WO2012026413A1 - Composition de résine polyamide utilisée comme plaque réfléchissante pour del montées en surface - Google Patents

Composition de résine polyamide utilisée comme plaque réfléchissante pour del montées en surface Download PDF

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Publication number
WO2012026413A1
WO2012026413A1 PCT/JP2011/068831 JP2011068831W WO2012026413A1 WO 2012026413 A1 WO2012026413 A1 WO 2012026413A1 JP 2011068831 W JP2011068831 W JP 2011068831W WO 2012026413 A1 WO2012026413 A1 WO 2012026413A1
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Prior art keywords
polyamide resin
resin composition
acid
carbon atoms
copolymerized
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PCT/JP2011/068831
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English (en)
Japanese (ja)
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順一 中尾
貴司 清水
誠 玉津島
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東洋紡績株式会社
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Priority to CN201180011596XA priority Critical patent/CN102782048B/zh
Priority to JP2011541418A priority patent/JP4998841B2/ja
Priority to KR1020127016769A priority patent/KR101212917B1/ko
Publication of WO2012026413A1 publication Critical patent/WO2012026413A1/fr

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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
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

Definitions

  • the present invention relates to a polyamide resin composition suitable for use in a reflector for a surface mount LED having excellent moldability, fluidity, dimensional stability, low water absorption, solder heat resistance, surface reflectance, and the like. Furthermore, the present invention relates to a polyamide resin composition suitable for use in a reflector for a surface mount LED having excellent gold / tin solder heat resistance, light resistance, and low water absorption.
  • LEDs light-emitting diodes
  • LEDs are used for lighting fixtures, optical elements, mobile phones, backlights for liquid crystal displays, automobile console panels, traffic lights, etc. by utilizing features such as low power consumption, long life, high brightness, and miniaturization. It is applied to display boards.
  • surface mounting technology is used to achieve lightness, thinness, and miniaturization.
  • a surface-mounted LED is generally composed of a light-emitting LED chip, a lead wire, a reflector that also serves as a case, and a sealing resin.
  • each component In order to join the entire component mounted on an electronic board with lead-free solder
  • each component In addition, each component must be formed of a material that can withstand the soldering reflow temperature of 260 ° C.
  • the reflector in addition to these heat resistances, surface reflectivity for efficiently extracting light and durability against heat and ultraviolet rays are required. From this point of view, various heat-resistant plastic materials such as ceramics, semi-aromatic polyamides, liquid crystal polymers, thermosetting silicones, etc. have been studied.
  • high refractive fillers such as titanium oxide are dispersed in semi-aromatic polyamides.
  • Resins have a good balance of mass productivity, heat resistance, and surface reflectance, and are most commonly used.
  • semi-aromatic polyamides injection moldability at low mold temperatures and solder reflow processes are required. Yield improvement is required.
  • Patent Documents 1 to 3 have been proposed as polyamide resin compositions for LED reflectors.
  • a polyamide resin composition containing wollastonite is disclosed. Although this resin composition is excellent in whiteness and mechanical properties, since the glass transition temperature is 130 ° C., the mold temperature at the time of injection molding must be 140 ° C. or higher in order to sufficiently complete crystallization. Necessary.
  • the lead frame and the resin are greatly shrunk during the cooling process, and problems such as deformation and peeling are likely to occur. Even if it can be molded at a low mold temperature, because crystallization is not completed sufficiently, deformation or crystal shrinkage occurs during heating in the subsequent process, causing a problem of peeling from the sealing material or lead frame, Lack of reliability. Furthermore, the copolyamide used has a saturated water absorption of about 5%, which is easy to absorb water, and there is a problem in workability such as the occurrence of swelling on the surface in the reflow soldering process.
  • Patent Document 2 30 to 100 mol% of a dicarboxylic acid unit derived from terephthalic acid, 0 to 70 mol% of an aromatic dicarboxylic acid unit other than terephthalic acid, and / or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. From 100 mol% of a diamine unit consisting of a dicarboxylic acid unit consisting of 0 to 70 mol% units and a linear aliphatic diamine unit having 4 to 20 carbon atoms and / or an aliphatic diamine unit having a side chain having 4 to 20 carbon atoms.
  • a polyamide resin composition containing a polyamide resin (in the examples, only polyamide 6T66 composed of terephthalic acid, adipic acid and hexamethylenediamine is described), an inorganic filler, and a white pigment is disclosed. Since the polyamide 6T66 resin composition implemented in this patent document has a glass transition temperature of about 85 ° C., the mold temperature at the time of molding may be about 120 ° C., but the saturated water absorption rate is close to 6%. There are problems with dimensional changes and solder resistance.
  • Patent Document 3 contains 60 to 100 mol% of a dicarboxylic acid unit containing 60 to 100 mol% of a terephthalic acid unit and 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit.
  • a polyamide resin composition containing a polyamide composed of diamine units (hereinafter, polyamide 9T) and titanium oxide is disclosed. Although this resin composition is excellent in low water absorption, there is room for improvement in terms of moldability in that the mold transition temperature is as high as 140 ° C. because the glass transition temperature is 125 ° C.
  • Patent Documents 1 and 3 are not suitable for multi-cavity because the glass transition temperature is high and the fluidity is drastically lowered in the mold during injection molding.
  • the resin composition of Patent Document 2 since the resin is solidified too quickly, the gate seal at the time of injection molding is fast and is not suitable for multi-cavity.
