the present invention in order to improve releasability during molding.
- the release agent include long-chain aliphatic carboxylic acids having 14 or more carbon atoms such as stearic acid and palmitic acid, and derivatives thereof.
- esters, alkali metal salts, alkaline earth metal salts, amides, etc. higher aliphatic alcohols having 14 or more carbon atoms such as stearyl alcohol and derivatives thereof, amines having 14 or more carbon atoms such as stearylamine, and Derivatives thereof, waxes such as low molecular weight polyethylene wax and paraffin wax, silicone oil, silicone gum and the like.
- the content of the release agent is usually 0.03 to 1.5 parts by weight, preferably 0.03 to 0.5 parts by weight, with respect to 100 parts by weight of the total of component (A) and component (B). .
- additives generally used in polyamide resin compositions for example, flame retardants, stabilizers, pigments, dyes, weather resistance improvers, and the like can be appropriately added as necessary. .
- Stabilizers include copper halides common to polyamide resins (eg, copper iodide, copper chloride, copper bromide) and Z or alkali metal halides (eg, potassium iodide, potassium bromide, etc.). Mixtures, organic stabilizers (eg, hindered phenols, phosphites, etc.).
- the content of the stabilizer is usually 0.1 to 5 parts by weight, preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B). Part. If the content is less than 0.01 part by weight, thermal discoloration improvement, weather resistance, Z light resistance improvement may be insufficient, and if the content exceeds 5 parts by weight, mechanical properties May decrease. Two or more of these stabilizers may be used in combination.
- an elastomer may be added to the resin composition of the present invention in order to further improve the impact strength.
- Elastomers include, for example, polyolefin elastomers, gen elastomers, polystyrene elastomers, polyamide elastomers, polyester elastomers, polyurethane elastomers, fluorine elastomers, silicon elastomers, etc. Is mentioned. Of these, polyolefin elastomers or polystyrene elastomers are preferred. When these elastomers are used after being modified for compatibilization with polyamide, the effect is further enhanced.
- Modification with acid preferably maleic acid or maleic anhydride
- epoxy modification and the like are suitable modifications for the resin composition of the present invention.
- the content of the elastomer is usually 0.5 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to the total of 10 parts by weight of the component (A) and the component (B).
- the method for producing the resin composition of the present invention is not particularly limited. Manufactured by blending a predetermined amount of the above components (A), (B) and (C 2) and, if necessary, the component (C 1) and other additives, and melt-kneading them. .
- the melt kneading method may be any known method. For example, using a single-screw or twin-screw extruder, a Banbury mixer or similar equipment, all the materials are put together from the root of the extruder and melt kneaded to produce pellets. I can do it.
- component (A) and component (B) and other components added as necessary are added and melted
- side feed of component (C 2) and component (C 1) if necessary
- the components (A), (B), (C2) and other components added as necessary are melted while adding the components (C1) if necessary.
- a method of kneading by side feeding can also be employed.
- a method of producing a resin composition pellets blend within the composition range defined in the present invention by blending two or more compounds having different additives and compositions, or some powder components and liquids A method of blending the components separately can also be employed.
- the resin composition of the present invention can be formed into various molded articles by a molding method generally used for thermoplastic resin compositions, that is, an injection molding method, a hollow molding method, an extrusion molding method and the like. Since it is excellent in fluidity and mechanical properties, it is particularly useful as a thin molded product by an injection molding method.
- the resulting thin-walled molded product has both high impact resistance and rigidity, as well as low anisotropy and low warpage, so it can be used in electronic notebooks, portable computers such as PAD, pagers, and mobile phones.
- Components such as internal structures and casings used for portable electronic devices such as telephones and PHS, especially for plate-shaped components.
- the plate shape referred to in the present invention refers to a thin plate shape as a whole, and the cross section may be slightly curved or curved. Also, it may be provided with unevenness, windows, holes, etc. for functionality and design.
- the product shape of portable electronic devices as described above is thin, and many parts such as internal structures and housings can be said to be substantially plate-shaped except for the rib portion and hinge portion.
