WO2014129364A1 - Semi-aromatic polyamide resin composition - Google Patents

Semi-aromatic polyamide resin composition Download PDF

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WO2014129364A1
WO2014129364A1 PCT/JP2014/053242 JP2014053242W WO2014129364A1 WO 2014129364 A1 WO2014129364 A1 WO 2014129364A1 JP 2014053242 W JP2014053242 W JP 2014053242W WO 2014129364 A1 WO2014129364 A1 WO 2014129364A1
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semi
aromatic polyamide
resin composition
polyamide resin
acid
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PCT/JP2014/053242
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French (fr)
Japanese (ja)
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洋平 椛島
淳一 三井
太陽 甘利
佑次 記虎
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ユニチカ株式会社
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Priority to KR1020157014596A priority Critical patent/KR20150120331A/en
Priority to CN201480004931.7A priority patent/CN104919001B/en
Priority to JP2014530834A priority patent/JP5646120B1/en
Publication of WO2014129364A1 publication Critical patent/WO2014129364A1/en

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    • 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
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
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    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
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    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
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    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
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    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
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    • 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
    • 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
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
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    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/45144—Gold (Au) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched
    • H—ELECTRICITY
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    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481—Disposition
    • H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item

Definitions

  • the present invention relates to a semi-aromatic polyamide resin composition excellent in fluidity, reflow resistance and reflectivity in addition to heat resistance, whiteness and mechanical properties.
  • LEDs light-emitting diodes
  • a reflector that also serves as a housing is an important component.
  • the resin material constituting the reflector is required to have excellent whiteness and reflectivity, and heat resistance (reflow resistance) that can withstand a reflow soldering process generally performed when mounting on an electronic substrate. .
  • a semi-aromatic polyamide containing titanium oxide or calcium carbonate is known as a resin material suitable for a reflector.
  • Patent Document 1 discloses a resin composition in which titanium oxide is blended with polynonamethylene terephthalamide (PA9T), and Patent Document 2 discloses polyhexamethylene terephthalamide (PA6T) and polydecamethylene terephthalamide.
  • PA9T polynonamethylene terephthalamide
  • PA6T polyhexamethylene terephthalamide
  • PA10T polydecamethylene terephthalamide
  • the present invention solves the above-mentioned problems, and in addition to excellent heat resistance, whiteness, and mechanical properties, it is a semi-aromatic polyamide resin excellent in fluidity, reflow resistance, and reflectivity during injection molding.
  • An object is to provide a composition.
  • the present inventors have found that the above object can be achieved by using a semi-aromatic polyamide having a specific monocarboxylic acid component, and have reached the present invention. did. That is, the gist of the present invention is as follows.
  • the semi-aromatic polyamide (A) is composed of an aromatic dicarboxylic acid component, an aliphatic diamine component, and a monocarboxylic acid component
  • a semiaromatic polyamide resin composition comprising a monocarboxylic acid having a molecular weight of 140 or more as a monocarboxylic acid component, the content of which is 1 to 8% by mass of the semiaromatic polyamide (A) .
  • C fibrous reinforcing material
  • the present invention in addition to excellent heat resistance, whiteness, and mechanical properties, it is possible to provide a semi-aromatic polyamide resin composition excellent in fluidity, reflow resistance, and reflectivity during injection molding. .
  • the semi-aromatic polyamide resin composition of the present invention contains a semi-aromatic polyamide (A) and a white pigment (B), and the semi-aromatic polyamide (A) comprises an aromatic dicarboxylic acid component, an aliphatic diamine component, and the like. And a monocarboxylic acid component.
  • the aromatic dicarboxylic acid component constituting the semi-aromatic polyamide (A) preferably contains terephthalic acid in order to improve heat resistance.
  • aromatic dicarboxylic acids other than terephthalic acid include phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.
  • aromatic dicarboxylic acid component oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc.
  • dicarboxylic acids such as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
  • the aromatic dicarboxylic acid, aliphatic dicarboxylic acid and alicyclic dicarboxylic acid other than terephthalic acid have a copolymerization amount of the total number of moles of raw material monomers. It is preferable that it is 5 mol% or less with respect to this, and it is more preferable that it is not contained substantially.
  • examples of the aliphatic diamine component constituting the semiaromatic polyamide (A) include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,5-pentanediamine. 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, -Methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine.
  • 1,8-decanediamine, 1,10-decanediamine, and 1,12-dodecanediamine are preferable because of high crystallinity and improved whiteness and reflectivity. Molding fluidity and mechanical strength are preferred. In view of good balance, 1,10-decanediamine is more preferred.
  • the above-mentioned aliphatic diamine components may be used in combination.
  • the copolymerizable component other than the aliphatic diamine component examples include alicyclic diamines such as cyclohexanediamine, and diamine components such as aromatic diamines such as xylylenediamine and benzenediamine.
  • the alicyclic diamine and aromatic diamine may have a copolymerization amount of 5 mol% or less with respect to the total number of moles of raw material monomers. Preferably, it is substantially not included.
  • the semiaromatic polyamide (A) may be copolymerized with lactams such as caprolactam and laurolactam, and ⁇ -aminocarboxylic acids such as aminocaproic acid and 11-aminoundecanoic acid, if necessary.
  • the monocarboxylic acid component constituting the semi-aromatic polyamide (A) needs to contain a monocarboxylic acid having a molecular weight of 140 or more, and the molecular weight of the monocarboxylic acid is preferably 170 or more. .
  • the molecular weight of the monocarboxylic acid is less than 140, the effect of improving the molding fluidity of the semi-aromatic polyamide resin (A) is poor, the mold filling property at the time of molding is not sufficient, and the reflection of the obtained LED package In the plate, cracks (cracks) may occur due to heat during the reflow test, or peeling may occur between the transparent sealing resin.
  • Examples of monocarboxylic acids include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. Among these, aliphatic monocarboxylic acids are preferred because of their high effect of improving fluidity. Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Of these, stearic acid is preferred because of its high versatility.
  • Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid.
  • Examples of aromatic monocarboxylic acids having a molecular weight of 140 or more include alkylbenzoic acids such as 4-ethylbenzoic acid, 4-hexylbenzoic acid and 4-laurylbenzoic acid, and naphthoic acids such as 1-naphthoic acid and 2-naphthoic acid. And their derivatives.
  • a plurality of monocarboxylic acid components may be used in combination.
  • a monocarboxylic acid having a molecular weight of 140 or more and a monocarboxylic acid having a molecular weight of less than 140 may be used in combination.
  • the content of the monocarboxylic acid having a molecular weight of 140 or more needs to be 1 to 8% by mass, and preferably 2 to 5% by mass.
  • the content of the monocarboxylic acid having a molecular weight of 140 or more is less than 1% by mass, the molding fluidity is lowered, the molding cycle becomes long, and the appearance of the resulting molded article may be inferior.
  • the content exceeds 8% by mass the mechanical strength may be lowered.
  • the monocarboxylic acid content refers to the content of the monocarboxylic acid residue in the semi-aromatic polyamide (A), that is, the content of the monocarboxylic acid from which the terminal hydroxyl group is eliminated.
  • a polymer has a crystalline phase and an amorphous phase, and crystal characteristics such as a melting point are determined solely by the state of the crystalline phase. Since the terminal group in the polymer exists in an amorphous phase, the melting point does not change depending on the presence or absence and type of the terminal group. And since the monocarboxylic acid which acts as a terminal blocker also exists in an amorphous phase, unlike the case where other components are melt-kneaded, the melting point of the semi-aromatic polyamide is not lowered by the inclusion of the monocarboxylic acid.
  • the semi-aromatic polyamide (A) preferably has a melting point of 300 ° C. or higher.
  • the semi-aromatic polyamide (A) preferably has a relative viscosity of 1.8 or more when measured in 96% sulfuric acid at 25 ° C. and at a concentration of 1 g / dL. 2.6 is more preferable, and 1.9 to 2.4 is even more preferable.
  • the relative viscosity can be used as an index of molecular weight.
  • Semi-aromatic polyamide (A) can be produced using a conventionally known method such as a heat polymerization method or a solution polymerization method. Of these, the heat polymerization method is preferably used because it is industrially advantageous.
  • the heat polymerization method includes a step (i) of obtaining a reaction product from an aromatic dicarboxylic acid component, an aliphatic diamine component, and a monocarboxylic acid, and a step (ii) of polymerizing the obtained reaction product. Is mentioned.
  • aromatic dicarboxylic acid powder and monocarboxylic acid are mixed and heated in advance to a temperature not lower than the melting point of the aliphatic diamine and not higher than the melting point of the aromatic dicarboxylic acid.
  • a method of adding an aliphatic diamine to the dicarboxylic acid powder and the monocarboxylic acid without substantially containing water so as to keep the state of the aromatic dicarboxylic acid powder can be mentioned.
  • a suspension of a molten aliphatic diamine and a solid aromatic dicarboxylic acid is stirred and mixed to obtain a mixed solution, and then the melting point of the semi-aromatic polyamide finally produced
  • the salt formation reaction by the reaction of the aromatic dicarboxylic acid, the aliphatic diamine and the monocarboxylic acid, and the formation reaction of the low polymer by polymerization of the generated salt are carried out at a temperature of less than
  • the method of obtaining is mentioned. In this case, crushing may be performed while the reaction is performed, or crushing may be performed after the reaction is once taken out. In the step (i), the former is preferred because the shape of the reactant can be easily controlled.
  • the reaction product obtained in the step (i) is solid-phase polymerized at a temperature lower than the melting point of the semi-aromatic polyamide to be finally produced, and the molecular weight is increased to a predetermined molecular weight.
  • a method for obtaining a semi-aromatic polyamide is mentioned.
  • the solid phase polymerization is preferably performed in a stream of inert gas such as nitrogen at a polymerization temperature of 180 to 270 ° C. and a reaction time of 0.5 to 10 hours.
  • reaction apparatus for step (i) and step (ii) is not particularly limited, and a known apparatus may be used. Step (i) and step (ii) may be performed by the same apparatus or may be performed by different apparatuses.
  • the heating method in the heat polymerization method is not particularly limited, but the method of heating the reaction vessel with a medium such as water, steam, heat transfer oil, the method of heating the reaction vessel with an electric heater, the stirring generated by stirring A method using frictional heat accompanying the movement of contents such as heat can be mentioned. Moreover, you may combine these methods.
  • a polymerization catalyst may be used in order to increase the polymerization efficiency.
  • the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid or salts thereof, and the addition amount of the polymerization catalyst is usually based on the total moles of aromatic dicarboxylic acid and aliphatic diamine. It is preferable to use at 2 mol% or less.
  • Examples of the white pigment (B) constituting the semi-aromatic polyamide resin composition of the present invention include titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, calcium carbonate, and aluminum oxide. Titanium, barium sulfate and calcium carbonate are preferred. By using two or more kinds of white pigments among titanium oxide, barium sulfate, and calcium carbonate, the reflectance retention can be improved.
  • Titanium oxide is preferably a rutile type having a high refractive index and good light stability.
  • the particle diameter of titanium oxide is preferably 0.05 to 2.0 ⁇ m, and more preferably 0.05 to 0.5 ⁇ m.
  • the barium sulfate may be naturally produced or synthetic, and the former includes barite and the latter includes precipitated barium sulfate.
  • the particle size of barium sulfate is preferably 0.005 to 10 ⁇ m, and more preferably 0.01 to 1 ⁇ m.
  • Examples of calcium carbonate include calcite (calcite), aragonite (aragonite), natural calcium carbonate (heavy calcium carbonate), and synthetic calcium carbonate (precipitated calcium carbonate). Among them, calcite and aragonite are preferable.
  • the particle size of calcium carbonate is preferably 0.05 to 10 ⁇ m, and more preferably 0.1 to 5 ⁇ m.
  • the white pigment (B) may be surface-treated for neutralization or for improving wettability with the resin.
  • the surface treatment agent include metal oxides such as alumina, silica, zinc oxide and zirconium oxide, organic acids such as stearic acid or metal salts thereof, polyols, silane coupling agents, and titanium coupling agents.
  • the content of the white pigment (B) needs to be 10 to 150 parts by weight, preferably 20 to 130 parts by weight, with respect to 100 parts by weight of the semi-aromatic polyamide (A).
  • the amount is more preferably part by mass, and further preferably 30 to 100 parts by mass.
  • the content of the white pigment (B) is less than 10 parts by mass, the whiteness and the reflectance may be lowered, and the obtained molded product may be discolored by heat and have poor reflow resistance.
  • the content exceeds 150 parts by mass not only the reinforcement efficiency of the mechanical strength is lowered, but also the workability at the time of melt kneading is lowered, and it becomes difficult to obtain a semi-aromatic polyamide resin composition pellet. Sometimes.
  • the semi-aromatic polyamide resin composition of the present invention may contain a fibrous reinforcing material (C) from the viewpoint of improving mechanical strength.
  • the fibrous reinforcing material (C) include glass fiber, potassium titanate fiber, alumina fiber, silica fiber, zirconia fiber, silicon carbide fiber, ceramic fiber, wollastonite, sepiolite, and attapulgite.
  • glass fiber, potassium titanate fiber, wollastonite, sepiolite, and attapulgite are preferable in terms of maintaining whiteness without melting at the melting temperature of the semi-aromatic polyamide (A), and glass fiber and potassium titanate fiber.
  • the combined use of glass fiber and wollastonite is preferred.
  • the glass fiber is preferably surface-treated with a silane coupling agent.
  • a silane coupling agent may be dispersed in a sizing agent for bundling glass fibers to treat the glass fibers.
  • the silane coupling agent include vinyl silanes, acrylic silanes, epoxy silanes, and amino silanes, and aminosilanes are preferred because it is easy to obtain an adhesion effect between the semi-aromatic polyamide (A) and the glass fiber. .
  • the fiber length of the fibrous reinforcing material (C) is preferably 0.1 to 7 mm, and more preferably 0.5 to 6 mm.
  • the fiber diameter is preferably 3 to 20 ⁇ m, more preferably 5 to 13 ⁇ m. When the fiber length is 0.1 to 7 mm and the fiber diameter is 3 to 20 ⁇ m, the fiber can be efficiently reinforced without adversely affecting the moldability.
  • the content thereof is preferably 10 to 80 parts by mass, and preferably 15 to 60 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide (A). More preferred is 20 to 40 parts by mass.
  • the content of the fibrous reinforcing material (C) is 5 parts by mass, the effect of improving the mechanical strength may not be obtained.
  • the reinforcing efficiency of the mechanical strength is lowered, the workability at the time of melt kneading is lowered, and it may be difficult to obtain a semi-aromatic polyamide resin composition pellet.
  • the reflectance may decrease due to the fibrous reinforcing material floating on the surface of the molded body.