  • the conventionally proposed aromatic polyamide resin compositions have been used with problems in moldability, dimensional stability, solder heat resistance, and fluidity.
  • the surface mount LED reflector As reported in Patent Document 3 and Patent Document 4, it is composed of polyamide 9T composed of nonanediamine and terephthalic acid (hereinafter referred to as PA9T), decanediamine and terephthalic acid.
  • Polyamide 10T (hereinafter referred to as PA10T) has been investigated as a low water-absorbing polyamide.
  • PA10T polyamide using a diamine having 9 or more carbon atoms has a melting point around 300 ° C. or less than 300 ° C. Therefore, in the gold / tin eutectic solder process, these materials are melted and have no heat resistance, so that they cannot be used.
  • polyamide 6T composed of hexamethylenediamine and terephthalic acid (hereinafter referred to as PA6T) has a melting point essentially close to 370 ° C., and is therefore a material capable of processing gold / tin eutectic solder.
  • the surface mounting type is adjusted to a melting point that is easy to process by copolymerizing adipic acid, 2-methyl-pentamethylenediamine, tetramethylenediamine, and the like. Used as a reflector for LED.
  • the polyamide obtained by copolymerization using these PA6T as a skeleton can be adjusted so as not to have a melting point at 310 ° C.
  • PA6T as a surface mount LED reflector has a high amide bond concentration in the resin, so it has a high water absorption rate in the usage environment, and bubbles are generated on the surface of molded products even in the lead-free reflow soldering process. It is easy to become. Furthermore, foaming becomes significant in gold / tin eutectic solder joints that require higher temperatures. Further, when the amount of amide bonds is large as in the case of conventional PA6T, the amide bond is the starting point and oxidation deterioration proceeds and colors at a high temperature, so that the reliability as a reflector is greatly reduced.
  • the polyamide resin composition used for the reflector for a surface-mounted LED has a high melting point of 310 ° C. or higher, low water absorption, and a low aromatic ring concentration.
  • a polyamide resin composition used for a surface mount LED reflector satisfying these requirements has not been reported so far.
  • JP 2002-294070 A JP 2005-194513 A JP 2004-75994 A JP 2008-274288 A JP 2005-194513 A JP 2002-294070 A Special table 2003-528165 gazette
  • the present invention was devised in view of the above-mentioned problems of the prior art, and its purpose is to formability at injection molding, fluidity, dimensional stability, low water absorption, solder heat resistance, and surface reflectance.
  • An object of the present invention is to provide a polyamide resin composition suitable for use in an excellent surface mount LED reflector. Furthermore, an object of the present invention is to provide a high melting point that can be applied to a gold / tin eutectic soldering process and to ensure a long-term reliability, and a low water absorption for reducing swelling of a molded product due to moisture in the soldering process.
  • Another object of the present invention is to provide a polyamide resin composition suitable for use in a reflector for a surface-mounted LED that achieves a low aromatic concentration for improving light resistance during outdoor use or long-term use.
  • the present inventor can advantageously perform injection molding and reflow soldering processes while satisfying the characteristics as an LED reflector, and further, gold / tin eutectic solder heat resistance, low water absorption As a result of intensive studies on the composition of polyamide having excellent properties and light resistance, the present invention has been completed.
  • the present invention has the following configurations (1) to (10).
  • a surface-mount type LED comprising 50 mol% or more of a structural unit obtained from a molar salt, further satisfying the following (a) and (b), and the polyamide resin composition satisfying the following (
  • the copolymerized polyamide resin (A) is a component other than a structural unit obtained from an equimolar molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid, a diamine having 10 to 18 carbon atoms, a dicarboxylic acid, amino
  • the polyamide resin composition according to (1) which is obtained by copolymerizing one or more of carboxylic acid or lactam.
  • the copolymerized polyamide resin (A) is a component other than a structural unit obtained from an equimolar molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid.
  • Copolymerized polyamide resin (A) is composed of 55 to 75 mol% of a structural unit obtained from an equimolar molar salt of hexamethylenediamine and terephthalic acid, and a structural unit 45 obtained from 11-aminoundecanoic acid or undecanactam.
  • the copolymer polyamide resin (A) is a structural unit obtained from an equimolar salt of the diamine having 2 to 8 carbon atoms and terephthalic acid, or the diamine, dicarboxylic acid or aminocarboxylic acid having 10 to 18 carbon atoms.
  • the non-fibrous or non-needle filler (D) is talc, and is contained in a proportion of 0.1 to 5 parts by mass of talc with respect to 100 parts by mass of the copolymerized polyamide resin (A).
  • Tc1 temperature rise crystallization temperature of the polyamide resin composition
  • the polyamide resin composition of the present invention uses a specific copolymerized polyamide resin having excellent processability such as moldability at the time of injection molding and solder heat resistance.
  • a reflector for a surface-mounted LED that highly satisfies the required characteristics can be industrially advantageously produced.
  • the polyamide resin composition of the present invention is adaptable to a gold / tin eutectic solder process because the main component copolymer polyamide resin has a high melting point exceeding 300 ° C. and excellent heat resistance, The number of carbon atoms per amide bond in the polyamide resin is in a specific range and the aromatic ring concentration is low, so it has excellent heat resistance, toughness, light resistance, and excellent adhesion to the sealing material. Can be shown.
  • the polyamide resin composition of the present invention is intended for use in a reflector for a surface-mounted LED.