- the overall shape is substantially plate-like except for the rib and hinges. There may be a large number of holes, bosses, etc. in this part. In the present invention, if such a part is less than 50% of the total area, it is assumed that the part has a plate shape.
- the resin composition of the present invention is suitable.
- the resin composition of the present invention is particularly suitable for a flat plate (substrate) that supports internal structural components incorporated in a portable electronic device.
- the resin composition of the present invention is excellent in crystallization performance, for example, when the resin composition of the present invention is used and a portable electronic device part is manufactured by injection molding, it is usually sufficient. Mold temperature controller temperature at which crystallinity is difficult to obtain, specifically under low mold temperature controller temperature conditions of less than 1300 ° C, further less than 110 ° C, and even less than 90 ° C. Even when shaped, it is possible to produce parts with sufficiently high crystallinity, specifically, a degree of crystallinity of 28% or more. This tendency is particularly noticeable when the thickness of the parts is thin, specifically when the thickness is 1.2 mm or less.
- EMI shielding properties are required for the portable electronic device component of the present invention
- fibrous filler (C 1) carbon fiber, metal fiber, or metal-plated glass fiber
- carbon fiber is used as the fibrous filler (C 1).
- organic fibers it is preferable to use organic fibers.
- the EMI shield property can be imparted to the portable electronic device component of the present invention by conducting conductive coating, metal plating or metal deposition.
- a flask with a capacity of 3 liters equipped with a stirrer, thermometer, reflux condenser, raw material dripping device, heating device, etc. was charged with 7 30 g of adipic acid, and the temperature inside the flask was adjusted to 1 6 The temperature was raised to 0 ° C. to melt adipic acid.
- the p-xylylenediamine 3 0 mole 0/0, m-xylylenediamine 7 680 g of mixed xylylenediamine containing 0 mol% was successively added dropwise over about 2.5 hours.
- the reaction was continued with stirring while maintaining the internal temperature always above the melting point of the product, and the temperature was raised to 270 ° C at the end of the reaction.
- Water generated by the reaction was discharged out of the reaction system by a condenser.
- the reaction was continued by stirring at a temperature of 275 ° C., and the reaction was terminated after 1 hour.
- the product was removed from the flask, cooled with water and pelletized.
- the resulting polyamide resin has a melting point of 25 8 ° C, a crystallization temperature of 2 16 ° C, and a relative viscosity (measured in a 96% sulfuric acid solution at a concentration of 1 g / 10 Om and 23 ° C) of 2.08.
- Polyamide 66 DuPont product, trade name “Zytel 100”, melting point 264 ° C., relative viscosity 3.0
- Mold release agent Montanate ester wax, manufactured by Clariant Japan, trade name “
- each component excluding the fibrous filler (C 1) was weighed so as to have the composition shown in Tables 1 to 3 below, blended with a tumbler, and then a twin screw extruder manufactured by Toshiba Machine Co., Ltd. “Ding EM35B (barrel) 1 0 block configuration) ” Then, the resin composition pellets ⁇ were prepared by side-feeding the component (C 1) from the seventh block counted from the hopper side. The temperature setting of the extruder was uniformly 280 ° C.
- the desired performance of the molded article of the present invention is that the bending strength is 150 MPa or more, the bending elastic modulus is 10 GPa or more, and the notched Charpy impact strength is 2 MPa or more.
- Crystallinity was evaluated by the crystallinity obtained by DSC.
- DSC when a material is melted or vaporized by raising the temperature, it is possible to investigate the melting point, heat amount, and crystallization state by observing the heat generation or absorption of the material. Evaluation was made by the following method.
- Crystallinity (%) (Heat of endothermic peak (JZg) —Heat of exothermic peak (J Zg)) Z (Theoretical heat of fusion (JZg) in each resin composition) X 1 00 ⁇ ⁇ ⁇ (1)
- the method of measuring the theoretical heat of fusion in the present invention is as follows. That is, the endothermic peak heat at the melting point of the polyamide resin having various crystallinity is measured by DSC, and the calibration curve is created by plotting the obtained endothermic peak heat and crystallinity on two axes, The calorific value of the calibration curve was 100%.