  • the method of incorporating the fibrous reinforcing material (C) is not particularly limited as long as the reinforcing effect is not impaired, but melt kneading using a biaxial kneader is preferable.
  • the kneading temperature must be equal to or higher than the melting point of the semi-aromatic polyamide (A), and is preferably less than (melting point + 80 ° C.). If the kneading temperature is lower than the melting point, the kneader is overloaded, and problems such as vent-up may occur. When the kneading temperature is too high, the semi-aromatic polyamide (A) may be decomposed or yellowed.
  • the semi-aromatic polyamide resin composition of the present invention preferably further contains a metal hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide.
  • a metal hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide.
  • the metal hydroxide may be surface-treated for neutralization or for improving wettability with the resin.
  • the content of the metal hydroxide is preferably 0.1 to 30 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide (A).
  • the semi-aromatic polyamide resin composition of the present invention may further contain an antioxidant.
  • the antioxidant is usually contained for the purpose of preventing the molecular weight of the semi-aromatic polyamide (A) from being lowered and preventing the color from deteriorating.
  • the residence stability of the resin composition can be improved. That is, when the semi-aromatic polyamide resin composition containing the fibrous reinforcement (C) stays in a high-temperature cylinder for a long time, the surface treatment agent of the fibrous reinforcement (C) is thermally decomposed and mechanically May cause a decrease in strength.
  • the resin composition stays in the cylinder for a long time, that is, when the molding cycle is long at the time of injection molding or the injection amount is small and the resin stays in the cylinder for a long time. Even in this case, a decrease in the tensile strength of the resin composition can be suppressed.
  • the content thereof is preferably 0.05 to 5 parts by mass and preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide (A). Further preferred.
  • the content is less than 0.05 parts by mass, the above effects are small, and when it exceeds 5 parts by mass, the mold is likely to become dirty during molding, and molding defects may occur.
  • antioxidants examples include phosphorus antioxidants, hindered phenol antioxidants, hindered amine antioxidants, triazine compounds, and sulfur compounds, among which phosphorus antioxidants and hindered phenols. Of these, antioxidants and sulfur compounds are preferred.
  • the phosphorus-based antioxidant may be an inorganic compound or an organic compound.
  • Phosphorus antioxidants include, for example, monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, and other inorganic salts, triphenyl phosphate Phyto, trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (nonyl
  • bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4-biphenylylene phosphite are preferable. . These may be used alone or in combination. Examples of commercially available phosphorus antioxidants include “ADEKA STAB” PEP-8, PEP-36 and PEP-4C manufactured by Adeka, and “Hostanox” P-EPQ manufactured by Clariant.
  • hindered phenol antioxidant examples include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′- Methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6- Hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl -4-hydroxyphenyl) -propionate], 2,2'-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl)
  • hindered phenol antioxidants examples include “ADEKA STAB” AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, and AO— manufactured by Adeka Corporation. 330, “Irganox” 245, 259, 565, 1010, 1035, 1076, 1098, 1222, 1330, 1425, 1520, 3114, 5057 manufactured by Ciba Specialty Chemical Co., Ltd.
  • sulfur-based antioxidants include distearyl 3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole, didodecyl 3,3′-thiodiprote. Pionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,4'-thiodipropionate, 2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3 Mention may be made of propanediyl esters.
  • distearyl 3,3′-thiodipropionate and pentaerythrityl tetrakis (3-laurylthiopropionate) are preferable. These may be used alone or in combination.
  • sulfur-based antioxidants include “Sumilyzer” TP-D manufactured by Sumitomo Chemical Co., Ltd.
  • the semi-aromatic polyamide resin composition of the present invention may further contain a light stabilizer.
  • a light stabilizer when titanium oxide is used as the white pigment, it is preferable to contain a light stabilizer because titanium oxide may promote photolysis.
  • the light stabilizer include a benzophenone compound, a benzotriazole compound, a salicylate compound, a hindered amine compound (HALS), and a hindered phenol compound, and among them, affinity with a semi-aromatic polyamide and heat resistance. Is high, hindered amine compounds are preferred.
  • Light stabilizers include, for example, “Nyrostub” S-EED manufactured by Clariant Japan, “Biosorb” 04 manufactured by Kyodo Yakuhin Co., Ltd., “Tinubin” 622, 765 manufactured by Ciba Specialty Chemicals, and “Siasorb” manufactured by Cytec. UV-3346, “Adeka Stub” LA-57 manufactured by Asahi Denka Kogyo Co., Ltd., and “Timasorb” 119, 944 manufactured by BASF.
  • the content thereof is preferably 0.1 to 5 parts by mass and preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide (A). Further preferred.
  • the reflectance retention can be improved.
  • an antioxidant and a light stabilizer in combination.
  • an antioxidant and a light stabilizer in combination, it is possible to improve the retention stability during molding, efficiently prevent light deterioration due to ultraviolet rays during use, and improve reflectance and whiteness. .
  • the semi-aromatic polyamide resin composition of the present invention may further contain an optical brightener.
  • optical brightener include bisbenzoxazole, bis (styryl) biphenyl, phenylcoumarin (specifically, triazine-phenylcoumarin, benzotriazole-phenylcoumarin and naphthotriazole-phenylcoumarin), and triazine-stilbene. It is done.
  • fluorescent brighteners include “Chino Pearl” OB manufactured by Ciba Specialty Chemicals, “Hostanox” KS manufactured by Clariant, and “East Bright” OB-1 manufactured by Eastman.
  • the semi-aromatic polyamide resin composition of the present invention may contain other additives as necessary.
  • the other additives include fillers such as plate-like reinforcing materials, talc, swellable clay minerals, silica and glass beads, antistatic agents, flame retardants, and flame retardant aids.
  • the effect of the method of adding the fibrous reinforcing material, white pigment, antioxidant, light stabilizer, fluorescent whitening agent and other additives to the semi-aromatic polyamide resin composition of the present invention must be impaired.
  • the method is not particularly limited, and examples thereof include a method of adding at the time of polymerization or melt kneading of the semi-aromatic polyamide (A).
  • Examples of the method for molding the semi-aromatic polyamide resin composition of the present invention include an injection molding method, an extrusion molding method, and a blow molding method, and among these, the injection molding method is preferable.
  • the injection molding machine is not particularly limited, and examples thereof include a screw inline type injection molding machine and a plunger type injection molding machine.
  • a semi-aromatic polyamide resin composition heated and melted in a cylinder of an injection molding machine is weighed for each shot, injected into a mold in a molten state, cooled to a predetermined shape, solidified, and then formed into a molded body. Removed from the mold.
  • the resin temperature at the time of injection molding must be equal to or higher than the melting point of the semi-aromatic polyamide resin composition, and is preferably less than (melting point + 100 ° C.).
  • the semi-aromatic polyamide resin composition is heated and melted, it is preferable to use a semi-aromatic polyamide resin composition that has been sufficiently dried. If the water content is large, the resin foams in the cylinder of the injection molding machine, and it may be difficult to obtain an optimal molded body.
  • the water content of the semi-aromatic polyamide resin composition used for injection molding is preferably less than 0.3% by mass, and more preferably less than 0.1% by mass.
  • the semi-aromatic polyamide (A) constituting the resin composition of the present invention has a higher melting point than the polyamide 6 and the polyamide 66 and a high melting temperature for obtaining a molded product.
  • the resin is likely to deteriorate and decomposition gas is likely to be generated. Therefore, in order to obtain a molded article having excellent heat resistance by molding the semi-aromatic polyamide resin composition of the present invention, the molding cycle should be shortened and the residence of the molten resin in the molding machine cylinder should be suppressed as much as possible. Is preferred.
  • the semi-aromatic polyamide resin composition of the present invention is excellent in whiteness, reflectance, and reflow resistance in addition to mechanical strength, heat resistance and moldability. Can be used for applications.
  • Examples of automobile parts include electrical components such as a lamp reflector, a lamp housing, a lamp extension, and a lamp socket.
  • Examples of the electric / electronic component include a reflector of an LED package.
  • the LED package can be used for an LED lighting device.
  • Measuring method (1) Relative viscosity of semi-aromatic polyamide 96% by mass sulfuric acid was used as a solvent, and the concentration was measured at a concentration of 1 g / dL and 25 ° C.
  • MFR Melt flow rate
  • the whiteness W was calculated by the following formula.
  • Reflectivity of semi-aromatic polyamide resin composition, retention ratio of reflectance after heat treatment The molded piece obtained in (6) above is heat-treated in an oven at 140 ° C. for 300 hours, and molded before and after the treatment. About the piece, the reflectance at a wavelength of 460 nm was measured with a spectrophotometer SE6000 (light source: C-2) manufactured by Nippon Denshoku.
  • the reflectance before treatment is preferably 85% or more, more preferably 90% or more
  • the reflectance after treatment is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more.
  • a semi-aromatic polyamide resin composition is injection-molded on a lead frame set in a mold to produce a reflector, and then a blue LED element made of InGaN-based blue is used as a semiconductor light emitting element. And fixed with silver paste.
  • a gold wire was attached, and then a transparent sealing resin was injected, heated at 150 ° C. for 1 hour, and cured to obtain a surface-mounted LED package shown in FIG.
  • 1 is a reflecting plate
  • 2 is a lead frame
  • 3 is a gold wire
  • 4 is a transparent sealing resin
  • 5 is a semiconductor light emitting element.
  • the reflecting plate 1 has discoloration or cracks, or there is peeling between the reflecting plate 1 and the transparent sealing resin 4.
  • Non-defective product The reflecting plate 1 is not discolored or cracked, and there is no peeling between the reflecting plate 1 and the transparent sealing resin 4.
  • the defective product rate is 95% or more “ ⁇ ”, 90% or more “ ⁇ ”. , Less than 90% was evaluated as “x”, and the reflow resistance was evaluated.
  • Aromatic dicarboxylic acid component / TPA terephthalic acid / IPA: isophthalic acid
  • White pigment Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Tyco PC-3, average particle size 0.21 ⁇ m)
  • BS barium sulfate (manufactured by Sakai Chemical Industry, Varifine BF-20, average particle size 0.03 ⁇ m)
  • CC calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Brilliant-1500, average particle size 0.20 ⁇ m)
  • Fibrous reinforcing material / GF-1 Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-786H, average fiber diameter 10.5 ⁇ m, average fiber length 3 mm)
  • GF-2 glass fiber (manufactured by Nittobo, CS3J256, average fiber diameter 11 ⁇ m, average fiber length 3 mm)
  • Antioxidant AO-1 Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (phosphorus antioxidant, manufactured by Adeka, Adeka Stub PEP-36)
  • AO-2 3,9-bis [2- ⁇ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ⁇ -1,1-dimethylethyl] 2,4,8,10 -Tetraoxaspiro (5,5) undecane (hindered phenol-based antioxidant, manufactured by Adeka, AO-80)
  • AO-3 Pentaerythrityl tetrakis (3-lauryl thiopropionate) (sulfur-based antioxidant, manufactured by Sumitomo Chemical Co., Ltd., Smither TP-D)
  • Light stabilizer LS 2-ethyl-2-ethoxy-oxalanilide (manufactured by Clariant Japan, Nyrostab S-EED)
  • Fluorescent whitening agent • FB 2,2 ′-(1,2-ethylenediyldi-4,1-phenylene) bisbenzoxazole (Eastman, East Bright OB-1)
  • Production Example 1 8.70 kg of powdered terephthalic acid (TPA) as an aromatic dicarboxylic acid component, 0.32 kg of stearic acid (STA) having a molecular weight of 284 as monocarboxylic acid, and sodium hypophosphite monohydrate as a polymerization catalyst. 3 g was put into a ribbon blender type reactor and heated to 170 ° C. with stirring at a rotation speed of 30 rpm under nitrogen sealing. Thereafter, while maintaining the temperature at 170 ° C. and maintaining the rotation speed at 30 rpm, 4.98 kg of 1,10-decanediamine (DDA) heated to 100 ° C. as an aliphatic diamine component was added using a liquid injection device.
  • TPA powdered terephthalic acid
  • STA stearic acid
  • DDA 1,10-decanediamine
  • reaction product was polymerized by heating at 250 ° C. and a rotation speed of 30 rpm for 8 hours in the same reaction apparatus in a nitrogen stream, taken into a strand, and then cooled and solidified by passing it through a water bath. Cutting with a pelletizer gave semi-aromatic polyamide (P-1) pellets.
  • Production Examples 2 to 17 Semi-aromatic polyamide pellets (P-2 to P-17) were obtained in the same manner as in Production Example 1 except that the types and blending amounts of the components were changed so that the resin composition shown in Table 1 was obtained.
  • Table 1 shows the composition, melting point and relative viscosity of the semi-aromatic polyamides obtained in Production Examples 1 to 17.
  • Example 1 Semi-fragrance weighed using Kubota's loss-in-weight continuous quantitative feeder CE-W-1 at the main supply port of the same-direction twin-screw extruder (TEM 26SS, Toshiba Machine, screw diameter 26 mm, L / D49) Group polyamide (P-1) 100 parts by weight, white pigment (TI) 40 parts by weight, antioxidant (AO-1) 0.5 part by weight, light stabilizer (LS) 0.5 part by weight, fluorescent whitening agent (FB) 0.1 parts by mass was supplied, and 25 parts by mass of the fibrous reinforcing material (GF-1) was supplied from the side feeder, and melt kneading was performed. The melting temperature was 320 ° C.
  • the screw rotation speed was 250 rpm, and the discharge rate was 35 kg / hour. Then, after taking up in the form of a strand, it was cooled and solidified through a water tank, and cut with a pelletizer to obtain a semi-aromatic polyamide resin composition.
  • Examples 2-31 and Comparative Examples 1, 3-7 A semi-aromatic polyamide resin composition was obtained in the same manner as in Example 1 except that the resin composition was changed so as to have the types and contents shown in Tables 2 and 3. Glass fiber was supplied from the side feeder, and the other was supplied from the main supply port.
  • Comparative Example 2 Except for changing the content of the white content, the same operation as in Example 1 was performed, but since the content of the white pigment was high, the strands were cut and a semi-aromatic polyamide resin composition could not be obtained. It was.
  • Tables 2 and 3 show the compositions and characteristics of the semi-aromatic polyamide resin compositions obtained in Examples and Comparative Examples.
  • Example 1 to 31 in addition to heat resistance, whiteness, bending strength, and flexural modulus, the fluidity, reflow resistance, and reflectance were all excellent.
  • Example 26 and 27 in which two types of titanium oxide, calcium carbonate, and barium sulfate were used in combination as white pigments, the retention rate of reflectance was improved as compared with Example 25 using only titanium oxide. It was.
  • Example 31 containing a metal hydroxide (magnesium hydroxide) an improvement in the retention rate of the reflectance was observed as compared with Example 1 not containing a metal hydroxide.