  • the surface mount type LED includes a chip LED type using a printed wiring board, a gull wing type using a lead frame, and a PLCC type.
  • the polyamide resin composition of the present invention injection-molds all these reflectors. Can be manufactured.
  • the polyamide resin composition of the present invention comprises a copolymerized polyamide resin (A), titanium oxide (B), at least one reinforcing material (C) selected from the group consisting of a fibrous reinforcing material and an acicular reinforcing material, and Contains non-fibrous or non-needle filler (D), 0.5 to 100 parts by mass of titanium oxide (B), 100 to 100 parts by mass of copolyamide resin (A), and 0 to 100 of reinforcing material (C)
  • a polyamide resin composition containing 0 to 50 parts by mass of non-fibrous or non-needle filler (D) wherein the copolymerized polyamide resin (A) comprises a diamine having 2 to 8 carbon atoms and It contains 50 mol% or more of structural units obtained from an equivalent molar salt with terephthalic acid, further satisfies the following (a) and (b), and the polyamide resin composition satisfies the following (c): To: (A) 7.5 ⁇
  • the copolymerized polyamide resin (A) is blended to realize excellent UV resistance in addition to a high melting point and low water absorption in order to impart high reliability, and has at least 2 carbon atoms. It is characterized by containing 50 mol% or more of a structural unit obtained from an equimolar molar salt of diamine 8 and terephthalic acid.
  • Examples of the diamine component having 2 to 8 carbon atoms include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 2-methyl-1,5- Pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, piperazine, cyclohexanediamine, bisaminomethylcyclohexane, xylylenediamine, and phenylenediamine Single or multiple use is possible.
  • the copolymerized polyamide resin (A) needs to contain at least 50 mol% of a structural unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid.
  • the resulting polyamide has a plurality of melting points, and the DSC melting peak temperature existing on the lowest temperature side is not more than 300 ° C., which is not preferable.
  • the structural unit obtained from an equimolar molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid is less than 50 mol%, the crystallinity and mechanical properties are undesirably lowered.
  • copolymerized polyamide resin (A) other components can be copolymerized at less than 50% mol in the structural unit.
  • copolymerizable diamine components include 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12- Of dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine
  • examples thereof include aliphatic diamines such as bis (3-methyl-4-aminohexyl) methane, bis- (4,4′-aminocyclohexyl) methane, and alicyclic diamines such as isophorone diamine, aromatic diamines, and the like.
  • copolymerizable acid components include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 2,2′-diphenyldicarboxylic acid, 4 , 4'-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid, 5-hydroxyisophthalic acid and other aromatic dicarboxylic acids, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1 , 11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid
  • lactams such as ⁇ -caprolactam, 11-aminoundecanoic acid, undecane lactam, 12-aminododecanoic acid, lauryllactam, and aminocarboxylic acids having a structure in which they are ring-opened can be used.
  • the copolymer component it is preferable to copolymerize one or more of diamines having 10 to 18 carbon atoms, dicarboxylic acids, aminocarboxylic acids, and lactams. More preferably, one or more of an aminocarboxylic acid having 11 to 18 carbon atoms or a lactam are copolymerized.
  • an aminocarboxylic acid or lactam having 11 to 18 carbon atoms plays a role of adjusting the melting point and the temperature rising crystallization temperature to improve the moldability, reducing the water absorption rate, and improving troubles due to changes in physical properties and dimensional changes during water absorption. It has the role of improving the fluidity at the time of melting by introducing a role and a flexible skeleton.
  • the copolymerized polyamide resin (A) in the present invention is (A) 7.5 ⁇ [number of carbon atoms in copolymerized polyamide resin / number of amide bonds in copolymerized polyamide resin] ⁇ 8.2 It is necessary to satisfy (Hereinafter, [number of carbon atoms in copolymerized polyamide resin / number of amide bonds in copolymerized polyamide resin] may be simply abbreviated as the average number of carbon atoms between amide bonds.)
  • the copolymerized polyamide resin (A) of the present invention is: It is necessary to satisfy 0.27 ⁇ [the number of carbon atoms on the aromatic ring in the copolymerized polyamide resin / the total number of carbon atoms in the copolymerized polyamide resin] ⁇ 0.35. (Hereinafter, [the number of carbon atoms on the aromatic ring in the copolymerized polyamide resin / the total number of carbon atoms in the copolymerized polyamide resin] may be simply abbreviated as the carbon atom ratio on the aromatic ring.)
  • the structural unit obtained from the equimolar salt of hexamethylene diamine and terephthalic acid is used as the structural unit obtained from the equimolar molar salt of the diamine having 2 to 8 carbon atoms and terephthalic acid.
  • the structural unit obtained from the equimolar molar salt of the diamine having 2 to 8 carbon atoms and terephthalic acid has, in order to realize excellent moldability in addition to high heat resistance, fluidity and low water absorption, 55 to 75 mol% of the structural unit and a structural unit obtained from 11-aminoundecanoic acid or undecane lactam
  • a copolymerized polyamide resin comprising 45 to 25 mol% is preferred.