- the crystallinity of the polyamide resin used for the DSC measurement was measured in accordance with the J I S K7 1 1 2 standard using a generally used density gradient tube method.
- the degree of crystallinity is 28% or more, it is determined that the crystallization of the molded product has been sufficiently advanced.
- the crystallinity 250/0 or more and less than 280/0, the crystallization of the molded product is slightly insufficient, but it is judged that there is no problem as an actual molded product.
- the degree of crystallinity is 15% or more and less than 25%, crystallization of the molded product is insufficient, and it is judged that there is a problem as an actual molded product. If the degree of crystallinity is less than 15%, the molded product is hardly crystallized, and it is judged that it cannot be used as an actual molded product.
- Burr exists mainly near the fange bowl, burr length ⁇ 100 m ⁇ : Burr exists mainly near the fange bowl, 100 m burr length ⁇ 500 m
- Burr exists mainly near the fan gate, 500 m ⁇ burr length
- X Burr exists on the entire surface of the molded product
- Polyamide MXD 6 is used instead of polyamide MP, and the contents of polyamide MXD 6 and polyamide 6 6 are outside the range defined in the present invention. , Warpage and crystallinity of thin-walled molded products are inferior, and burrs are likely to occur. In particular, when the mold temperature is low, the crystallinity of the molded product is low.
- Example 1 and Comparative Examples 13 and 14 are compared, the use of polyamide MP and polyamide 66 as the polyamide resin improves the crystallinity of the molded product, and reduces burrs. It can be seen that the occurrence is also reduced. The improvement in crystallinity is particularly noticeable when molded at a low mold temperature.
- the content ratio of the polyamide MP and the polyamide 66 is within the range specified by the present invention and the plate-like filler is used, preferably, the fibrous and plate-like fillers are specified. It can be seen that the object of the present invention can be achieved when the ratio is used in combination.
- the crystallization speed and thin-wall moldability of the resin composition can be improved, thin-wall molding at a low mold temperature not reaching 130 ° C is possible, and It is less likely to occur and the deburring process can be omitted, enabling production at low cost.
- the resin composition of the present invention has high rigidity and impact resistance required for portable electronic device parts. In addition to impact properties, it has excellent low warpage performance, so it is used for mobile electronic device parts that have a circuit board inside, such as PDA, portable game machine, mobile phone, ID card, automotive electronic key. It is suitable for etc.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/302,095 US20090280311A1 (en) | 2006-05-30 | 2007-05-25 | Polyamide resin composition and molded article |
CN2007800154120A CN101432364B (zh) | 2006-05-30 | 2007-05-25 | 聚酰胺树脂组合物和成型品 |
EP07737218A EP2025716A4 (en) | 2006-05-30 | 2007-05-25 | POLYAMIDE RESIN COMPOSITION AND FORM BODY |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2006-149623 | 2006-05-30 | ||
JP2006149623 | 2006-05-30 |
Publications (1)
Publication Number | Publication Date |
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WO2007138743A1 true WO2007138743A1 (ja) | 2007-12-06 |
Family
ID=38778270
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/000562 WO2007138743A1 (ja) | 2006-05-30 | 2007-05-25 | ポリアミド樹脂組成物および成形品 |
Country Status (5)
Country | Link |
---|---|