  • Comparative Example 1 since the content of the white pigment was small, the whiteness and reflectance were low, and the reflow resistance was inferior.
  • Comparative Example 3 since the monocarboxylic acid content in the semi-aromatic polyamide was less than the range specified in the present invention, the molding fluidity was lowered and the flow length was short.
  • Comparative Example 4 the bending strength was low because the content of monocarboxylic acid in the semi-aromatic polyamide was larger than the range specified in the present invention.
  • caproic acid having a molecular weight of less than 140 was used as the monocarboxylic acid in the semi-aromatic polyamide, so the molding fluidity improvement effect was poor and the flow length was short.
  • Comparative Example 6 since benzoic acid having a molecular weight of less than 140 was used as the monocarboxylic acid in the semi-aromatic polyamide, the flow length was short as in Comparative Example 5. Moreover, it was inferior to reflow resistance. In Comparative Example 7, when a semi-aromatic polyamide having a reduced benzoic acid content and a lower relative viscosity was used, the flow length increased, but the reflow resistance remained inferior. In contrast to Example 1, although the monocarboxylic acid content was almost the same, the reflectance before the treatment was low, and the reflectance retention was also low.

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Abstract

A semi-aromatic polyamide resin composition comprising 100 parts by mass of a semi-aromatic polyamide (A) and 10 to 150 parts by mass of a white pigment (B), said semi-aromatic polyamide resin composition being characterized in that the semi-aromatic polyamide (A) comprises an aromatic dicarboxylic acid component, an aliphatic diamine component and a monocarboxylic acid component, the monocarboxylic acid component comprises a monocarboxylic acid having a molecular weight of 140 or more, and the content of the monocarboxylic acid is 1 to 8 mass% relative to the whole amount of the semi-aromatic polyamide (A).

Description

半芳香族ポリアミド樹脂組成物Semi-aromatic polyamide resin composition
　本発明は、耐熱性、白色度、機械的特性に加えて、流動性、耐リフロー性、反射性に優れた半芳香族ポリアミド樹脂組成物に関するものである。 The present invention relates to a semi-aromatic polyamide resin composition excellent in fluidity, reflow resistance and reflectivity in addition to heat resistance, whiteness and mechanical properties.
　発光ダイオード（ＬＥＤ）は、低消費電力、長寿命の光源であることから、照明や表示素子として需要が急速に拡大し、また大型化、ハイパワー化が進んでいる。ＬＥＤにおいては、光を効率的に利用するため、ハウジングを兼ねたリフレクターは重要な構成部品である。リフレクターを構成する樹脂材料には、優れた白色度や反射率が求められるとともに、電子基板への実装時に一般的に行なわれるリフロー半田工程に耐えられる耐熱性（耐リフロー性）が求められている。 Since light-emitting diodes (LEDs) are light sources with low power consumption and long life, the demand for lighting and display elements is rapidly expanding, and the size and power are increasing. In the LED, in order to efficiently use light, a reflector that also serves as a housing is an important component. The resin material constituting the reflector is required to have excellent whiteness and reflectivity, and heat resistance (reflow resistance) that can withstand a reflow soldering process generally performed when mounting on an electronic substrate. .
　リフレクターに適した樹脂材料として、酸化チタンや炭酸カルシウムを含有させた半芳香族ポリアミドが知られている。例えば、特許文献１には、ポリノナメチレンテレフタルアミド（ＰＡ９Ｔ）に酸化チタンを配合した樹脂組成物が開示され、特許文献２には、ポリヘキサメチレンテレフタルアミド（ＰＡ６Ｔ）系やポリデカメチレンテレフタルアミド（ＰＡ１０Ｔ）系の共重合樹脂に酸化チタン、炭酸カルシウムおよびガラス繊維を配合した樹脂組成物が開示されている。 A semi-aromatic polyamide containing titanium oxide or calcium carbonate is known as a resin material suitable for a reflector. For example, Patent Document 1 discloses a resin composition in which titanium oxide is blended with polynonamethylene terephthalamide (PA9T), and Patent Document 2 discloses polyhexamethylene terephthalamide (PA6T) and polydecamethylene terephthalamide. A resin composition in which titanium oxide, calcium carbonate, and glass fiber are blended with a (PA10T) copolymer resin is disclosed.
特開２００４－７５９９４号公報JP 2004-75994 A 特開２０１１－２４１３９８号公報JP 2011-241398 A
　しかしながら、特許文献１、２の半芳香族ポリアミド樹脂組成物は、射出成形時の流動性が低いため、射出成形時に薄肉部の充填が不足したり、金型転写性が不良となり、成形されたリフレクターは、表面の平滑性が低下して、反射率が低下する問題や、耐リフロー性が低下し、ひび割れ（クラック）が発生したり、透明封止樹脂との間に剥離が生じたりする問題があった。 However, since the semi-aromatic polyamide resin compositions of Patent Documents 1 and 2 have low fluidity at the time of injection molding, the thin-walled portion was insufficiently filled at the time of injection molding, or the mold transferability was poor and molded. The reflector has a problem that the smoothness of the surface is lowered and the reflectivity is lowered, the reflow resistance is lowered, cracks are generated, and peeling is caused between the transparent sealing resin and the reflector. was there.
　本発明は、上記課題を解決するものであって、優れた耐熱性、白色度、機械的特性に加えて、射出成形時の流動性、耐リフロー性、反射性に優れた半芳香族ポリアミド樹脂組成物を提供することを目的とする。 The present invention solves the above-mentioned problems, and in addition to excellent heat resistance, whiteness, and mechanical properties, it is a semi-aromatic polyamide resin excellent in fluidity, reflow resistance, and reflectivity during injection molding. An object is to provide a composition.
　本発明者らは、前記課題を解決するため鋭意研究を重ねた結果、特定のモノカルボン酸成分を有する半芳香族ポリアミドを用いることにより、上記目的が達成されることを見出し、本発明に到達した。すなわち、本発明の要旨は下記の通りである。
［１］半芳香族ポリアミド（Ａ）１００質量部と、白色顔料（Ｂ）１０～１５０質量部とを含有する半芳香族ポリアミド樹脂組成物であって、
半芳香族ポリアミド（Ａ）が、芳香族ジカルボン酸成分と、脂肪族ジアミン成分と、モノカルボン酸成分とから構成され、
モノカルボン酸成分として、分子量が１４０以上のモノカルボン酸を含有し、その含有量が、半芳香族ポリアミド（Ａ）の１～８質量％であることを特徴とする半芳香族ポリアミド樹脂組成物。
［２］さらに繊維状強化材（Ｃ）を１０～８０質量部含有することを特徴とする［１］記載の半芳香族ポリアミド樹脂組成物。
［３］モノカルボン酸が、脂肪族モノカルボン酸であることを特徴とする［１］または［２］記載の半芳香族ポリアミド樹脂組成物。
［４］脂肪族モノカルボン酸が、ステアリン酸であることを特徴とする［３］記載の半芳香族ポリアミド樹脂組成物。
［５］脂肪族ジアミン成分が、１，１０－デカンジアミンを含有することを特徴とする［１］～［４］のいずれかに記載の半芳香族ポリアミド樹脂組成物。
［６］白色顔料（Ｂ）が、酸化チタン、炭酸カルシウムおよび硫酸バリウムからなる群より選ばれる１種以上であることを特徴とする［１］～［５］のいずれかに記載の半芳香族ポリアミド樹脂組成物。
［７］さらに、水酸化アルミニウム、水酸化マグネシウムおよび水酸化カルシウムからなる群より選ばれる１種以上の金属水酸化物を０．１～３０質量部含有することを特徴とする［１］～［６］のいずれかに記載の半芳香族ポリアミド樹脂組成物。
［８］上記［１］～［７］のいずれかに記載の半芳香族ポリアミド樹脂組成物を成形してなる反射板。
［９］上記［８］記載の反射板を備えるＬＥＤパッケージ。
［１０］上記［９］記載のＬＥＤパッケージを備える照明装置。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by using a semi-aromatic polyamide having a specific monocarboxylic acid component, and have reached the present invention. did. That is, the gist of the present invention is as follows.
[1] A semi-aromatic polyamide resin composition containing 100 parts by mass of a semi-aromatic polyamide (A) and 10 to 150 parts by mass of a white pigment (B),
The semi-aromatic polyamide (A) is composed of an aromatic dicarboxylic acid component, an aliphatic diamine component, and a monocarboxylic acid component,
A semiaromatic polyamide resin composition comprising a monocarboxylic acid having a molecular weight of 140 or more as a monocarboxylic acid component, the content of which is 1 to 8% by mass of the semiaromatic polyamide (A) .
[2] The semi-aromatic polyamide resin composition according to [1], further comprising 10 to 80 parts by mass of a fibrous reinforcing material (C).
[3] The semiaromatic polyamide resin composition according to [1] or [2], wherein the monocarboxylic acid is an aliphatic monocarboxylic acid.
[4] The semi-aromatic polyamide resin composition according to [3], wherein the aliphatic monocarboxylic acid is stearic acid.
[5] The semi-aromatic polyamide resin composition according to any one of [1] to [4], wherein the aliphatic diamine component contains 1,10-decanediamine.
[6] The semi-aromatic according to any one of [1] to [5], wherein the white pigment (B) is at least one selected from the group consisting of titanium oxide, calcium carbonate, and barium sulfate. Polyamide resin composition.
[7] Further comprising 0.1 to 30 parts by mass of one or more metal hydroxides selected from the group consisting of aluminum hydroxide, magnesium hydroxide and calcium hydroxide [1] to [1] 6] The semi-aromatic polyamide resin composition according to any one of [6].
[8] A reflector obtained by molding the semi-aromatic polyamide resin composition according to any one of [1] to [7].
[9] An LED package comprising the reflector according to [8] above.
[10] A lighting device comprising the LED package according to [9].
　本発明によれば、優れた耐熱性、白色度、機械的特性に加えて、射出成形時の流動性、耐リフロー性、反射性に優れた半芳香族ポリアミド樹脂組成物を提供することができる。 According to the present invention, in addition to excellent heat resistance, whiteness, and mechanical properties, it is possible to provide a semi-aromatic polyamide resin composition excellent in fluidity, reflow resistance, and reflectivity during injection molding. .
本発明の樹脂組成物を反射板に用いた表面実装型ＬＥＤパッケージの断面を示す模式図である。It is a schematic diagram which shows the cross section of the surface mount type LED package which used the resin composition of this invention for the reflecting plate.
　以下、本発明を詳細に説明する。
　本発明の半芳香族ポリアミド樹脂組成物は、半芳香族ポリアミド（Ａ）と白色顔料（Ｂ）とを含有し、半芳香族ポリアミド（Ａ）は、芳香族ジカルボン酸成分と脂肪族ジアミン成分とモノカルボン酸成分とから構成される。 Hereinafter, the present invention will be described in detail.
The semi-aromatic polyamide resin composition of the present invention contains a semi-aromatic polyamide (A) and a white pigment (B), and the semi-aromatic polyamide (A) comprises an aromatic dicarboxylic acid component, an aliphatic diamine component, and the like. And a monocarboxylic acid component.
　本発明において、半芳香族ポリアミド（Ａ）を構成する芳香族ジカルボン酸成分は、耐熱性を高めるために、テレフタル酸を含有することが好ましい。 In the present invention, the aromatic dicarboxylic acid component constituting the semi-aromatic polyamide (A) preferably contains terephthalic acid in order to improve heat resistance.
　テレフタル酸以外の芳香族ジカルボン酸としては、例えば、フタル酸、イソフタル酸、ナフタレンジカルボン酸が挙げられる。また芳香族ジカルボン酸成分以外に、共重合する成分として、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸等の脂肪族ジカルボン酸や、シクロヘキサンジカルボン酸等の脂環式ジカルボン酸等のジカルボン酸が挙げられる。しかしながら、半芳香族ポリアミド（Ａ）の耐熱性を低下させないために、テレフタル酸以外の芳香族ジカルボン酸や脂肪族ジカルボン酸や脂環式ジカルボン酸は、共重合量が、原料モノマーの総モル数に対し、５モル％以下であることが好ましく、実質的に含まれないことがより好ましい。 Examples of aromatic dicarboxylic acids other than terephthalic acid include phthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. In addition to the aromatic dicarboxylic acid component, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc. And dicarboxylic acids such as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. However, in order not to lower the heat resistance of the semi-aromatic polyamide (A), the aromatic dicarboxylic acid, aliphatic dicarboxylic acid and alicyclic dicarboxylic acid other than terephthalic acid have a copolymerization amount of the total number of moles of raw material monomers. It is preferable that it is 5 mol% or less with respect to this, and it is more preferable that it is not contained substantially.
　本発明において、半芳香族ポリアミド（Ａ）を構成する脂肪族ジアミン成分としては、例えば、１，２－エタンジアミン、１，３－プロパンジアミン、１，４－ブタンジアミン、１，５－ペンタンジアミン、１，６－ヘキサンジアミン、１，７－ヘプタンジアミン、１，８－オクタンジアミン、１，９－ノナンジアミン、１，１０－デカンジアミン、１，１１－ウンデカンジアミン、１，１２－ドデカンジアミン、２－メチル－１，５－ペンタンジアミン、２－メチル－１，８－オクタンジアミンが挙げられる。中でも、結晶性が高くなり、白色度や反射率が向上することから、１，８－デカンジアミン、１，１０－デカンジアミン、１，１２－ドデカンジアミンが好ましく、成形流動性、機械的強度のバランスがよいことから、１，１０－デカンジアミンがより好ましい。前記した脂肪族ジアミン成分は複数種を併用してもよい。 In the present invention, examples of the aliphatic diamine component constituting the semiaromatic polyamide (A) include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, and 1,5-pentanediamine. 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, -Methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine. Among them, 1,8-decanediamine, 1,10-decanediamine, and 1,12-dodecanediamine are preferable because of high crystallinity and improved whiteness and reflectivity. Molding fluidity and mechanical strength are preferred. In view of good balance, 1,10-decanediamine is more preferred. The above-mentioned aliphatic diamine components may be used in combination.
　脂肪族ジアミン成分以外に共重合する成分として、シクロヘキサンジアミン等の脂環式ジアミンや、キシリレンジアミン、ベンゼンジアミン等の芳香族ジアミン等のジアミン成分が挙げられる。しかしながら、脂肪族ジアミン成分によってもたらされる上記特性を損なうことがあるため、脂環式ジアミンや芳香族ジアミンは、共重合量が、原料モノマーの総モル数に対し、５モル％以下であることが好ましく、実質的に含まれないことがより好ましい。 Examples of the copolymerizable component other than the aliphatic diamine component include alicyclic diamines such as cyclohexanediamine, and diamine components such as aromatic diamines such as xylylenediamine and benzenediamine. However, since the above characteristics brought about by the aliphatic diamine component may be impaired, the alicyclic diamine and aromatic diamine may have a copolymerization amount of 5 mol% or less with respect to the total number of moles of raw material monomers. Preferably, it is substantially not included.