  • Such copolymerized polyamide resin (A) includes conventional 6T nylon (for example, polyamide 6T6I composed of terephthalic acid / isophthalic acid / hexamethylenediamine, polyamide 6T66 composed of terephthalic acid / adipic acid / terephthalic acid, terephthalic acid / isophthalic acid / Polyamide 6T6I66 made of adipic acid / hexamethylenediamine, Polyamide 6T / M-5T made of terephthalic acid / hexamethylenediamine / 2-methyl-1,5-pentamethylenediamine, Made of terephthalic acid / hexamethylenediamine / ⁇ -caprolactam Polyamide 6T6, polyamide 6T / 4T, which is a defect of terephthalic acid / hexamethylenediamine / tetramethylenediamine), is not only greatly improved in water absorption, but also acid derived
  • a component (hereinafter referred to as 6T) corresponding to polyamide 6T obtained by co-condensation polymerization of hexamethylenediamine (6) and terephthalic acid (T) in an equimolar amount is specifically represented by the following formula (I). It is what is done.
  • the 6T component is a main component of the copolymerized polyamide resin (A) and has a role of imparting excellent heat resistance, mechanical properties, slidability and the like to the copolymerized polyamide resin (A).
  • the blending ratio of the 6T component in the copolymerized polyamide (A) is preferably 55 to 75 mol%, more preferably 60 to 70 mol%, still more preferably 62 to 68 mol%. If the blending ratio of the 6T component is less than the above lower limit, the polyamide component 6T, which is a crystal component, may be subjected to crystal inhibition by the copolymerization component, leading to a decrease in moldability and high temperature characteristics. Since it may become too high and may decompose during processing, it is not preferable.
  • PA11 polyamide 11 component obtained by polycondensation of 11-aminoundecanoic acid or undecane lactam is represented by the following formula (II).
  • the PA11 component is for improving water absorption and fluidity, which are disadvantages of the 6T component, and has the role of improving the moldability by adjusting the melting point and the temperature rising crystallization temperature of the copolymerized polyamide resin (A). It has the role of improving the fluidity at the time of melting by introducing a flexible skeleton by reducing the rate and improving troubles due to changes in physical properties and dimensional changes during water absorption.
  • the blending ratio of the PA11 component in the copolymerized polyamide resin (A) is preferably 45 to 25 mol%, more preferably 40 to 30 mol%, still more preferably 38 to 32 mol%.
  • the melting point of the copolymerized polyamide resin (A) is not sufficiently lowered, the moldability may be insufficient, and the water absorption rate of the obtained resin is reduced. Insufficient and may cause instability of physical properties such as deterioration of mechanical properties upon water absorption.
  • the melting point of the copolymerized polyamide resin (A) is too low, the crystallization speed is slow, the moldability may be adversely affected, and the amount of 6T component is reduced, resulting in mechanical properties. And heat resistance may be insufficient.
  • the copolymerized polyamide resin (A) is a structural unit obtained from an equimolar molar salt of the diamine having 2 to 8 carbon atoms and terephthalic acid, or the diamine, dicarboxylic acid, aminocarboxylic acid or lactam having 10 to 18 carbon atoms.
  • the structural unit other than the structural unit obtained from the above may be copolymerized up to a maximum of 20 mol%.
  • the component (X) has a role of imparting other characteristics not obtainable by the polyamide 6T or polyamide 11 to the copolymerized polyamide resin (A), or further improving the characteristics obtained by the polyamide 6T or polyamide 11. It is.
  • preferable component (X) examples include polyhexamethylene adipamide for imparting high crystallinity to the copolymerized polyamide resin (A), polydecamethylene terephthalamide for imparting further low water absorption, And dodecanamide.
  • the blending ratio of the component (X) in the copolymerized polyamide resin (A) is preferably up to 20 mol%, more preferably 10 to 20 mol%. When the proportion of the component (X) is less than the above lower limit, the effect of the component (X) may not be sufficiently exhibited. When the proportion exceeds the above upper limit, the amount of the essential component is reduced, and the original content of the copolymerized polyamide resin (A) The intended effect may not be sufficiently exhibited, which is not preferable.
  • Examples of the catalyst used for producing the copolymerized polyamide resin (A) include phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt, ammonium salt and ester thereof.
  • Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony.
  • As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like can be added.
  • alkali compounds such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, from a viewpoint of melt retention stability improvement.
  • the relative viscosity (RV) of the copolymerized polyamide resin (A) measured at 20 ° C. in 96% concentrated sulfuric acid is 0.4 to 4.0, preferably 1.0 to 3.0, more preferably 1.5. ⁇ 2.5.
  • Examples of a method for setting the relative viscosity of the polyamide within a certain range include a means for adjusting the molecular weight.
  • the copolymerized polyamide resin (A) can adjust the end group amount and the molecular weight of the polyamide by adjusting the molar ratio between the amino group amount and the carboxyl group to carry out polycondensation or adding a terminal blocking agent. it can.
  • timing for adding the end-capping agent examples include starting raw materials, starting polymerization, late polymerization, or finishing polymerization.
  • the end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but acid anhydrides such as monocarboxylic acid or monoamine, phthalic anhydride, Monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can be used.
  • end capping agent examples include aliphatic monoacids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
  • Alicyclic monocarboxylic acids such as carboxylic acid and cyclohexanecarboxylic acid, benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid, maleic anhydride Acid, phthalic anhydride, acid anhydrides such as hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc.
  • Aliphatic monoamines examples thereof include alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.
  • the acid value and amine value of the copolymerized polyamide resin (A) are preferably 0 to 200 eq / ton and 0 to 100 eq / ton, respectively.
  • the terminal functional group exceeds 200 eq / ton, not only gelation and deterioration are promoted during the melt residence, but also problems such as coloring and hydrolysis are caused even in the use environment.