US (1) | US20090280311A1 (ja) |
EP (1) | EP2025716A4 (ja) |
KR (1) | KR20090014260A (ja) |
CN (1) | CN101432364B (ja) |
WO (1) | WO2007138743A1 (ja) |
Cited By (4)
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WO2009137548A1 (en) * | 2008-05-08 | 2009-11-12 | E. I. Du Pont De Nemours And Company | Portable electronic device cover comprising renewable polyamide resin composition |
JP2011148267A (ja) * | 2010-01-25 | 2011-08-04 | Mitsubishi Engineering Plastics Corp | ポリアミド樹脂成形品の製造方法 |
US20110288194A1 (en) * | 2008-11-21 | 2011-11-24 | Arkema France | Polyamide and bioresourced reinforcement compositions having improved mechanical properties |
JP2012017429A (ja) * | 2010-07-09 | 2012-01-26 | Mitsubishi Gas Chemical Co Inc | ポリアミド樹脂組成物およびそれからなる成形品 |
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US20100227122A1 (en) * | 2006-01-13 | 2010-09-09 | Teruhisa Kumazawa | Polyamide Resin Composition for Portable Electronic Device and Molded Article for Portable Electronic Device |
WO2011030742A1 (ja) * | 2009-09-11 | 2011-03-17 | 旭化成ケミカルズ株式会社 | ポリアミド及びポリアミド組成物 |
EP2479218B1 (en) | 2009-09-14 | 2018-12-26 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin composition |
TWI541278B (zh) * | 2012-12-18 | 2016-07-11 | 夸茲沃克公司 | 導熱性塑膠材料 |
FR2999593A1 (fr) * | 2012-12-19 | 2014-06-20 | Solvay Specialty Polymers Usa | Composants de dispositifs electroniques portables |
JP6131151B2 (ja) * | 2013-09-03 | 2017-05-17 | 三菱エンジニアリングプラスチックス株式会社 | ポリアミド樹脂組成物、樹脂成形品、及びメッキ層付樹脂成形品の製造方法 |
CN106536632B (zh) * | 2014-07-25 | 2019-06-11 | 帝斯曼知识产权资产管理有限公司 | 热稳定的聚酰胺组合物 |
KR102012061B1 (ko) * | 2015-07-31 | 2019-08-19 | 롯데첨단소재(주) | 폴리아미드 수지 조성물 및 이로부터 형성된 성형품 |
JP6259142B2 (ja) | 2016-04-27 | 2018-01-10 | 花王株式会社 | ファン |
FR3071503B1 (fr) * | 2017-09-25 | 2020-06-19 | Arkema France | Utilisation d'une composition de copolyamide comme matrice de materiau charge avec des fibres de verre a section circulaire pour limiter le gauchissement |
EP3922680B1 (en) * | 2017-10-03 | 2022-05-18 | Mitsubishi Engineering-Plastics Corporation | Thermoplastic resin composition, resin molding, method for manufacturing plated resin molding, and method for manufacturing portable electronic device part |
US20210002471A1 (en) * | 2018-03-27 | 2021-01-07 | Basf Se | A polyamide composition, manufacturing method, an application and article thereof |
US11056441B2 (en) * | 2019-12-05 | 2021-07-06 | Apple Inc. | Electromagnetic shielding of compact electronic modules |
BR112022020201A2 (pt) * | 2020-04-09 | 2023-02-23 | Basf Se | Composição de poliamida, método para preparar a composição de poliamida, peça e uso da composição de poliamida |
CN115836111A (zh) * | 2020-07-10 | 2023-03-21 | 东洋纺株式会社 | 无机增强聚酰胺树脂组合物 |
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- 2007-05-25 CN CN2007800154120A patent/CN101432364B/zh active Active
- 2007-05-25 US US12/302,095 patent/US20090280311A1/en not_active Abandoned
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WO2009137548A1 (en) * | 2008-05-08 | 2009-11-12 | E. I. Du Pont De Nemours And Company | Portable electronic device cover comprising renewable polyamide resin composition |
US20110288194A1 (en) * | 2008-11-21 | 2011-11-24 | Arkema France | Polyamide and bioresourced reinforcement compositions having improved mechanical properties |
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Also Published As
Publication number | Publication date |
---|---|
CN101432364A (zh) | 2009-05-13 |
KR20090014260A (ko) | 2009-02-09 |
EP2025716A4 (en) | 2011-05-18 |
EP2025716A1 (en) | 2009-02-18 |
CN101432364B (zh) | 2011-06-01 |
US20090280311A1 (en) | 2009-11-12 |
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