　本発明において、半芳香族ポリアミド（Ａ）は、必要に応じて、カプロラクタムやラウロラクタム等のラクタム類、アミノカプロン酸や１１－アミノウンデカン酸等のω－アミノカルボン酸が共重合してもよい。 In the present invention, the semiaromatic polyamide (A) may be copolymerized with lactams such as caprolactam and laurolactam, and ω-aminocarboxylic acids such as aminocaproic acid and 11-aminoundecanoic acid, if necessary.
　本発明において、半芳香族ポリアミド（Ａ）を構成するモノカルボン酸成分は、分子量が１４０以上のモノカルボン酸を含有することが必要であり、モノカルボン酸の分子量は１７０以上であることが好ましい。モノカルボン酸の分子量が１４０未満であると、半芳香族ポリアミド樹脂（Ａ）の成形流動性を向上する効果が乏しく、成形時の金型充填性が十分でなく、得られたＬＥＤパッケージの反射板においては、リフロー試験時の熱によって、ひび割れ（クラック）が発生したり、透明封止樹脂との間に剥離が生じることがある。 In the present invention, the monocarboxylic acid component constituting the semi-aromatic polyamide (A) needs to contain a monocarboxylic acid having a molecular weight of 140 or more, and the molecular weight of the monocarboxylic acid is preferably 170 or more. . When the molecular weight of the monocarboxylic acid is less than 140, the effect of improving the molding fluidity of the semi-aromatic polyamide resin (A) is poor, the mold filling property at the time of molding is not sufficient, and the reflection of the obtained LED package In the plate, cracks (cracks) may occur due to heat during the reflow test, or peeling may occur between the transparent sealing resin.
　モノカルボン酸としては、脂肪族モノカルボン酸、脂環族モノカルボン酸、芳香族モノカルボン酸が挙げられ、中でも、流動性の向上効果が高いことから、脂肪族モノカルボン酸が好ましい。
　分子量が１４０以上の脂肪族モノカルボン酸としては、カプリル酸、ノナン酸、デカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸が挙げられる。中でも、汎用性が高いことから、ステアリン酸が好ましい。
　分子量が１４０以上の脂環族モノカルボン酸としては、４－エチルシクロヘキサンカルボン酸、４－へキシルシクロヘキサンカルボン酸、４－ラウリルシクロヘキサンカルボン酸が挙げられる。
　分子量が１４０以上の芳香族モノカルボン酸としては、４－エチル安息香酸、４－へキシル安息香酸、４－ラウリル安息香酸などのアルキル安息香酸類、１－ナフトエ酸、２－ナフトエ酸などのナフトエ酸類およびそれらの誘導体が挙げられる。
　モノカルボン酸成分は複数種を併用してもよく、例えば、分子量が１４０以上のモノカルボン酸と分子量が１４０未満のモノカルボン酸とを併用してもよい。 Examples of monocarboxylic acids include aliphatic monocarboxylic acids, alicyclic monocarboxylic acids, and aromatic monocarboxylic acids. Among these, aliphatic monocarboxylic acids are preferred because of their high effect of improving fluidity.
Examples of the aliphatic monocarboxylic acid having a molecular weight of 140 or more include caprylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Of these, stearic acid is preferred because of its high versatility.
Examples of the alicyclic monocarboxylic acid having a molecular weight of 140 or more include 4-ethylcyclohexanecarboxylic acid, 4-hexylcyclohexanecarboxylic acid, and 4-laurylcyclohexanecarboxylic acid.
Examples of aromatic monocarboxylic acids having a molecular weight of 140 or more include alkylbenzoic acids such as 4-ethylbenzoic acid, 4-hexylbenzoic acid and 4-laurylbenzoic acid, and naphthoic acids such as 1-naphthoic acid and 2-naphthoic acid. And their derivatives.
A plurality of monocarboxylic acid components may be used in combination. For example, a monocarboxylic acid having a molecular weight of 140 or more and a monocarboxylic acid having a molecular weight of less than 140 may be used in combination.
　半芳香族ポリアミド（Ａ）における、分子量が１４０以上のモノカルボン酸の含有量は、１～８質量％であることが必要であり、２～５質量％であることが好ましい。分子量が１４０以上のモノカルボン酸の含有量が１質量％未満であると、成形流動性が低下し、成形サイクルが長くなり、得られる成形体の外観が劣ることがある。一方、含有量が８質量％を超えると、機械的強度が低くなることがある。なお、本発明において、モノカルボン酸の含有量は、半芳香族ポリアミド（Ａ）中のモノカルボン酸の残基、すなわち、モノカルボン酸から末端基の水酸基が脱離したものの含有量をいう。 In the semi-aromatic polyamide (A), the content of the monocarboxylic acid having a molecular weight of 140 or more needs to be 1 to 8% by mass, and preferably 2 to 5% by mass. When the content of the monocarboxylic acid having a molecular weight of 140 or more is less than 1% by mass, the molding fluidity is lowered, the molding cycle becomes long, and the appearance of the resulting molded article may be inferior. On the other hand, when the content exceeds 8% by mass, the mechanical strength may be lowered. In the present invention, the monocarboxylic acid content refers to the content of the monocarboxylic acid residue in the semi-aromatic polyamide (A), that is, the content of the monocarboxylic acid from which the terminal hydroxyl group is eliminated.
　一般に、ポリマーには結晶相と非晶相が存在し、融点等の結晶特性はもっぱら結晶相の状態によって定まることが知られている。ポリマー中の末端基は非晶相に存在するので、末端基の有無、種類によって融点が変化することはない。そして、末端封鎖剤として作用するモノカルボン酸も非晶相に存在するので、他成分を溶融混練した場合とは異なり、モノカルボン酸の含有によって半芳香族ポリアミドの融点を下げることはない。 Generally, it is known that a polymer has a crystalline phase and an amorphous phase, and crystal characteristics such as a melting point are determined solely by the state of the crystalline phase. Since the terminal group in the polymer exists in an amorphous phase, the melting point does not change depending on the presence or absence and type of the terminal group. And since the monocarboxylic acid which acts as a terminal blocker also exists in an amorphous phase, unlike the case where other components are melt-kneaded, the melting point of the semi-aromatic polyamide is not lowered by the inclusion of the monocarboxylic acid.
　本発明において、半芳香族ポリアミド（Ａ）は、融点が３００℃以上であることが好ましい。 In the present invention, the semi-aromatic polyamide (A) preferably has a melting point of 300 ° C. or higher.
　また、本発明において、半芳香族ポリアミド（Ａ）は、９６％硫酸中、２５℃、濃度１ｇ／ｄＬで測定した場合の相対粘度が、１．８以上であることが好ましく、１．８～２．６であることがより好ましく、１．９～２．４であることがさらに好ましい。相対粘度が１．８未満の場合、そもそも樹脂組成物の成形流動性が優れたものとなるため、本発明でおこなうような流動性改良の手法を必ずしも必要としない。なお、相対粘度は、分子量の指標とすることができる。 In the present invention, the semi-aromatic polyamide (A) preferably has a relative viscosity of 1.8 or more when measured in 96% sulfuric acid at 25 ° C. and at a concentration of 1 g / dL. 2.6 is more preferable, and 1.9 to 2.4 is even more preferable. When the relative viscosity is less than 1.8, the molding fluidity of the resin composition is excellent in the first place, and thus the fluidity improvement technique as in the present invention is not necessarily required. The relative viscosity can be used as an index of molecular weight.
　半芳香族ポリアミド（Ａ）は、従来から知られている加熱重合法や溶液重合法の方法を用いて製造することができる。中でも、工業的に有利である点から、加熱重合法が好ましく用いられる。加熱重合法としては、芳香族ジカルボン酸成分と、脂肪族ジアミン成分と、モノカルボン酸とから反応物を得る工程（ｉ）と、得られた反応物を重合する工程（ｉｉ）とからなる方法が挙げられる。 Semi-aromatic polyamide (A) can be produced using a conventionally known method such as a heat polymerization method or a solution polymerization method. Of these, the heat polymerization method is preferably used because it is industrially advantageous. The heat polymerization method includes a step (i) of obtaining a reaction product from an aromatic dicarboxylic acid component, an aliphatic diamine component, and a monocarboxylic acid, and a step (ii) of polymerizing the obtained reaction product. Is mentioned.
　工程（ｉ）としては、例えば、芳香族ジカルボン酸粉末とモノカルボン酸とを混合し、予め脂肪族ジアミンの融点以上、かつ芳香族ジカルボン酸の融点以下の温度に加熱し、この温度の芳香族ジカルボン酸粉末とモノカルボン酸とに、芳香族ジカルボン酸の粉末の状態を保つように、実質的に水を含有させずに、脂肪族ジアミンを添加する方法が挙げられる。あるいは、別の方法としては、溶融状態の脂肪族ジアミンと固体の芳香族ジカルボン酸とからなる懸濁液を攪拌混合し、混合液を得た後、最終的に生成する半芳香族ポリアミドの融点未満の温度で、芳香族ジカルボン酸と脂肪族ジアミンとモノカルボン酸の反応による塩の生成反応と、生成した塩の重合による低重合物の生成反応とをおこない、塩および低重合物の混合物を得る方法が挙げられる。この場合、反応をさせながら破砕をおこなってもよいし、反応後に一旦取り出してから破砕をおこなってもよい。工程（ｉ）は、反応物の形状の制御が容易な前者の方が好ましい。 As the step (i), for example, aromatic dicarboxylic acid powder and monocarboxylic acid are mixed and heated in advance to a temperature not lower than the melting point of the aliphatic diamine and not higher than the melting point of the aromatic dicarboxylic acid. A method of adding an aliphatic diamine to the dicarboxylic acid powder and the monocarboxylic acid without substantially containing water so as to keep the state of the aromatic dicarboxylic acid powder can be mentioned. Alternatively, as another method, a suspension of a molten aliphatic diamine and a solid aromatic dicarboxylic acid is stirred and mixed to obtain a mixed solution, and then the melting point of the semi-aromatic polyamide finally produced The salt formation reaction by the reaction of the aromatic dicarboxylic acid, the aliphatic diamine and the monocarboxylic acid, and the formation reaction of the low polymer by polymerization of the generated salt are carried out at a temperature of less than The method of obtaining is mentioned. In this case, crushing may be performed while the reaction is performed, or crushing may be performed after the reaction is once taken out. In the step (i), the former is preferred because the shape of the reactant can be easily controlled.
　工程（ｉｉ）としては、例えば、工程（ｉ）で得られた反応物を、最終的に生成する半芳香族ポリアミドの融点未満の温度で固相重合し、所定の分子量まで高分子量化させ、半芳香族ポリアミドを得る方法が挙げられる。固相重合は、重合温度１８０～２７０℃、反応時間０．５～１０時間で、窒素等の不活性ガス気流中でおこなうことが好ましい。 As the step (ii), for example, the reaction product obtained in the step (i) is solid-phase polymerized at a temperature lower than the melting point of the semi-aromatic polyamide to be finally produced, and the molecular weight is increased to a predetermined molecular weight. A method for obtaining a semi-aromatic polyamide is mentioned. The solid phase polymerization is preferably performed in a stream of inert gas such as nitrogen at a polymerization temperature of 180 to 270 ° C. and a reaction time of 0.5 to 10 hours.
　工程（ｉ）および工程（ｉｉ）の反応装置としては、特に限定されず、公知の装置を用いればよい。工程（ｉ）と工程（ｉｉ）を同じ装置で実施してもよいし、異なる装置で実施してもよい。 The reaction apparatus for step (i) and step (ii) is not particularly limited, and a known apparatus may be used. Step (i) and step (ii) may be performed by the same apparatus or may be performed by different apparatuses.
　また、加熱重合法における加熱の方法として、特に限定されないが、水、蒸気、熱媒油等の媒体にて反応容器を加熱する方法、電気ヒーターで反応容器を加熱する方法、攪拌により発生する攪拌熱等内容物の運動に伴う摩擦熱を利用する方法が挙げられる。また、これらの方法を組み合わせてもよい。 In addition, the heating method in the heat polymerization method is not particularly limited, but the method of heating the reaction vessel with a medium such as water, steam, heat transfer oil, the method of heating the reaction vessel with an electric heater, the stirring generated by stirring A method using frictional heat accompanying the movement of contents such as heat can be mentioned. Moreover, you may combine these methods.
　半芳香族ポリアミド（Ａ）の製造において、重合の効率を高めるため重合触媒を用いてもよい。重合触媒としては、例えば、リン酸、亜リン酸、次亜リン酸またはそれらの塩が挙げられ、重合触媒の添加量は、通常、芳香族ジカルボン酸と脂肪族ジアミンの総モルに対して、２モル％以下で用いることが好ましい。 In the production of the semi-aromatic polyamide (A), a polymerization catalyst may be used in order to increase the polymerization efficiency. Examples of the polymerization catalyst include phosphoric acid, phosphorous acid, hypophosphorous acid or salts thereof, and the addition amount of the polymerization catalyst is usually based on the total moles of aromatic dicarboxylic acid and aliphatic diamine. It is preferable to use at 2 mol% or less.
　本発明の半芳香族ポリアミド樹脂組成物を構成する白色顔料（Ｂ）としては、例えば、酸化チタン、酸化亜鉛、硫化亜鉛、硫酸亜鉛、硫酸バリウム、炭酸カルシウム、酸化アルミニウムが挙げられ、中でも、酸化チタン、硫酸バリウム、炭酸カルシウムが好ましい。白色顔料として、酸化チタン、硫酸バリウム、炭酸カルシウムのうち、２種以上を併用することにより、反射率の保持率を向上させることができる。 Examples of the white pigment (B) constituting the semi-aromatic polyamide resin composition of the present invention include titanium oxide, zinc oxide, zinc sulfide, zinc sulfate, barium sulfate, calcium carbonate, and aluminum oxide. Titanium, barium sulfate and calcium carbonate are preferred. By using two or more kinds of white pigments among titanium oxide, barium sulfate, and calcium carbonate, the reflectance retention can be improved.