  • the acid value and / or amine value is preferably 5 to 100 eq / ton in accordance with the reactivity and the reactive group.
  • the copolymerized polyamide resin (A) can be produced by a conventionally known method, and can be easily synthesized, for example, by subjecting a raw material monomer to a cocondensation reaction.
  • the order of the copolycondensation reaction is not particularly limited, and all the raw material monomers may be reacted at once, or a part of the raw material monomers may be reacted first, followed by the remaining raw material monomers.
  • the polymerization method is not particularly limited, but from raw material charging to polymer production may proceed in a continuous process, and after producing an oligomer once, the polymerization is advanced by an extruder or the like in another process, or the oligomer is solidified.
  • a method of increasing the molecular weight by phase polymerization may be used.
  • the proportion of each structural unit in the copolymerized polyamide to be synthesized can be controlled.
  • a copolymerized polyamide resin can also be produced by melt-kneading two or more types of polyamide resins in an extruder or a polymerization kettle to cause an amide exchange reaction.
  • the copolymerized polyamide resin (A) is present in a proportion of 25 to 90% by mass, preferably 40 to 75% by mass in the polyamide resin composition of the present invention.
  • the proportion of the copolymerized polyamide resin (A) is less than the above lower limit, the mechanical strength becomes low, and when it exceeds the above upper limit, the blending amount of the titanium oxide (B) and the reinforcing material (C) is insufficient, It becomes difficult to obtain the effect.
  • Titanium oxide (B) is blended to increase the surface reflectance of the reflector.
  • TiO dititanium trioxide
  • TiO 2 rutile type titanium dioxide
  • the average particle diameter of titanium oxide (B) is generally in the range of 0.05 to 2.0 ⁇ m, preferably 0.15 to 0.5 ⁇ m, and may be used alone or may have different particle diameters. Titanium may be used in combination.
  • the titanium oxide component concentration is 90% or more, preferably 95% or more, and more preferably 97% or more.
  • the titanium oxide (B) may be one that has been surface-treated with a metal oxide such as silica, alumina, zinc oxide, zirconia, a coupling agent, an organic acid, an organic polyhydric alcohol, or siloxane. it can.
  • a metal oxide such as silica, alumina, zinc oxide, zirconia, a coupling agent, an organic acid, an organic polyhydric alcohol, or siloxane. it can.
  • the proportion of titanium oxide (B) is 0.5 to 100 parts by mass, preferably 10 to 80 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A). If the ratio of titanium oxide (B) is less than the above lower limit, the surface reflectivity is lowered, and if it exceeds the upper limit, molding processability may be lowered, such as a significant decrease in physical properties and fluidity.
  • the reinforcing material (C) is blended to improve the moldability of the polyamide resin composition and the strength of the molded product, and uses at least one selected from a fibrous reinforcing material and a needle-shaped reinforcing material.
  • a fibrous reinforcing material include glass fiber, carbon fiber, boron fiber, ceramic fiber, and metal fiber.
  • the acicular reinforcing material include potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, and carbonic acid. Calcium whiskers, magnesium sulfate whiskers, wollastonite and the like can be mentioned.
  • glass fibers chopped strands or continuous filament fibers having a length of 0.1 mm to 100 mm can be used.
  • a glass fiber having a circular cross section and a non-circular cross section can be used as the cross-sectional shape of the glass fiber.
  • the diameter of the circular cross-section glass fiber is 20 ⁇ m or less, preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less.
  • a glass fiber having a non-circular cross section is preferred from the viewpoint of physical properties and fluidity.
  • Non-circular cross-section glass fibers include those that are substantially oval, substantially oval, or substantially bowl-shaped in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8. It is preferable.
  • the flatness is assumed to be a rectangle with the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of the rectangle is the major axis, and the length of the short side is the minor axis. It is the ratio of major axis / minor axis.
  • the thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 ⁇ m and the major axis is about 2 to 100 ⁇ m. Further, glass fibers are preferably used in the form of chopped strands which are formed into fiber bundles and cut to a fiber length of about 1 to 20 mm.
  • the difference in refractive index from the copolymerized polyamide resin is large. Therefore, the one having a higher refractive index by changing the glass composition or surface treatment is used. It is preferable to do.
  • the ratio of the reinforcing material (C) is 0 to 100 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A).
  • the reinforcing material (C) is not an essential component, but the proportion of 5 parts by mass or more is preferable because the mechanical strength of the molded product is improved.
  • the ratio of the reinforcing material (C) exceeds the above upper limit, the surface reflectance and the moldability tend to be lowered.
  • non-fibrous or non-needle filler (D) examples include reinforcing fillers, conductive fillers, magnetic fillers, flame retardant fillers, thermal conductive fillers, thermal yellowing suppression fillers, etc., according to purpose.
  • fillers may be used not only alone but also in combination of several kinds. Among these, talc is preferable because Tc1 is lowered and moldability is improved.
  • the addition amount of the filler may be selected as an optimum amount, but it is possible to add up to 50 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A), but the mechanical strength of the resin composition In view of the above, 0.1 to 20 parts by mass is preferable, and 1 to 10 parts by mass is more preferable.
  • the fibrous reinforcing material and filler are preferably treated with an organic treatment or a coupling agent, or are preferably used in combination with a coupling agent at the time of melt compounding.
  • the ring agent any of a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent may be used, and among them, an aminosilane coupling agent and an epoxy silane coupling agent are particularly preferable.
  • additives of conventional polyamide resin compositions for LED reflectors can be used.
  • Additives include stabilizers, impact modifiers, flame retardants, mold release agents, slidability improvers, colorants, fluorescent brighteners, plasticizers, crystal nucleating agents, thermoplastic resins other than polyamide, and the like.
  • Stabilizers include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and copper compounds. Copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate, and copper acetate can be used. Further, as a component other than the copper compound, an alkali metal halide compound is preferably contained.
  • organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and
  • alkali metal halide compound examples include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, bromide.
  • examples thereof include sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like.
  • These additives may be used alone or in combination of several kinds.
  • the addition amount of the stabilizer may be an optimal amount, but it is possible to add a maximum of 5 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A).
  • thermoplastic resin other than polyamide having a composition different from that of the copolymerized polyamide resin (A) may be added to the polyamide resin composition of the present invention.
  • Polymers other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polytetrafluoroethylene (PTFE), fluororesin, aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyether Imide (PEI), thermoplastic polyimide, polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyethersulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, Polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene ( E), polymethyl pentene (TPX), polys
  • thermoplastic resins can be blended in a molten state by melt kneading.
  • the thermoplastic resin may be made into a fiber or particle and dispersed in the polyamide resin composition of the present invention.
  • An optimum amount of the thermoplastic resin may be selected, but a maximum of 50 parts by mass can be added to 100 parts by mass of the copolymerized polyamide resin (A).
  • Impact modifiers include ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene- Polyolefin resins such as methacrylic acid ester copolymer, ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -Styrene copolymer (SIS), vinyl polymer resin such as acrylate copolymer, polybutylene terephthalate or polybutylene naphthalate as hard segment, polytetramethylene glycol or polycaprolactone or poly Polyester block copolymer in which the turbo sulfonate diol as
  • a reactive group capable of reacting with the polyamide is copolymerized.
  • the reactive group is a group capable of reacting with an amino group, a carboxyl group and a main chain amide group which are terminal groups of the polyamide resin.
  • Specific examples include a carboxylic acid group, an acid anhydride group, an epoxy group, an oxazoline group, an amino group, an isocyanate group, etc. Among them, an acid anhydride group is most excellent in reactivity.
  • thermoplastic resin having a reactive group that reacts with the polyamide resin is finely dispersed in the polyamide and is finely dispersed, so that the distance between the particles is shortened and the impact resistance is greatly improved [ S, Wu: Polymer 26, 1855 (1985)].
  • a combination of a halogen flame retardant and a flame retardant aid is good.
  • a halogen flame retardant brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride Polymers, brominated epoxy resins, brominated phenoxy resins, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, brominated cross-linked aromatic polymers, etc. are preferred.
  • halogen flame retardant is preferably a combination of dibromopolystyrene and the flame retardant auxiliary is any combination of antimony trioxide, sodium antimonate, and zinc stannate.
  • Non-halogen flame retardants include melamine cyanurate, red phosphorus, phosphinic acid metal salts, and nitrogen-containing phosphoric acid compounds. In particular, a combination of a phosphinic acid metal salt and a nitrogen-containing phosphoric acid compound is preferable.
  • the nitrogen-containing phosphoric acid compound a reaction product of melamine or a melamine condensate such as melam, melem, melon and polyphosphoric acid Or a mixture thereof.
  • flame retardants and flame retardant aids addition of hydrotalcite-based compounds and alkali compounds is preferable as metal corrosion prevention for molds and the like when these flame retardants are used.
  • the addition amount of the flame retardant may be an optimum amount, but it is possible to add a maximum of 50 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A).
  • the release agent examples include long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicone, polyethylene oxide, and the like.
  • the long chain fatty acid preferably has 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. Or a metal salt may be formed.
  • the amide compound include ethylene bisterephthalamide and methylene bisstearyl amide. These release agents may be used alone or as a mixture.
  • the addition amount of the release material may be selected as an optimum amount, but it is possible to add up to 5 parts by mass with respect to 100 parts by mass of the copolymerized polyamide resin (A).
  • the polyamide resin composition of the present invention has a DSC melting peak temperature present on the lowest temperature side due to the copolymerized polyamide resin (A) (in the case of a double peak, the melting peak temperature on the low temperature side), that is, the low temperature melting point.
  • Tm is 300 to 340 ° C., preferably 310 to 340 ° C.
  • Tm when Tm is less than the above lower limit, the crystallization rate is slow, and in some cases, molding may be difficult, and further, solder heat resistance may be reduced.
  • a Tm of 310 to 340 ° C. is preferable because it satisfies the reflow solder heat resistance of 280 ° C. and can be applied to a gold / tin eutectic solder process.
  • the polyamide resin composition of the present invention preferably has a temperature rising crystallization temperature (Tc1) existing on the lowest temperature side of 90 to 120 ° C. in DSC measurement.
  • Tc1 temperature rising crystallization temperature
  • the temperature rise crystallization temperature Tc1 is a temperature at which crystallization starts when the temperature is raised from room temperature. If the ambient temperature of the resin composition at the time of molding is lower than Tc1, crystallization hardly proceeds. On the other hand, when the temperature of the resin composition becomes higher than Tc1, crystallization proceeds easily, and dimensional stability, physical properties, etc. can be sufficiently exhibited. Since the reflector for LED is a very thin and fine molded product, the resin temperature after injection molding is considered to be almost the same as the mold temperature.