　酸化チタンは、屈折率が高く光安定性が良好なルチル型が好ましい。酸化チタンの粒子径は、０．０５～２．０μｍであることが好ましく、０．０５～０．５μｍであることがより好ましい。硫酸バリウムとしては、天然に産出するものでも合成品でもよく、前者としては、重晶石（バライト）、後者としては、沈降性硫酸バリウムが挙げられる。硫酸バリウムの粒径は、０．００５～１０μｍであることが好ましく、０．０１～１μｍであることがより好ましい。炭酸カルシウムとしては、例えば、方解石（カルサイト）、霰石（アラゴナイト）、天然炭酸カルシウム（重質炭酸カルシウム）、合成炭酸カルシウム（沈降炭酸カルシウム）が挙げられ、中でも、方解石、霰石が好ましい。炭酸カルシウムの粒子径は、０．０５～１０μｍであることが好ましく、０．１～５μｍであることがより好ましい。 Titanium oxide is preferably a rutile type having a high refractive index and good light stability. The particle diameter of titanium oxide is preferably 0.05 to 2.0 μm, and more preferably 0.05 to 0.5 μm. The barium sulfate may be naturally produced or synthetic, and the former includes barite and the latter includes precipitated barium sulfate. The particle size of barium sulfate is preferably 0.005 to 10 μm, and more preferably 0.01 to 1 μm. Examples of calcium carbonate include calcite (calcite), aragonite (aragonite), natural calcium carbonate (heavy calcium carbonate), and synthetic calcium carbonate (precipitated calcium carbonate). Among them, calcite and aragonite are preferable. The particle size of calcium carbonate is preferably 0.05 to 10 μm, and more preferably 0.1 to 5 μm.
　白色顔料（Ｂ）は、中性化のためや、樹脂との濡れ性改善のために、表面処理されていてもよい。表面処理剤としては、例えば、アルミナ、シリカ、酸化亜鉛、酸化ジルコニウム等の金属酸化物、ステアリン酸等の有機酸またはそれらの金属塩、ポリオール、シランカップリング剤、チタンカップリング剤が挙げられる。 The white pigment (B) may be surface-treated for neutralization or for improving wettability with the resin. Examples of the surface treatment agent include metal oxides such as alumina, silica, zinc oxide and zirconium oxide, organic acids such as stearic acid or metal salts thereof, polyols, silane coupling agents, and titanium coupling agents.
　白色顔料（Ｂ）の含有量は、半芳香族ポリアミド（Ａ）１００質量部に対し、１０～１５０質量部であることが必要であり、２０～１３０質量部であることが好ましく、２０～１００質量部であることがより好ましく、３０～１００質量部であることがさらに好ましい。白色顔料（Ｂ）の含有量が１０質量部未満の場合、白色度や反射率が低下することがあり、また得られる成形体は、熱により変色して耐リフロー性が劣ることがある。一方、含有量が１５０質量部を超える場合、機械的強度の補強効率が低下するばかりでなく、溶融混練時の作業性が低下し、半芳香族ポリアミド樹脂組成物のペレットを得ることが難しくなることがある。 The content of the white pigment (B) needs to be 10 to 150 parts by weight, preferably 20 to 130 parts by weight, with respect to 100 parts by weight of the semi-aromatic polyamide (A). The amount is more preferably part by mass, and further preferably 30 to 100 parts by mass. When the content of the white pigment (B) is less than 10 parts by mass, the whiteness and the reflectance may be lowered, and the obtained molded product may be discolored by heat and have poor reflow resistance. On the other hand, when the content exceeds 150 parts by mass, not only the reinforcement efficiency of the mechanical strength is lowered, but also the workability at the time of melt kneading is lowered, and it becomes difficult to obtain a semi-aromatic polyamide resin composition pellet. Sometimes.
　本発明の半芳香族ポリアミド樹脂組成物は、機械的強度の向上の観点から、繊維状強化材（Ｃ）を含有してもよい。繊維状強化材（Ｃ）としては、例えば、ガラス繊維、チタン酸カリウム繊維、アルミナ繊維、シリカ繊維、ジルコニア繊維、炭化ケイ素繊維、セラミックス繊維、ワラストナイト、セピオライト、アタパルジャイトが挙げられる。中でも、半芳香族ポリアミド（Ａ）の溶融温度において溶融せず、白色度を保持する点で、ガラス繊維、チタン酸カリウム繊維、ワラストナイト、セピオライト、アタパルジャイトが好ましく、ガラス繊維とチタン酸カリウム繊維の併用、ガラス繊維とワラストナイトの併用が好ましい。 The semi-aromatic polyamide resin composition of the present invention may contain a fibrous reinforcing material (C) from the viewpoint of improving mechanical strength. Examples of the fibrous reinforcing material (C) include glass fiber, potassium titanate fiber, alumina fiber, silica fiber, zirconia fiber, silicon carbide fiber, ceramic fiber, wollastonite, sepiolite, and attapulgite. Among them, glass fiber, potassium titanate fiber, wollastonite, sepiolite, and attapulgite are preferable in terms of maintaining whiteness without melting at the melting temperature of the semi-aromatic polyamide (A), and glass fiber and potassium titanate fiber. The combined use of glass fiber and wollastonite is preferred.
　ガラス繊維は、シランカップリング剤で表面処理されていることが好ましい。シランカップリング剤を、ガラス繊維を束ねるための集束剤に分散して、ガラス繊維の表面処理をしてもよい。シランカップリング剤としては、例えば、ビニルシラン系、アクリルシラン系、エポキシシラン系、アミノシラン系が挙げられ、半芳香族ポリアミド（Ａ）とガラス繊維との密着効果を得やすいことから、アミノシラン系が好ましい。 The glass fiber is preferably surface-treated with a silane coupling agent. A silane coupling agent may be dispersed in a sizing agent for bundling glass fibers to treat the glass fibers. Examples of the silane coupling agent include vinyl silanes, acrylic silanes, epoxy silanes, and amino silanes, and aminosilanes are preferred because it is easy to obtain an adhesion effect between the semi-aromatic polyamide (A) and the glass fiber. .
　繊維状強化材（Ｃ）の繊維長は、０．１～７ｍｍであることが好ましく、０．５～６ｍｍであることがより好ましい。また、繊維径は３～２０μｍであることが好ましく、５～１３μｍであることがより好ましい。繊維長が０．１～７ｍｍ、繊維径が３～２０μｍであることで、成形性に悪影響を及ぼすことなく、効率よく補強することができる。 The fiber length of the fibrous reinforcing material (C) is preferably 0.1 to 7 mm, and more preferably 0.5 to 6 mm. The fiber diameter is preferably 3 to 20 μm, more preferably 5 to 13 μm. When the fiber length is 0.1 to 7 mm and the fiber diameter is 3 to 20 μm, the fiber can be efficiently reinforced without adversely affecting the moldability.
　繊維状強化材（Ｃ）を含有する場合、その含有量は、半芳香族ポリアミド（Ａ）１００質量部に対し、１０～８０質量部であることが好ましく、１５～６０質量部であることがより好ましく、２０～４０質量部であることがさらに好ましい。繊維状強化材（Ｃ）の含有量が５質量部の場合、機械的強度向上の効果が得られないことがある。一方、８０質量部を超える場合、機械的強度の補強効率が低下したり、溶融混練時の作業性が低下して、半芳香族ポリアミド樹脂組成物のペレットを得ることが難しくなることがある。また、繊維状強化材が成形体表面に浮き出ることにより、反射率が低下することがある。 When the fibrous reinforcing material (C) is contained, the content thereof is preferably 10 to 80 parts by mass, and preferably 15 to 60 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide (A). More preferred is 20 to 40 parts by mass. When the content of the fibrous reinforcing material (C) is 5 parts by mass, the effect of improving the mechanical strength may not be obtained. On the other hand, when it exceeds 80 parts by mass, the reinforcing efficiency of the mechanical strength is lowered, the workability at the time of melt kneading is lowered, and it may be difficult to obtain a semi-aromatic polyamide resin composition pellet. In addition, the reflectance may decrease due to the fibrous reinforcing material floating on the surface of the molded body.
　繊維状強化材（Ｃ）を含有させる方法は、その補強効果が損なわれなければ特に限定されないが、二軸混練機を用いた溶融混練が好ましい。混練温度は半芳香族ポリアミド（Ａ）の融点以上とする必要があり、（融点＋８０℃）未満とすることが好ましい。混練温度が融点未満では混練機が過負荷となり、ベントアップ等の不具合が生じることがある。また混練温度が高すぎると、半芳香族ポリアミド（Ａ）の分解、黄変が起こることある。 The method of incorporating the fibrous reinforcing material (C) is not particularly limited as long as the reinforcing effect is not impaired, but melt kneading using a biaxial kneader is preferable. The kneading temperature must be equal to or higher than the melting point of the semi-aromatic polyamide (A), and is preferably less than (melting point + 80 ° C.). If the kneading temperature is lower than the melting point, the kneader is overloaded, and problems such as vent-up may occur. When the kneading temperature is too high, the semi-aromatic polyamide (A) may be decomposed or yellowed.
　本発明の半芳香族ポリアミド樹脂組成物は、さらに、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム等の金属水酸化物を含有することが好ましい。金属水酸化物を含有することにより、反射率の保持率を向上することができる。なお、金属水酸化物は、中性化のためや、樹脂との濡れ性改善のために、表面処理されていてもよい。金属水酸化物の含有量は、半芳香族ポリアミド（Ａ）１００質量部に対し、０．１～３０質量部であることが好ましく、１～２０質量部であることがより好ましい。 The semi-aromatic polyamide resin composition of the present invention preferably further contains a metal hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide. By containing a metal hydroxide, the reflectance retention can be improved. The metal hydroxide may be surface-treated for neutralization or for improving wettability with the resin. The content of the metal hydroxide is preferably 0.1 to 30 parts by mass and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide (A).
　本発明の半芳香族ポリアミド樹脂組成物は、さらに酸化防止剤を含有してもよい。
　酸化防止剤は、通常、半芳香族ポリアミド（Ａ）の分子量低下や色の退化防止を目的に含有させるものである。本発明においては、これらの効果に加えて、樹脂組成物の滞留安定性を向上させることができる。すなわち、繊維状強化材（Ｃ）を含有する半芳香族ポリアミド樹脂組成物は、高温のシリンダー内に長時間滞留した場合、繊維状強化材（Ｃ）の表面処理剤が熱分解し、機械的強度の低下を引き起こす場合がある。しかしながら、酸化防止剤を含有することにより、シリンダー内で長時間樹脂組成物を滞溜させた場合、すなわち、射出成形時において成形サイクルが長い場合や射出量が少なくシリンダー内に樹脂が長く滞留する場合でも、樹脂組成物の引張強度の低下を抑制することができる。 The semi-aromatic polyamide resin composition of the present invention may further contain an antioxidant.
The antioxidant is usually contained for the purpose of preventing the molecular weight of the semi-aromatic polyamide (A) from being lowered and preventing the color from deteriorating. In the present invention, in addition to these effects, the residence stability of the resin composition can be improved. That is, when the semi-aromatic polyamide resin composition containing the fibrous reinforcement (C) stays in a high-temperature cylinder for a long time, the surface treatment agent of the fibrous reinforcement (C) is thermally decomposed and mechanically May cause a decrease in strength. However, by containing an antioxidant, the resin composition stays in the cylinder for a long time, that is, when the molding cycle is long at the time of injection molding or the injection amount is small and the resin stays in the cylinder for a long time. Even in this case, a decrease in the tensile strength of the resin composition can be suppressed.
　酸化防止剤を含有する場合、その含有量は、半芳香族ポリアミド（Ａ）１００質量部に対し、０．０５～５質量部であることが好ましく、０．２～５質量部であることがさらに好ましい。含有量が０．０５質量部未満の場合、上記の効果が小さく、５質量部を超えると成形時に金型が汚れやすく、成形不良が発生することがある。 When the antioxidant is contained, the content thereof is preferably 0.05 to 5 parts by mass and preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide (A). Further preferred. When the content is less than 0.05 parts by mass, the above effects are small, and when it exceeds 5 parts by mass, the mold is likely to become dirty during molding, and molding defects may occur.
　酸化防止剤としては、例えば、リン系酸化防止剤、ヒンダードフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、トリアジン系化合物、硫黄系化合物が挙げられ、中でも、リン系酸化防止剤、ヒンダードフェノール系酸化防止剤、硫黄系化合物が好ましい。 Examples of the antioxidant include phosphorus antioxidants, hindered phenol antioxidants, hindered amine antioxidants, triazine compounds, and sulfur compounds, among which phosphorus antioxidants and hindered phenols. Of these, antioxidants and sulfur compounds are preferred.
　リン系酸化防止剤は、無機化合物でも有機化合物でもよい。リン系酸化防止剤としては、例えば、リン酸一ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム、亜リン酸ナトリウム、亜リン酸カルシウム、亜リン酸マグネシウム、亜リン酸マンガン等の無機塩、トリフェニルホスファイト、トリオクタデシルホスファイト、トリデシルホスファイト、トリノニルフェニルホスファイト、ジフェニルイソデシルホスファイト、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）－４，４－ビフェニリレンジフォスファイトが挙げられる。中でも、ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト、テトラキス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）－４，４－ビフェニリレンジフォスファイトが好ましい。これらは単独で用いてもよいし、併用してもよい。
　市販のリン系酸化防止剤としては、例えば、アデカ社製“アデカスタブ”ＰＥＰ－８、ＰＥＰ－３６、ＰＥＰ－４Ｃ、クラリアント社製“ホスタノックス”Ｐ－ＥＰＱが挙げられる。 The phosphorus-based antioxidant may be an inorganic compound or an organic compound. Phosphorus antioxidants include, for example, monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, and other inorganic salts, triphenyl phosphate Phyto, trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2 , 4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4- Biphenylylen range Sufaito and the like. Of these, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4-biphenylylene phosphite are preferable. . These may be used alone or in combination.
Examples of commercially available phosphorus antioxidants include “ADEKA STAB” PEP-8, PEP-36 and PEP-4C manufactured by Adeka, and “Hostanox” P-EPQ manufactured by Clariant.