  • Tc1 of the resin composition is high, it is necessary to increase the mold temperature accordingly, leading to a decrease in workability.
  • Tc1 exceeds the upper limit, not only the mold temperature required for injection molding of the polyamide resin composition of the present invention becomes high and molding becomes difficult, but also in a short cycle of injection molding. Crystallization may not progress, causing molding difficulties such as insufficient mold release, or because crystallization is not sufficiently completed, deformation and crystal shrinkage occur during heating in the subsequent process, and sealing materials and lead frames The problem of peeling off occurs and the reliability is lacking.
  • Tc1 is less than the above lower limit, it is necessary to inevitably lower the glass transition temperature as a resin composition.
  • Tc1 is generally a temperature higher than the glass transition temperature, when Tc1 is less than 90 ° C., a lower value is required as the glass transition temperature. In that case, the physical properties greatly decrease or the physical properties after water absorption. Problems that cannot be maintained. Since the glass transition temperature needs to be kept relatively high, Tc1 needs to be at least 90 ° C. or higher.
  • the copolymerized polyamide resin (A) in the present invention is mainly composed of a structural unit obtained from an equimolar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid, and specifies an amide bond concentration and an aromatic ring concentration. Therefore, in addition to a high melting point and moldability, it has an excellent balance of low water absorption and fluidity, and also has excellent light resistance. For this reason, the polyamide resin composition of the present invention obtained from such a copolymerized polyamide resin (A) has a high melting point of 300 ° C. or higher and low water absorption in the molding of a reflector of a surface mount LED. Thin-walled, high-cycle molding is possible.
  • the polyamide resin composition of the present invention can be produced by blending the above-described constituent components by a conventionally known method. For example, each component is added during the polycondensation reaction of the copolymerized polyamide resin (A), the blended polyamide resin (A) and other components are dry blended, or a twin screw type extruder is used. The method of melt-kneading each structural component can be mentioned.
  • the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
  • the measured value described in the Example is measured by the following method.
  • Relative viscosity 0.25 g of polyamide resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C. using an Ostwald viscometer.
  • the cylinder temperature is set to the melting point of the resin + 20 ° C.
  • the mold temperature is set to 120 ° C.
  • the film gate has a length of 100 mm, a width of 100 mm
  • Injection molding was performed using a flat plate forming mold having a thickness of 1 mm. Molding was performed at an injection speed of 50 mm / sec, a holding pressure of 30 MPa, an injection time of 10 seconds, and a cooling time of 10 seconds.
  • the quality of the moldability was evaluated as follows. ⁇ : A molded product can be obtained without problems. ⁇ : Sprue sometimes remains in the mold.
  • the cylinder temperature is set to the melting point of the resin + 20 ° C.
  • the mold temperature is set to 140 ° C.
  • the length is 127 mm
  • the width is 12.6 mm
  • the thickness is 0.8 mm.
  • the test piece for the UL combustion test was injection molded to produce a test piece.
  • the test piece was left in an atmosphere of 85 ° C. and 85% RH (relative humidity) for 72 hours.
  • the test piece was heated in an air reflow oven (AIS-20-82C manufactured by ATEC) over 60 seconds from room temperature to 150 ° C, preheated, and then heated to 190 ° C at a rate of 0.5 ° C / min.
  • Preheating was performed. Thereafter, the temperature was raised to a predetermined set temperature at a rate of 100 ° C./min, held at the predetermined temperature for 10 seconds, and then cooled. The set temperature was increased from 240 ° C. every 5 ° C., and the highest set temperature at which surface swelling and deformation did not occur was defined as the reflow heat resistant temperature, which was used as an index of solder heat resistance.
  • ⁇ Reflow heat resistance temperature is 280 ° C or higher
  • Reflow heat resistance temperature is 260 ° C or higher and lower than 280 ° C
  • Reflow heat resistance temperature is lower than 260 ° C
  • Diffuse reflectance Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature is set to the melting point of the resin + 20 ° C, the mold temperature is set to 140 ° C, and a flat plate of 100mm length, 100mm width and 2mm thickness is injection molded. Then, a test piece for evaluation was produced. Using this test piece, an integrating sphere manufactured by Hitachi, Ltd. was installed in a self-recording spectrophotometer “U3500” manufactured by Hitachi, Ltd., and the reflectance at wavelengths from 350 nm to 800 nm was measured. For comparison of reflectance, diffuse reflectance at a wavelength of 460 nm was obtained. Barium sulfate was used as a reference.
  • the light reflectance at a wavelength of 460 nm of the test piece was measured at the time of non-irradiation and 48 hours after the irradiation, and evaluated by determining the retention rate relative to the time of non-irradiation.
  • ⁇ Retention rate 90% or more
  • ⁇ Retention rate less than 90%
  • the mixture was charged into a liter autoclave, pressurized with N 2 from normal pressure to 0.05 MPa, released, and returned to normal pressure. This operation was performed 3 times, N 2 substitution was performed, and then uniform dissolution was performed at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, heated to 240 ° C.
  • Examples 1 to 11 and Comparative Examples 1 to 6 The polyamide resin compositions of Examples 1 to 11 and Comparative Examples 1 to 6 were melt kneaded at a melting point of + 15 ° C. using a twin screw extruder STS-35 manufactured by Coperion Co., Ltd. in the proportions and weight ratios shown in Table 2. Got. In Table 2, the materials used other than the copolymerized polyamide resin are as follows. Titanium oxide (B): Ipehara Sangyo Co., Ltd.