　ヒンダードフェノール系酸化防止剤としては、例えば、ｎ－オクタデシル－３－（３′，５′－ジ－ｔ－ブチル－４′－ヒドロキシフェニル）－プロピオネート、ｎ－オクタデシル－３－（３′－メチル－５′－ｔ－ブチル－４′－ヒドロキシフェニル）－プロピオネート、ｎ－テトラデシル－３－（３′，５′－ジ－ｔ－ブチル－４′－ヒドロキシフェニル）－プロピオネート、１，６－ヘキサンジオール－ビス－［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）－プロピオネート］、１，４－ブタンジオール－ビス－［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）－プロピオネート］、２，２′－メチレンビス－（４－メチル－ｔ－ブチルフェノール）、トリエチレングリコール－ビス－［３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）－プロピオネート］、テトラキス［メチレン－３－（３′，５′－ジ－ｔ－ブチル－４′－ヒドロキシフェニル）プロピオネート］メタン、３，９－ビス［２－｛３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝－１，１－ジメチルエチル］２，４，８，１０－テトラオキサスピロ（５，５）ウンデカン、Ｎ，Ｎ′－ビス－３－（３′，５′－ジ－ｔ－ブチル－４′－ヒドロキシフェニル）プロピオニルヘキサメチレンジアミン、Ｎ，Ｎ′－テトラメチレン－ビス－３－（３′－メチル－５′－ｔ－ブチル－４′－ヒドロキシフェノール）プロピオニルジアミン、Ｎ，Ｎ′－ビス－［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェノール）プロピオニル］ヒドラジン、Ｎ－サリチロイル－Ｎ′－サリチリデンヒドラジン、３－（Ｎ－サリチロイル）アミノ－１，２，４－トリアゾール、Ｎ，Ｎ′－ビス［２－｛３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオニルオキシ｝エチル］オキシアミド、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ′－ヘキサメチレンビス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロシンナマイドが挙げられる。中でも、トリエチレングリコール－ビス－［３－（３－ｔ－ブチル－５－メチル－４－ヒドロキシフェニル）－プロピオネート］、テトラキス［メチレン－３－（３′，５′－ジ－ｔ－ブチル－４′－ヒドロキシフェニル）プロピオネート］メタン、１，６－ヘキサンジオール－ビス－［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）－プロピオネート］、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ′－ヘキサメチレンビス－（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロシンナマイドが好ましい。これらは単独で用いてもよいし、併用してもよい。
　市販のヒンダードフェノール系酸化防止剤としては、例えば、アデカ社製“アデカスタブ”ＡＯ－２０、ＡＯ－３０、ＡＯ－４０、ＡＯ－５０、ＡＯ－６０、ＡＯ－７０、ＡＯ－８０、ＡＯ－３３０、チバスペシャリティケミカル社製“イルガノックス”２４５、２５９、５６５、１０１０、１０３５、１０７６、１０９８、１２２２、１３３０、１４２５、１５２０、３１１４、５０５７、住友化学工業社製“スミライザー”ＢＨＴ－Ｒ、ＭＤＰ－Ｓ、ＢＢＭ－Ｓ、ＷＸ－Ｒ、ＮＷ、ＢＰ－７６、ＢＰ－１０１、ＧＡ－８０、ＧＭ、ＧＳ、サイアナミド社製“サイアノックス”ＣＹ－１７９０が挙げられる。 Examples of the hindered phenol antioxidant include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′- Methyl-5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6- Hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl -4-hydroxyphenyl) -propionate], 2,2'-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl) 5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [ 2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N'-bis-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionylhexamethylenediamine, N, N'-tetramethylene-bis-3- (3'-methyl -5'-t-butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propioni ] Hydrazine, N-salicyloyl-N'-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis [2- {3- (3,5-di -T-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexa And methylene bis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide. Among them, triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxy Phenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] meta 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], pentaerythrityl-tetrakis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) is preferred. These may be used alone or in combination.
Examples of commercially available hindered phenol antioxidants include “ADEKA STAB” AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, and AO— manufactured by Adeka Corporation. 330, “Irganox” 245, 259, 565, 1010, 1035, 1076, 1098, 1222, 1330, 1425, 1520, 3114, 5057 manufactured by Ciba Specialty Chemical Co., Ltd. “Sumilyzer” BHT-R, MDP manufactured by Sumitomo Chemical -S, BBM-S, WX-R, NW, BP-76, BP-101, GA-80, GM, GS, “Cyanox” CY-1790 manufactured by Cyanamid Co., Ltd.
　硫黄系酸化防止剤としては、例えば、ジステアリル３，３′－チオジプロピオネート、ペンタエリスリチルテトラキス（３－ラウリルチオプロピオネート）、２－メルカプトベンズイミダゾール、ジドデシル３，３′－チオジプロピオネート、ジオクタデシル３，３′－チオジプロピオネート、ジトリデシル３，４′－チオジプロピオネート、２，２－ビス［［３－（ドデシルチオ）－１－オキソプロポキシ］メチル］－１，３－プロパンジイルエステル挙げられる。中でも、ジステアリル３，３′－チオジプロピオネート、ペンタエリスリチルテトラキス（３－ラウリルチオプロピオネート）が好ましい。これらは単独で用いてもよいし、併用してもよい。
　市販の硫黄系酸化防止剤としては、例えば、住友化学工業社製“スミライザー”ＴＰ－Ｄが挙げられる。 Examples of sulfur-based antioxidants include distearyl 3,3′-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 2-mercaptobenzimidazole, didodecyl 3,3′-thiodiprote. Pionate, dioctadecyl 3,3'-thiodipropionate, ditridecyl 3,4'-thiodipropionate, 2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3 Mention may be made of propanediyl esters. Of these, distearyl 3,3′-thiodipropionate and pentaerythrityl tetrakis (3-laurylthiopropionate) are preferable. These may be used alone or in combination.
Examples of commercially available sulfur-based antioxidants include “Sumilyzer” TP-D manufactured by Sumitomo Chemical Co., Ltd.
　本発明の半芳香族ポリアミド樹脂組成物は、さらに光安定剤を含有してもよい。特に、白色顔料として酸化チタンを用いる場合は、酸化チタンが光分解を促進する場合があるので、光安定剤を含有することが好ましい。光安定剤としては、例えば、ベンゾフェノン系化合物、ベンゾトリアゾール系化合物、サリシレート系化合物、ヒンダードアミン系化合物（ＨＡＬＳ）、ヒンダードフェノール系化合物が挙げられ、中でも、半芳香族ポリアミドとの親和性や耐熱性が高いことからヒンダードアミン系化合物が好ましい。
　市販の光安定剤としては、例えば、クラリアントジャパン社製“ナイロスタブ”Ｓ－ＥＥＤ、共同薬品社製“バイオソーブ”０４、チバ・スペシャリティ・ケミカルズ社製“チヌビン”６２２、７６５、Ｃｙｔｅｃ社製“サイアソーブ”ＵＶ－３３４６、旭電化工業社製“アデカスタブ”ＬＡ－５７、ＢＡＳＦ社製“チマソーブ”１１９、９４４が挙げられる。 The semi-aromatic polyamide resin composition of the present invention may further contain a light stabilizer. In particular, when titanium oxide is used as the white pigment, it is preferable to contain a light stabilizer because titanium oxide may promote photolysis. Examples of the light stabilizer include a benzophenone compound, a benzotriazole compound, a salicylate compound, a hindered amine compound (HALS), and a hindered phenol compound, and among them, affinity with a semi-aromatic polyamide and heat resistance. Is high, hindered amine compounds are preferred.
Commercially available light stabilizers include, for example, “Nyrostub” S-EED manufactured by Clariant Japan, “Biosorb” 04 manufactured by Kyodo Yakuhin Co., Ltd., “Tinubin” 622, 765 manufactured by Ciba Specialty Chemicals, and “Siasorb” manufactured by Cytec. UV-3346, “Adeka Stub” LA-57 manufactured by Asahi Denka Kogyo Co., Ltd., and “Timasorb” 119, 944 manufactured by BASF.
　光安定剤を含有する場合、その含有量は、半芳香族ポリアミド（Ａ）１００質量部に対し、０．１～５質量部であることが好ましく、０．２～５質量部であることがさらに好ましい。光安定剤の含有量を、０．１～５質量部とすることにより、反射率の保持率を向上させることができる。 When the light stabilizer is contained, the content thereof is preferably 0.1 to 5 parts by mass and preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the semi-aromatic polyamide (A). Further preferred. By setting the content of the light stabilizer to 0.1 to 5 parts by mass, the reflectance retention can be improved.
　本発明において、酸化防止剤と光安定剤を併用することが好ましい。酸化防止剤と光安定剤を併用することにより、成形時の滞留安定性を向上させつつ、使用時の紫外線等による光劣化を効率的に防止し、反射率や白色度を向上させることができる。 In the present invention, it is preferable to use an antioxidant and a light stabilizer in combination. By using an antioxidant and a light stabilizer in combination, it is possible to improve the retention stability during molding, efficiently prevent light deterioration due to ultraviolet rays during use, and improve reflectance and whiteness. .
　本発明の半芳香族ポリアミド樹脂組成物は、さらに蛍光増白剤を含有してもよい。蛍光増白剤としては、例えば、ビスベンゾオキサゾール、ビス（スチリル）ビフェニル、フェニルクマリン（具体的には、トリアジン－フェニルクマリン、ベンゾトリアゾール－フェニルクマリンおよびナフトトリアゾール－フェニルクマリン）、トリアジン－スチルベンが挙げられる。
　市販の蛍光増白剤としては、例えば、チバスペシャリティケミカル社製“チノパール”ＯＢ、クラリアント社製“ホスタノックス”ＫＳ、イーストマン社製“イーストブライト”ＯＢ－１が挙げられる。 The semi-aromatic polyamide resin composition of the present invention may further contain an optical brightener. Examples of the optical brightener include bisbenzoxazole, bis (styryl) biphenyl, phenylcoumarin (specifically, triazine-phenylcoumarin, benzotriazole-phenylcoumarin and naphthotriazole-phenylcoumarin), and triazine-stilbene. It is done.
Examples of commercially available fluorescent brighteners include “Chino Pearl” OB manufactured by Ciba Specialty Chemicals, “Hostanox” KS manufactured by Clariant, and “East Bright” OB-1 manufactured by Eastman.
　本発明の半芳香族ポリアミド樹脂組成物は、必要に応じて他の添加剤を含有してもよい。他の添加剤としては、例えば、板状強化材、タルク、膨潤性粘土鉱物、シリカ、ガラスビーズ等の充填材、帯電防止剤、難燃剤、難燃助剤が挙げられる。 The semi-aromatic polyamide resin composition of the present invention may contain other additives as necessary. Examples of the other additives include fillers such as plate-like reinforcing materials, talc, swellable clay minerals, silica and glass beads, antistatic agents, flame retardants, and flame retardant aids.
　本発明の半芳香族ポリアミド樹脂組成物に、上記繊維状強化材、白色顔料、酸化防止剤、光安定剤、蛍光増白剤および他の添加剤を添加する方法は、その効果が損なわれなければ特に限定されず、例えば、半芳香族ポリアミド（Ａ）の重合時または溶融混練時に添加する方法が挙げられる。 The effect of the method of adding the fibrous reinforcing material, white pigment, antioxidant, light stabilizer, fluorescent whitening agent and other additives to the semi-aromatic polyamide resin composition of the present invention must be impaired. The method is not particularly limited, and examples thereof include a method of adding at the time of polymerization or melt kneading of the semi-aromatic polyamide (A).
　本発明の半芳香族ポリアミド樹脂組成物を成形する方法としては、例えば、射出成形法、押出成形法、ブロー成形法が挙げられ、中でも、射出成形法が好ましい。
　射出成形機としては、特に限定されず、例えば、スクリューインライン式射出成形機、プランジャ式射出成形機が挙げられる。
　射出成形機のシリンダー内で加熱溶融された半芳香族ポリアミド樹脂組成物は、ショットごとに計量され、金型内に溶融状態で射出され、所定の形状で冷却、固化された後、成形体として金型から取り出される。射出成形時の樹脂温度は、半芳香族ポリアミド樹脂組成物の融点以上とする必要があり、（融点＋１００℃）未満とすることが好ましい。
　なお、半芳香族ポリアミド樹脂組成物の加熱溶融時には、用いる半芳香族ポリアミド樹脂組成物は十分に乾燥されたものを用いることが好ましい。含有する水分量が多いと、射出成形機のシリンダー内で樹脂が発泡し、最適な成形体を得ることが困難となることがある。射出成形に用いる半芳香族ポリアミド樹脂組成物の水分率は、０．３質量％未満が好ましく、０．１質量％未満がより好ましい。
　また、本発明の樹脂組成物を構成する半芳香族ポリアミド（Ａ）は、ポリアミド６、ポリアミド６６に比べ、融点が高く、成形体を得るための溶融温度が高いため、樹脂が長時間にわたって成形機シリンダー内に滞留する場合、前記樹脂が劣化しやすく、分解ガスが発生しやすい。したがって、本発明の半芳香族ポリアミド樹脂組成物を成形して耐熱性に優れた成形体を得るためには、成形サイクルを短くし、溶融樹脂の成形機シリンダー内への滞留を極力抑制することが好ましい。 Examples of the method for molding the semi-aromatic polyamide resin composition of the present invention include an injection molding method, an extrusion molding method, and a blow molding method, and among these, the injection molding method is preferable.
The injection molding machine is not particularly limited, and examples thereof include a screw inline type injection molding machine and a plunger type injection molding machine.
A semi-aromatic polyamide resin composition heated and melted in a cylinder of an injection molding machine is weighed for each shot, injected into a mold in a molten state, cooled to a predetermined shape, solidified, and then formed into a molded body. Removed from the mold. The resin temperature at the time of injection molding must be equal to or higher than the melting point of the semi-aromatic polyamide resin composition, and is preferably less than (melting point + 100 ° C.).
When the semi-aromatic polyamide resin composition is heated and melted, it is preferable to use a semi-aromatic polyamide resin composition that has been sufficiently dried. If the water content is large, the resin foams in the cylinder of the injection molding machine, and it may be difficult to obtain an optimal molded body. The water content of the semi-aromatic polyamide resin composition used for injection molding is preferably less than 0.3% by mass, and more preferably less than 0.1% by mass.
In addition, the semi-aromatic polyamide (A) constituting the resin composition of the present invention has a higher melting point than the polyamide 6 and the polyamide 66 and a high melting temperature for obtaining a molded product. When staying in the machine cylinder, the resin is likely to deteriorate and decomposition gas is likely to be generated. Therefore, in order to obtain a molded article having excellent heat resistance by molding the semi-aromatic polyamide resin composition of the present invention, the molding cycle should be shortened and the residence of the molten resin in the molding machine cylinder should be suppressed as much as possible. Is preferred.
　本発明の半芳香族ポリアミド樹脂組成物は、機械的強度、耐熱性、成形性に加えて、白色度、反射率、耐リフロー性に優れているため、自動車部品、電気電子部品等の広範な用途に使用できる。自動車部品としては、例えば、ランプリフレクタ、ランプハウジング、ランプエクステンション、ランプソケットの電装系部品が挙げられる。電気電子部品としては、例えば、ＬＥＤパッケージの反射板が挙げられる。ＬＥＤパッケージは、ＬＥＤ照明装置に用いることができる。 The semi-aromatic polyamide resin composition of the present invention is excellent in whiteness, reflectance, and reflow resistance in addition to mechanical strength, heat resistance and moldability. Can be used for applications. Examples of automobile parts include electrical components such as a lamp reflector, a lamp housing, a lamp extension, and a lamp socket. Examples of the electric / electronic component include a reflector of an LED package. The LED package can be used for an LED lighting device.
　以下、本発明を実施例によって具体的に説明するが、本発明はこれらによって限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
１．測定方法
（１）半芳香族ポリアミドの相対粘度
　９６質量％硫酸を溶媒とし、濃度１ｇ／ｄＬ、２５℃で測定した。 1. Measuring method (1) Relative viscosity of semi-aromatic polyamide 96% by mass sulfuric acid was used as a solvent, and the concentration was measured at a concentration of 1 g / dL and 25 ° C.
（２）半芳香族ポリアミドの融点
　パーキンエルマー社製示差走査型熱量計ＤＳＣ－７を用い、昇温速度２０℃／分で３５０℃まで昇温した後、３５０℃で５分間保持し、降温速度２０℃／分で２５℃まで降温し、さらに２５℃で５分間保持後、再び昇温速度２０℃／分で昇温測定した際の吸熱ピークのトップを融点とした。 (2) Melting point of semi-aromatic polyamide Using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer, Inc., the temperature was raised to 350 ° C. at a rate of temperature rise of 20 ° C./min, then held at 350 ° C. for 5 minutes, and the rate of temperature drop The temperature was lowered to 25 ° C. at 20 ° C./min, further held at 25 ° C. for 5 minutes, and the top of the endothermic peak when the temperature was measured again at a rate of temperature increase of 20 ° C./min was taken as the melting point.
（３）半芳香族ポリアミドの組成
　半芳香族ポリアミドについて、１Ｈ－ＮＭＲ測定をおこない、各成分の組成を求めた（溶媒：重水素化トリフルオロ酢酸、温度：２５℃）。 (3) Composition of semi-aromatic polyamide The semi-aromatic polyamide was subjected to 1 H-NMR measurement to determine the composition of each component (solvent: deuterated trifluoroacetic acid, temperature: 25 ° C.).
（４）半芳香族ポリアミド樹脂組成物のメルトフローレート（ＭＦＲ）
　半芳香族ポリアミド樹脂組成物を用いて、ＪＩＳ　Ｋ７２１０に従って、３４０℃、１．２ｋｇｆの荷重で測定した。実用上、１～８０ｇ／１０分が好ましく、２０～７０ｇ／１０分がより好ましい。 (4) Melt flow rate (MFR) of semi-aromatic polyamide resin composition
Using a semi-aromatic polyamide resin composition, measurement was performed at 340 ° C. and a load of 1.2 kgf in accordance with JIS K7210. Practically, 1 to 80 g / 10 min is preferable, and 20 to 70 g / 10 min is more preferable.
（５）半芳香族ポリアミド樹脂組成物の曲げ強度、曲げ弾性率
　半芳香族ポリアミド樹脂組成物を十分に乾燥した後、ファナック製射出成形機（α－１００ｉＡ）を用いて、樹脂温度３３０℃、金型温度１３５℃、成形サイクル２５秒の条件で、ＩＳＯ準拠の試験片を作製し、ＩＳＯ１７８に従って曲げ強度、曲げ弾性率を測定した。
　実用上、曲げ強度は１２０ＭＰａ以上が好ましく、曲げ弾性率は４．０ＧＰａ以上が好ましい。 (5) Flexural strength and flexural modulus of semi-aromatic polyamide resin composition After sufficiently drying the semi-aromatic polyamide resin composition, using a FANUC injection molding machine (α-100iA), a resin temperature of 330 ° C., Test pieces conforming to ISO were prepared under conditions of a mold temperature of 135 ° C. and a molding cycle of 25 seconds, and bending strength and flexural modulus were measured according to ISO178.
Practically, the bending strength is preferably 120 MPa or more, and the bending elastic modulus is preferably 4.0 GPa or more.
（６）半芳香族ポリアミド樹脂組成物の白色度
　半芳香族ポリアミド樹脂組成物を十分に乾燥した後、ニイガタマシンテクノ社製射出成形機（ＣＮＤ－１５ＡII）を用いて、樹脂温度３３０℃、金型温度１３５℃、成形サイクル１５秒の条件で、２０ｍｍ×２０ｍｍ×０．５ｍｍの成形片を作製した。得られた成形片を用いて、ＪＩＳ　Ｚ８７３０に従って、日本電色社製スペクトロフォトメーターＳＥ６０００（光源：Ｃ－２）により、ハンターの色差式による明度（Ｌ値）、赤色度（ａ値）および黄色度（ｂ値）を求め、下記式により、白色度Ｗを算出した。なお、標準あわせは、セラミックガラス製のピトロ白板を用いた。
　Ｗ＝１００－〔（１００－Ｌ）２＋ａ２＋ｂ２〕１／２
　実用上、白色度は９０以上が好ましい。 (6) Whiteness of the semi-aromatic polyamide resin composition After the semi-aromatic polyamide resin composition is sufficiently dried, the resin temperature is 330 ° C. using an injection molding machine (CND-15AII) manufactured by Niigata Machine Techno Co., Ltd. A molded piece of 20 mm × 20 mm × 0.5 mm was produced under conditions of a mold temperature of 135 ° C. and a molding cycle of 15 seconds. Using the obtained molded piece, in accordance with JIS Z8730, by a spectrophotometer SE6000 (light source: C-2) manufactured by Nippon Denshoku Co., Ltd., brightness (L value), redness (a value) and yellow color according to Hunter's color difference formula The degree (b value) was obtained, and the whiteness W was calculated by the following formula. In addition, the standard matching used the Pitro white board made from ceramic glass.
W = 100 − [(100−L) 2 + a 2 + b 2 ] 1/2
Practically, the whiteness is preferably 90 or more.
（７）半芳香族ポリアミド樹脂組成物の反射率、加熱処理後の反射率の保持率
　上記（６）で得られた成形片を１４０℃で３００時間、オーブンで加熱処理し、処理前後の成形片について、日本電色社製スペクトロフォトメーターＳＥ６０００（光源：Ｃ－２）により、４６０ｎｍの波長の反射率を測定した。
　実用上、処理前の反射率は８５％以上が好ましく、９０％以上がより好ましく、処理後の反射率は、６０％以上が好ましく、７０％以上がより好ましく、８０％以上がさらに好ましい。
　反射率の保持率は、以下の式を用いて求めた。
　保持率＝（［処理後の反射率］／［処理前の反射率］）×１００ (7) Reflectivity of semi-aromatic polyamide resin composition, retention ratio of reflectance after heat treatment The molded piece obtained in (6) above is heat-treated in an oven at 140 ° C. for 300 hours, and molded before and after the treatment. About the piece, the reflectance at a wavelength of 460 nm was measured with a spectrophotometer SE6000 (light source: C-2) manufactured by Nippon Denshoku.
In practice, the reflectance before treatment is preferably 85% or more, more preferably 90% or more, and the reflectance after treatment is preferably 60% or more, more preferably 70% or more, and further preferably 80% or more.
The reflectance retention was determined using the following equation.
Retention rate = ([reflectance after processing] / [reflectivity before processing]) × 100
（８）流動長
　ファナック社製射出成形機Ｓ２０００ｉ－１００Ｂを用いて、シリンダー温度を（融点＋２５℃）、金型温度を（融点－１８５℃）に設定した後、型締力１００トン、射出圧力１２０ＭＰａ、射出速度８０ｍｍ／秒、射出時間５秒の条件で、片側１点ゲートの専用金型を取り付けて成形をおこなった。専用金型は、厚さ０．４ｍｍ、幅２０ｍｍのＬ字状の成形品が採取できる形状で、流動長は最大１５０ｍｍであった。流動長が長いほど、流動性に優れていることを意味する。 (8) Flow length After setting the cylinder temperature (melting point + 25 ° C) and mold temperature (melting point -185 ° C) using the FANUC injection molding machine S2000i-100B, the mold clamping force was 100 tons, injection pressure Molding was performed by attaching a dedicated die with one-point gate on one side under the conditions of 120 MPa, injection speed of 80 mm / second, and injection time of 5 seconds. The dedicated mold had a shape in which an L-shaped molded product having a thickness of 0.4 mm and a width of 20 mm could be collected, and the flow length was 150 mm at the maximum. The longer the flow length, the better the fluidity.
（９）耐リフロー性
　金型内にセットされたリードフレームに、半芳香族ポリアミド樹脂組成物を射出成形し、反射板を作製し、次いで、半導体発光素子としてＩｎＧａＮ系青色からなる青色ＬＥＤ素子を、銀ペーストを用いて固定した。金線を取り付け、その後、透明封止樹脂を注入し、１５０℃、１時間加熱し、硬化させ、図１に示す表面実装型ＬＥＤパッケージを得た。図１において、１は反射板、２はリードフレーム、３は金線、４は透明封止樹脂、５は半導体発光素子を示す。
　得られた表面実装型ＬＥＤパッケージ２０個を、ＪＥＤＥＣ（電子機器技術評議会、Joint Electron Device Engineering Council）レベル３の吸湿処理（環境条件：温度６０℃、湿度６０％で５０時間処理）をおこなった後、ＪＥＤＥＣＪ－ＳＴＤ－０２０Ｄに準じて、ピーク温度２６０℃１０秒の温度条件におけるリフロー試験を２回繰り返した。リフロー試験後、ＬＥＤパッケージ内の反射板１と透明封止樹脂４を、実体顕微鏡を用いて観察し、以下の基準で評価した。
　不良品：反射板１に変色、ひび割れ（クラック）があるか、反射板１と透明封止樹脂４の間の剥離がある。
　良品：反射板１に変色、ひび割れ（クラック）がなく、反射板１と透明封止樹脂４の間の剥離もない。
　リフロー試験後の不良品率（＝（不良品の数／試験に用いたパッケージ数）×１００（％））を計算し、不良品率９５％以上を「◎」、９０％以上を「○」、９０％未満を「×」として、耐リフロー性を評価した。 (9) Reflow resistance A semi-aromatic polyamide resin composition is injection-molded on a lead frame set in a mold to produce a reflector, and then a blue LED element made of InGaN-based blue is used as a semiconductor light emitting element. And fixed with silver paste. A gold wire was attached, and then a transparent sealing resin was injected, heated at 150 ° C. for 1 hour, and cured to obtain a surface-mounted LED package shown in FIG. In FIG. 1, 1 is a reflecting plate, 2 is a lead frame, 3 is a gold wire, 4 is a transparent sealing resin, and 5 is a semiconductor light emitting element.
Twenty of the surface-mounted LED packages obtained were subjected to a JEDEC (Joint Electron Device Engineering Council) level 3 moisture absorption treatment (environmental conditions: temperature 60 ° C., humidity 60% for 50 hours). Thereafter, according to JEDECJ-STD-020D, a reflow test under a temperature condition of a peak temperature of 260 ° C. for 10 seconds was repeated twice. After the reflow test, the reflector 1 and the transparent sealing resin 4 in the LED package were observed using a stereomicroscope and evaluated according to the following criteria.
Defective product: The reflecting plate 1 has discoloration or cracks, or there is peeling between the reflecting plate 1 and the transparent sealing resin 4.
Non-defective product: The reflecting plate 1 is not discolored or cracked, and there is no peeling between the reflecting plate 1 and the transparent sealing resin 4.
Calculate the defective product rate after reflow test (= (number of defective products / number of packages used in the test) × 100 (%)). The defective product rate is 95% or more “◎”, 90% or more “○”. , Less than 90% was evaluated as “x”, and the reflow resistance was evaluated.
２．原材料
　用いた原材料を以下に示す。
（１）芳香族ジカルボン酸成分
・ＴＰＡ：テレフタル酸
・ＩＰＡ：イソフタル酸 2. Raw materials The raw materials used are shown below.
(1) Aromatic dicarboxylic acid component / TPA: terephthalic acid / IPA: isophthalic acid
（２）脂肪族ジアミン成分
・ＤＤＡ：１，１０－デカンジアミン
・ＨＭＤＡ：１，６－ヘキサンジアミン
・ＮＤＡ：１，９－ノナンジアミン (2) Aliphatic diamine component • DDA: 1,10-decanediamine • HMDA: 1,6-hexanediamine • NDA: 1,9-nonanediamine
（３）モノカルボン酸
・ＳＴＡ：ステアリン酸（分子量：２８４）
・ＣＰ：カプリル酸（分子量：１４４）
・ＬＡ：ラウリン酸（分子量：２００）
・ＬＢＡ：４－ラウリル安息香酸（分子量：２９０）
・ＢＨＡ：ベヘン酸（分子量：３４１）
・ＣＡ：カプロン酸（分子量：１１６）
・ＢＡ：安息香酸（分子量：１２２） (3) Monocarboxylic acid STA: Stearic acid (molecular weight: 284)
CP: caprylic acid (molecular weight: 144)
LA: Lauric acid (molecular weight: 200)
LBA: 4-lauryl benzoic acid (molecular weight: 290)
BHA: behenic acid (molecular weight: 341)
CA: caproic acid (molecular weight: 116)
BA: Benzoic acid (molecular weight: 122)
（４）白色顔料
・ＴＩ：酸化チタン（石原産業社製、タイペークＰＣ－３、平均粒径０．２１μｍ）
・ＢＳ：硫酸バリウム（堺化学社製、バリファインＢＦ－２０、平均粒径０．０３μｍ）
・ＣＣ：炭酸カルシウム（白石工業社製、Ｂｒｉｌｌｉａｎｔ－１５００、平均粒径０．２０μｍ） (4) White pigment, TI: Titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., Tyco PC-3, average particle size 0.21 μm)
BS: barium sulfate (manufactured by Sakai Chemical Industry, Varifine BF-20, average particle size 0.03 μm)
CC: calcium carbonate (manufactured by Shiroishi Kogyo Co., Ltd., Brilliant-1500, average particle size 0.20 μm)
（５）繊維状強化材
・ＧＦ－１：ガラス繊維（日本電気硝子社製、ＥＣＳ０３Ｔ－７８６Ｈ、平均繊維径１０．５μｍ、平均繊維長３ｍｍ）
・ＧＦ－２：ガラス繊維（日東紡社製、ＣＳ３Ｊ２５６、平均繊維径１１μｍ、平均繊維長３ｍｍ） (5) Fibrous reinforcing material / GF-1: Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-786H, average fiber diameter 10.5 μm, average fiber length 3 mm)
GF-2: glass fiber (manufactured by Nittobo, CS3J256, average fiber diameter 11 μm, average fiber length 3 mm)
（６）酸化防止剤
・ＡＯ－１：ビス（２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェニル）ペンタエリスリトールジホスファイト（リン系酸化防止剤、アデカ社製、アデカスタブＰＥＰ－３６）
・ＡＯ－２：３，９－ビス［２－｛３－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ｝－１，１－ジメチルエチル］２，４，８，１０－テトラオキサスピロ（５，５）ウンデカン（ヒンダードフェノール系酸化防止剤、アデカ社製、ＡＯ－８０）
・ＡＯ－３：ペンタエリスリチルテトラキス（３－ラウリルチオプロピオネート）（硫黄系酸化防止剤、住友化学工業社製、スミライザーＴＰ－Ｄ） (6) Antioxidant AO-1: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (phosphorus antioxidant, manufactured by Adeka, Adeka Stub PEP-36)
AO-2: 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10 -Tetraoxaspiro (5,5) undecane (hindered phenol-based antioxidant, manufactured by Adeka, AO-80)
AO-3: Pentaerythrityl tetrakis (3-lauryl thiopropionate) (sulfur-based antioxidant, manufactured by Sumitomo Chemical Co., Ltd., Smither TP-D)
（７）光安定剤
・ＬＳ：２－エチル－２－エトキシ－オキザルアニリド（クラリアントジャパン社製、ナイロスタブＳ－ＥＥＤ） (7) Light stabilizer LS: 2-ethyl-2-ethoxy-oxalanilide (manufactured by Clariant Japan, Nyrostab S-EED)
（８）蛍光増白剤
・ＦＢ：２，２′－（１，２－エチレンジイルジ－４，１－フェニレン）ビスベンゾオキサゾール（イーストマン社製、イーストブライトＯＢ－１） (8) Fluorescent whitening agent • FB: 2,2 ′-(1,2-ethylenediyldi-4,1-phenylene) bisbenzoxazole (Eastman, East Bright OB-1)
（９）金属水酸化物
・ＭＨ：水酸化マグネシウム（協和化学工業社製、キスマ５Ｅ） (9) Metal hydroxide / MH: Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., Kisuma 5E)
製造例１
　芳香族ジカルボン酸成分として粉末状のテレフタル酸（ＴＰＡ）４．７０ｋｇと、モノカルボン酸として分子量２８４のステアリン酸（ＳＴＡ）０．３２ｋｇと、重合触媒として次亜リン酸ナトリウム一水和物９．３ｇとを、リボンブレンダー式の反応装置に入れ、窒素密閉下、回転数３０ｒｐｍで撹拌しながら１７０℃に加熱した。その後、温度を１７０℃に保ち、かつ回転数を３０ｒｐｍに保ったまま、液注装置を用いて、脂肪族ジアミン成分として１００℃に加温した１，１０－デカンジアミン（ＤＤＡ）４．９８ｋｇを、２．５時間かけて連続的（連続液注方式）に添加し反応物を得た。
　その後、得られた反応物を、同じ反応装置で、窒素気流下、２５０℃、回転数３０ｒｐｍで８時間加熱して重合し、ストランド状に引き取った後、水槽に通して冷却固化し、それをペレタイザーでカッティングして半芳香族ポリアミド（Ｐ－１）ペレットを得た。 Production Example 1
8.70 kg of powdered terephthalic acid (TPA) as an aromatic dicarboxylic acid component, 0.32 kg of stearic acid (STA) having a molecular weight of 284 as monocarboxylic acid, and sodium hypophosphite monohydrate as a polymerization catalyst. 3 g was put into a ribbon blender type reactor and heated to 170 ° C. with stirring at a rotation speed of 30 rpm under nitrogen sealing. Thereafter, while maintaining the temperature at 170 ° C. and maintaining the rotation speed at 30 rpm, 4.98 kg of 1,10-decanediamine (DDA) heated to 100 ° C. as an aliphatic diamine component was added using a liquid injection device. And continuously added over 2.5 hours (continuous liquid injection method) to obtain a reaction product.