  • Reinforcing material C: Glass fiber (manufactured by Nittobo Co., Ltd., CS-3J-324), acicular wallast (manufactured by NYCO, NYGLOS8) Filler (D): Talc (Micron White 5000A, Hayashi Kasei Co., Ltd.)
  • Mold release agent Magnesium stearate Stabilizer: Pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Specialty Chemicals)
  • the average number of carbon atoms between amide bonds and the ratio of carbon atoms on the aromatic ring satisfy the specific range of the present invention, and the melting point by DSC of the polyamide resin composition (melting peak on the lowest temperature side) If the temperature exceeds 300 ° C, it can be applied to the reflow soldering process. If the melting point exceeds 310 ° C, the reflow heat resistance temperature is 280 ° C or higher. Applicable soldering heat resistance, excellent adhesion to sealing materials and surface reflectance, which are important characteristics for LED applications, as well as moldability, fluidity, dimensional stability, low water absorption, and light resistance We were able to confirm the exceptional effect of being excellent.
  • Comparative Examples 1 to 4 Although the melting point of the polyamide resin composition exceeds 300 ° C. or 310 ° C., the reflow heat resistance temperature is less than 260 ° C. due to the high water absorption, and the solder heat resistance is satisfactory. It wasn't. Comparative Examples 5 and 6 have poor moldability, dimensional stability, and adhesion to the sealing material, and the reflow heat resistance temperature is 260 ° C. or higher and lower than 280 ° C., and the solder heat resistance is suitable for the gold / tin eutectic solder process. It was not possible.
  • the polyamide resin composition of the present invention is not only excellent in heat resistance, moldability, fluidity, and low water absorption, but also has excellent adhesion to a sealing material in LED applications, and also has excellent light resistance. Since the copolymerized polyamide resin is used, the surface mount type LED reflector can be industrially advantageously manufactured while highly satisfying necessary characteristics.

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Abstract

La composition de résine polyamide utilisée comme plaque réfléchissante pour DEL montée en surface ci-décrite contient : une résine polyamide copolymérisée (A) qui contient 50 % en moles ou plus d'un motif constitutif obtenu à partir d'un sel équimolaire d'acide téréphtalique et d'une diamine ayant de 2 à 8 atomes de carbone et qui satisfait les conditions (a) et (b) décrites ci-dessous ; de l'oxyde de titane (B) ; au moins un matériau de renforcement (C) qui est choisi dans le groupe constitué par les matériaux de renforcement fibreux et les matériaux de renforcement de type aiguille ; et une charge non fibreuse ou de type non-aiguille (D). La composition de résine polyamide selon l'invention est caractérisée en ce qu'elle satisfait la condition (c) décrite ci-dessous. (a) 7,5 ≤ nombre d'atomes de carbone dans la résine polyamide copolymérisée/ nombre de liaisons amide dans ladite résine polyamide copolymérisée ≤ 8,2 (b) 0,27 ≤ nombre d'atomes de carbone sur les cycles aromatiques de la résine polyamide copolymérisée/nombre total d'atomes de carbone dans ladite résine polyamide copolymérisée ≤ 0,35 (c) La plus basse température de pic de fusion DSC affectée à la résine polyamide copolymérisée (A) dans la composition de résine polyamide selon l'invention est de 300 à 340°C.
PCT/JP2011/068831 2010-08-27 2011-08-22 Composition de résine polyamide utilisée comme plaque réfléchissante pour del montées en surface WO2012026413A1 (fr)

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JP2014520190A (ja) * 2011-06-24 2014-08-21 アルケマ フランス 半芳香族ポリアミドを含む組成物と特に発光ダイオードを有する反射板のためのその使用
CN102604375A (zh) * 2012-03-09 2012-07-25 深圳市科聚新材料有限公司 一种低成本高阻燃增强聚酰胺及其制备方法
JP2013197543A (ja) * 2012-03-22 2013-09-30 Dainippon Printing Co Ltd 半導体発光装置、半導体発光装置用部品、半導体発光装置用反射体、半導体発光装置用反射体組成物、半導体発光装置用反射体の製造方法
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JP5733871B2 (ja) * 2013-01-11 2015-06-10 旭化成ケミカルズ株式会社 ポリアミド組成物及び成形品
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WO2014129364A1 (fr) * 2013-02-19 2014-08-28 ユニチカ株式会社 Composition de résine polyamide semi-aromatique
JPWO2014132883A1 (ja) * 2013-02-26 2017-02-02 東洋紡株式会社 表面実装型電気電子部品に使用する難燃性ポリアミド樹脂組成物
WO2014132883A1 (fr) * 2013-02-26 2014-09-04 東洋紡株式会社 Composition de résine polyamide ignifuge destinée à être utilisée dans un composant électrique/électronique du type monté en surface
WO2015019882A1 (fr) * 2013-08-05 2015-02-12 東洋紡株式会社 Composition de résine polyamide ignifuge
WO2016105162A1 (fr) * 2014-12-24 2016-06-30 삼성에스디아이 주식회사 Composition de résine de polyamide et article moulé produit à partir de cette dernière
JP7014510B2 (ja) 2016-10-07 2022-02-01 三菱エンジニアリングプラスチックス株式会社 成形品および成形品の製造方法
JP2021181579A (ja) * 2016-10-07 2021-11-25 三菱エンジニアリングプラスチックス株式会社 成形品および成形品の製造方法
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