Thereafter, the obtained reaction product was polymerized by heating at 250 ° C. and a rotation speed of 30 rpm for 8 hours in the same reaction apparatus in a nitrogen stream, taken into a strand, and then cooled and solidified by passing it through a water bath. Cutting with a pelletizer gave semi-aromatic polyamide (P-1) pellets.
製造例２～１７
　表１に示す樹脂組成になるように各成分の種類や配合量を変更した以外は、製造例１と同様にして半芳香族ポリアミドペレット（Ｐ－２～Ｐ－１７）を得た。 Production Examples 2 to 17
Semi-aromatic polyamide pellets (P-2 to P-17) were obtained in the same manner as in Production Example 1 except that the types and blending amounts of the components were changed so that the resin composition shown in Table 1 was obtained.
　製造例１～１７で得られた半芳香族ポリアミドの組成、融点、相対粘度を表１に示す。 Table 1 shows the composition, melting point and relative viscosity of the semi-aromatic polyamides obtained in Production Examples 1 to 17.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
実施例１
　同方向二軸押出機（東芝機械社製ＴＥＭ２６ＳＳ、スクリュー径２６ｍｍ、Ｌ／Ｄ４９）の主供給口に、クボタ社製ロスインウェイト式連続定量供給装置ＣＥ－Ｗ－１を用いて計量した半芳香族ポリアミド（Ｐ－１）１００質量部、白色顔料（ＴＩ）４０質量部、酸化防止剤（ＡＯ－１）０．５質量部、光安定剤（ＬＳ）０．５質量部、蛍光増白剤（ＦＢ）０．１質量部を供給し、サイドフィーダーより繊維状強化材（ＧＦ－１）を２５質量部供給し、溶融混練をおこなった。溶融温度は３２０℃～３４０℃、スクリュー回転数は２５０ｒｐｍ、吐出量は３５ｋｇ／時間であった。その後、ストランド状に引き取った後、水槽に通して冷却固化し、それをペレタイザーでカッティングして半芳香族ポリアミド樹脂組成物を得た。 Example 1
Semi-fragrance weighed using Kubota's loss-in-weight continuous quantitative feeder CE-W-1 at the main supply port of the same-direction twin-screw extruder (TEM 26SS, Toshiba Machine, screw diameter 26 mm, L / D49) Group polyamide (P-1) 100 parts by weight, white pigment (TI) 40 parts by weight, antioxidant (AO-1) 0.5 part by weight, light stabilizer (LS) 0.5 part by weight, fluorescent whitening agent (FB) 0.1 parts by mass was supplied, and 25 parts by mass of the fibrous reinforcing material (GF-1) was supplied from the side feeder, and melt kneading was performed. The melting temperature was 320 ° C. to 340 ° C., the screw rotation speed was 250 rpm, and the discharge rate was 35 kg / hour. Then, after taking up in the form of a strand, it was cooled and solidified through a water tank, and cut with a pelletizer to obtain a semi-aromatic polyamide resin composition.
実施例２～３１、比較例１、３～７
　表２および表３に示す種類、含有量になるように樹脂組成を変更した以外は、実施例１と同様にして半芳香族ポリアミド樹脂組成物を得た。なお、ガラス繊維はサイドフィーダーから、その他は主供給口から供給した。 Examples 2-31 and Comparative Examples 1, 3-7
A semi-aromatic polyamide resin composition was obtained in the same manner as in Example 1 except that the resin composition was changed so as to have the types and contents shown in Tables 2 and 3. Glass fiber was supplied from the side feeder, and the other was supplied from the main supply port.
比較例２
　白色含量の含有量を変更した以外は、実施例１と同様の操作をおこなったが、白色顔料の含有量が高かったため、ストランドが切断し、半芳香族ポリアミド樹脂組成物を得ることができなかった。 Comparative Example 2
Except for changing the content of the white content, the same operation as in Example 1 was performed, but since the content of the white pigment was high, the strands were cut and a semi-aromatic polyamide resin composition could not be obtained. It was.
　実施例と比較例で得られた半芳香族ポリアミド樹脂組成物の組成およびその特性を表２、３に示す。 Tables 2 and 3 show the compositions and characteristics of the semi-aromatic polyamide resin compositions obtained in Examples and Comparative Examples.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１～３１では、耐熱性、白色度、曲げ強度、曲げ弾性率に加えて、流動性、耐リフロー性、反射率いずれにも優れていた。
　白色顔料として酸化チタン、炭酸カルシウム、硫酸バリウムのうちの２種を併用した実施例２６、２７では、酸化チタンのみを用いた実施例２５と比較して、反射率の保持率の向上がみられた。また、金属水酸化物（水酸化マグネシウム）を含有した実施例３１においても、金属水酸化物を含有しない実施例１と比較して、反射率の保持率の向上がみられた。 In Examples 1 to 31, in addition to heat resistance, whiteness, bending strength, and flexural modulus, the fluidity, reflow resistance, and reflectance were all excellent.
In Examples 26 and 27 in which two types of titanium oxide, calcium carbonate, and barium sulfate were used in combination as white pigments, the retention rate of reflectance was improved as compared with Example 25 using only titanium oxide. It was. Moreover, also in Example 31 containing a metal hydroxide (magnesium hydroxide), an improvement in the retention rate of the reflectance was observed as compared with Example 1 not containing a metal hydroxide.
　比較例１は、白色顔料の含有量が少なかったため、白色度、反射率が低く、耐リフロー性が劣っていた。
　比較例３は、半芳香族ポリアミド中のモノカルボン酸の含有量が本発明で規定する範囲よりも少なかったため、成形流動性が低下し、流動長が短かった。比較例４は、半芳香族ポリアミド中のモノカルボン酸の含有量が本発明で規定する範囲よりも多かったため、曲げ強度が低かった。
　比較例５は、半芳香族ポリアミド中のモノカルボン酸として、分子量が１４０未満のカプロン酸を用いたため、成形流動性向上効果が乏しく、流動長が短かった。
　比較例６は、半芳香族ポリアミド中のモノカルボン酸として、分子量が１４０未満の安息香酸を用いたため、比較例５と同様に、流動長が短かった。また、耐リフロー性にも劣っていた。
　比較例７において安息香酸の含有量を増やして相対粘度を下げた半芳香族ポリアミドを使用したところ、流動長は長くなったが、耐リフロー性は劣ったままであった。また、実施例１と対比して、モノカルボン酸の含有量はほぼ同じにもかかわらず、処理前の反射率が低く、反射率の保持率も低かった。 In Comparative Example 1, since the content of the white pigment was small, the whiteness and reflectance were low, and the reflow resistance was inferior.
In Comparative Example 3, since the monocarboxylic acid content in the semi-aromatic polyamide was less than the range specified in the present invention, the molding fluidity was lowered and the flow length was short. In Comparative Example 4, the bending strength was low because the content of monocarboxylic acid in the semi-aromatic polyamide was larger than the range specified in the present invention.
In Comparative Example 5, caproic acid having a molecular weight of less than 140 was used as the monocarboxylic acid in the semi-aromatic polyamide, so the molding fluidity improvement effect was poor and the flow length was short.
In Comparative Example 6, since benzoic acid having a molecular weight of less than 140 was used as the monocarboxylic acid in the semi-aromatic polyamide, the flow length was short as in Comparative Example 5. Moreover, it was inferior to reflow resistance.
In Comparative Example 7, when a semi-aromatic polyamide having a reduced benzoic acid content and a lower relative viscosity was used, the flow length increased, but the reflow resistance remained inferior. In contrast to Example 1, although the monocarboxylic acid content was almost the same, the reflectance before the treatment was low, and the reflectance retention was also low.
１　反射板
２　リードフレーム
３　金線
４　透明封止樹脂
５　半導体発光素子 DESCRIPTION OF SYMBOLS 1 Reflector 2 Lead frame 3 Gold wire 4 Transparent sealing resin 5 Semiconductor light emitting element

Claims (10)

  1. 　半芳香族ポリアミド（Ａ）１００質量部と、白色顔料（Ｂ）１０～１５０質量部とを含有する半芳香族ポリアミド樹脂組成物であって、
    半芳香族ポリアミド（Ａ）が、芳香族ジカルボン酸成分と、脂肪族ジアミン成分と、モノカルボン酸成分とから構成され、
    モノカルボン酸成分として、分子量が１４０以上のモノカルボン酸を含有し、その含有量が、半芳香族ポリアミド（Ａ）の１～８質量％であることを特徴とする半芳香族ポリアミド樹脂組成物。     A semi-aromatic polyamide resin composition containing 100 parts by weight of a semi-aromatic polyamide (A) and 10 to 150 parts by weight of a white pigment (B),
    The semi-aromatic polyamide (A) is composed of an aromatic dicarboxylic acid component, an aliphatic diamine component, and a monocarboxylic acid component,
    A semiaromatic polyamide resin composition comprising a monocarboxylic acid having a molecular weight of 140 or more as a monocarboxylic acid component, the content of which is 1 to 8% by mass of the semiaromatic polyamide (A) .
  2. 　さらに繊維状強化材（Ｃ）を１０～８０質量部含有することを特徴とする請求項１記載の半芳香族ポリアミド樹脂組成物。 The semi-aromatic polyamide resin composition according to claim 1, further comprising 10 to 80 parts by mass of a fibrous reinforcing material (C).
  3. 　モノカルボン酸が、脂肪族モノカルボン酸であることを特徴とする請求項１または２記載の半芳香族ポリアミド樹脂組成物。 The semiaromatic polyamide resin composition according to claim 1 or 2, wherein the monocarboxylic acid is an aliphatic monocarboxylic acid.
  4. 　脂肪族モノカルボン酸が、ステアリン酸であることを特徴とする請求項３記載の半芳香族ポリアミド樹脂組成物。 The semi-aromatic polyamide resin composition according to claim 3, wherein the aliphatic monocarboxylic acid is stearic acid.
  5. 　脂肪族ジアミン成分が、１，１０－デカンジアミンを含有することを特徴とする請求項１～４のいずれかに記載の半芳香族ポリアミド樹脂組成物。 The semi-aromatic polyamide resin composition according to any one of claims 1 to 4, wherein the aliphatic diamine component contains 1,10-decanediamine.
  6. 　白色顔料（Ｂ）が、酸化チタン、炭酸カルシウムおよび硫酸バリウムからなる群より選ばれる１種以上であることを特徴とする請求項１～５のいずれかに記載の半芳香族ポリアミド樹脂組成物。 The semiaromatic polyamide resin composition according to any one of claims 1 to 5, wherein the white pigment (B) is at least one selected from the group consisting of titanium oxide, calcium carbonate and barium sulfate.
  7. 　さらに、水酸化アルミニウム、水酸化マグネシウムおよび水酸化カルシウムからなる群より選ばれる１種以上の金属水酸化物を０．１～３０質量部含有することを特徴とする請求項１～６のいずれかに記載の半芳香族ポリアミド樹脂組成物。 7. The method according to claim 1, further comprising 0.1 to 30 parts by mass of one or more metal hydroxides selected from the group consisting of aluminum hydroxide, magnesium hydroxide and calcium hydroxide. The semi-aromatic polyamide resin composition described in 1.
  8. 　請求項１～７のいずれかに記載の半芳香族ポリアミド樹脂組成物を成形してなる反射板。 A reflector obtained by molding the semi-aromatic polyamide resin composition according to any one of claims 1 to 7.
  9. 　請求項８記載の反射板を備えるＬＥＤパッケージ。 An LED package comprising the reflector according to claim 8.
  10. 　請求項９記載のＬＥＤパッケージを備える照明装置。 A lighting device comprising the LED package according to claim 9.
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